US009358191 B2

(12) United States Patent (10) Patent No.: US 9,358,191 B2

Hiramoto et al. (45) Date of Patent: Jun. 7, 2016
(54) DEODORANT COMPOSITION (58) Field of Classification Search
None
(71) Applicant: TAKASAGO INTERNATIONAL See application file for complete search history.
CORPORATION, Tokyo (JP)
(56) References Cited
(72) Inventors: Tadahiro Hiramoto, Hiratsuka (JP); U.S. PATENT DOCUMENTS
Ryo Takeuchi, Hiratsuka (JP)
2,226,177 A 12/1940 Orelup et al.
(73) Assignee: TAKASAGO INTERNATIONAL 2,875,769 A 3, 1959 ROSmarinet al.
CORPORATION, Tokyo (JP)
(Continued)
(*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS
patent is extended or adjusted under 35
U.S.C. 154(b) by 0 days. JP 60-153778 8, 1985
JP 63-27O648 A 11, 1988
(21) Appl. No.: 14/293,681
(Continued)
(22) Filed: Jun. 2, 2014 OTHER PUBLICATIONS
XP-002390750 (1968) Hans Beyer “Lehrbuch der organischen
(65) Prior Publication Data Chemie', pp. 430-438.
US 2014/0271522 A1 Sep. 18, 2014 (Continued)
Related U.S. Application Data Primary Examiner — Bethany Barham
Assistant Examiner — Barbara Frazier
(62) Division of application No. 12/252,558, filed on Oct.
16, 2008, now Pat. No. 8,778,320, which is a division (74) Attorney, Agent, or Firm — Sughrue Mion, PLLC
of application No. 10/532.976, filed as application No. (57) ABSTRACT
PCT/JP03/13794 on Oct. 28, 2003, now abandoned.
It is intended to provide a novel deodorant composition which
(30) Foreign Application Priority Data is excellent in the deodorizing effect, is capable of affording
a deodorant composition by a convenient method, and shows
Oct. 28, 2002 (JP) ................................. 2002-312981 no decrease in the deodorizing performance even after a long
Oct. 28, 2002 (JP) ................................. 2002-312982 period of time, once the deodorant being prepared. Specifi
Oct. 9, 2003 (JP) ................................. 2003-351216 cally, there is provided a deodorant composition containing,
as the active component, a colored compound obtainable by
(51) Int. Cl. reacting a polyphenol in a solvent showing alkalinity in the
A6 IK 8/34 (2006.01) coexistence of an oxygen molecule at a reaction pH value of
A6 IK 8/44 (2006.01) 6.5 or more. As a Substitute for a polyphenol, use can be made
of a plant extract containing a polyphenol but containing
(Continued) substantially no amino acid. It is also possible to further
(52) U.S. Cl. employ an amino acid. Furthermore, use can be made of a
CPC. A61K 8/347 (2013.01); A61 K8/44 (2013.01); plant extract and/or a plant body containing a polyphenol and
A61K 8/97 (2013.01); A61L 9/01 (2013.01); an amino acid.

(Continued) 4 Claims, 1 Drawing Sheet

ADDITION OF EXAMPLE 30
ADDITION OF EXAMPLE 31
DEODORIZING EFFECT BLANK
 US 9,358,191 B2
Page 2

(51) Int. Cl. FOREIGN PATENT DOCUMENTS

A 6LX8/97 (2006.01) f
JP 64-016713 1, 1989
A6IL 9/01 (2006.01) JP 9-381.83 2, 1997
A6IL 9/03 (2006.01) JP 10-212221 8, 1998
JP 10-262690 10, 1998
A61O 5/02 (2006.01) JP 1 1-319051 11, 1999
A61O 15/00 (2006.01) JP 2000-135277 A 5, 2000
CID 3/00 (2006.01) JP 2003-102821 4/2003
CID 3/40 (2006.01) OTHER PUBLICATIONS
A61O II/00 (2006.01) Yabuta, et al., “Structure of Green Pigment Formed by the Reaction
(52) U.S. Cl. of Caffeic Acid Esters (or Chlorogenic acid) with a Primary Amino
CPC. A61L 9/013 (2013.01); A61O 5/02 (2013.01); Compound'. Biosci. Biotechnol. Biochem... vol. 65 No. 10 (2001),
A61O II/00 (2013.01); A61O 15/00 (2013.01); pp. 2121-2130.
CII D3/0068 (2013.01): CI ID 3/40 (2013.01) Negishi, et al. “Enzymatic Deodorization with Variegatic Acid from
Boletus subvelutipes and Its Mechanism'. Food Sci. Technol. Res.,
(56) References Cited vol. 6, No. 3, (2000), pp. 186-191.
European Patent Office, Office Action issued in European Applica
U.S. PATENT DOCUMENTS tion No. 03759009.8, dated Oct. 16, 2008.
European Patent Office, Office Action issued in European Applica
6,190,891 B1 2/2001 Echigo et al. tion No. 03759009.8, dated Nov. 25, 2010.
6,294,161 B1 9, 2001 Hiramoto et al. European Patent Office, Office Action dated Feb. 14, 2013, issued in
2003,004 1391 A1 3/2003 ROZZell et al. European Patent Application No. 03 759 009.8.
U.S. Patent Jun. 7, 2016 US 9,358,191 B2

FIG. 1

DEODORIZING EFFECT BLANK

ae
)
–
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CN
o+C<•iOLG-N,ºrO©I
ODOR INTENSTY

|E 6hr 24hr.
 US 9,358,191 B2
1. 2
DEODORANT COMPOSITION along period of time as far as possible. Moreover, a deodorant
composition having an excellent deodorizing effect on vari
CROSS REFERENCE TO RELATED ous malodorous components such as nitrogenous com
APPLICATIONS pounds, Sulfur compounds, and lower fatty acids is expected.
This is a Divisional of U.S. application Ser. No. 12/252, DISCLOSURE OF THE INVENTION
558, filed Oct. 16, 2008, which is a Divisional of U.S. appli
cation Ser. No. 10/532,976 filed Apr. 28, 2005, now aban An object of the invention is to provide a novel deodorant
doned, which is a 371 of PCT International Application No. composition which is excellent in the deodorizing effect and
PCT/JP2003/013794 filed Oct. 28, 2003, claiming priority of 10
obtainable by a simple process. Moreover, it is to provide a
JP 2002-312981, filed Oct. 28, 2002, JP 2002-312982 filed novel deodorant composition which shows no decrease in the
Oct. 28, 2002, and JP 2003-351216 filed Oct. 9, 2003, all of deodorizing performance even after a long period of time,
the above-noted applications are incorporated herein by ref once the deodorant being prepared. Furthermore, it is to pro
erence in their entirety. vide a deodorant composition having an excellent deodoriz
15
TECHNICAL FIELD ing effect on a wide range of malodorous components.
As a result of the extensive studies for solving the above
The present invention relates to a novel deodorant compo problems, the present inventors have found that a colored
sition. Specifically, it relates to a novel deodorant composi compound obtainable by reacting a specific polyphenol in a
tion comprising a colored compound obtainable by reacting a Solvent showing alkalinity in the coexistence of an oxygen
polyphenol in a solvent showing alkalinity in the coexistence molecule at a reaction pH value of 6.5 or more has an excel
of oxygen molecules at a reaction pH value of 6.5 or more. lent deodorizing effect. Also, they have found that a colored
Precisely, it relates to a novel deodorant composition com compound obtainable by reacting a specific polyphenol and
prising a colored compound obtainable by reacting a specific an amino acid in a solvent showing alkalinity in the coexist
polyphenol in a solvent showing alkalinity in the coexistence 25 ence of an oxygen molecule at a reaction pH value of 6.5 or
of oxygen molecules at a reaction pH value of 6.5 or more and more has an excellent deodorizing effect. Furthermore, even
to a novel deodorant composition comprising a colored com when a composition containing the deodorizing component is
pound obtainable by reacting a specific polyphenol and an stored for a long period of time, the deodorizing effect of the
amino acid in a solvent showing alkalinity in the coexistence deodorant composition is maintained for a long time. As a
of oxygen molecules at a reaction pH value of 6.5 or more. 30
result of further studies, they have finally reached the present
More precisely, it relates to a novel deodorant composition to invention.
be used for elimination or reduction of odors felt in daily life, Namely, the invention is as follows.
such as bad breath (halitosis), body odor, odor in refrigerator, (1) Adeodorant composition comprising, as an active com
odor of raw garbage, odor of footwear cupboard, body odor of ponent, a colored compound obtainable by reacting a
human and animals, odor of feces and urine of human and 35
polyphenol in a solvent showing alkalinity in the coexistence
animals, odors in factories and industrial wastes. of oxygen molecules at a reaction pH value of 6.5 or more.
BACKGROUND ART (2) The deodorant composition according to (1), wherein
an oxygen molecule Supply during the reaction is 1 mg/L or
O.
Recently, with diversification of lives, improvement of life 40
level, changes and improvement of attitudes, and the like, (3) The deodorant composition according to (1) or (2),
attention has been paid to various points around one’s life. wherein the reaction temperature is in the range of 0 to 60° C.
One of them is existence of various malodors. Main malodor (4) The deodorant composition according to any one of (1)
ous components to be targeted include nitrogenous com to (3), wherein a metal ion is further added to the reaction
pounds such as ammonia, urea, indole, skatole, and amines; 45 system and the reaction is carried out.
Sulfur compounds such as methyl mercaptan, hydrogen Sul (5) The deodorant composition according to any one of (1)
fide, and dimethyl sulfide; and lower fatty acids such as to (4), wherein the polyphenol is a polyphenol having an
butyric acid. Heretofore, there are a number of reports on o-diphenol structure.
deodorants that are used to eliminate or reduce the malodors. (6) The deodorant composition according to any one of (1)
For example, JP-A-11-319051 discloses a deodorant con 50 to (4), wherein the polyphenol is hydroquinone.
taining a polyphenol component extracted from apple as an (7) Adeodorant composition comprising, as an active com
active component. However, the deodorant is insufficient in ponent, a colored compound obtainable by reacting a plant
the deodorizing effect. Moreover, a deodorant composition extract containing a polyphenol but containing Substantially
containing a plant extract and a phenol oxidase as compo no amino acid in a solvent showing alkalinity in the coexist
nents is also known (cf. e.g., JP-A-9-38183, JP-A-10 55 ence of oxygen molecules at a reaction pH value of 6.5 or
212221, and so forth). However, although these deodorants O.
are excellent in the deodorizing effect, they have a problem (8) The deodorant composition according to any one of (1)
that preparation processes thereof are rather complicated. to (7), wherein an amino acid is further added to the reaction
On the other hand, there is a report in Food. Sci. Technol. system and the reaction is carried out.
Res., 6(3), 186-191, 2000 that the deodorizing effect of a 60 (9) The deodorant composition according to (8), wherein
specific polyphenol is confirmed in an NH-OH solution or in the amino acid is an O-amino acid.
an NaHCO solution. Moreover, in Biosci. Biotechnol. Bio (10) A deodorant composition comprising, as an active
chem. 65(10), 2121-2130, 2001, there is a report that a col component, a colored compound obtainable by reacting a
ored compound can be prepared by reacting a caffeic acid plant extract and/or a plant body containing a polyphenol and
ester and an amino acid. 65 an amino acid in a solvent showing alkalinity in the coexist
As the deodorant composition, there is desired a deodorant ence of oxygen molecules at a reaction pH value of 6.5 or
composition capable of maintaining a deodorizing ability for O.
 US 9,358,191 B2
3 4
BEST MODE FOR CARRYING OUT THE These polyphenols may be used solely or as a mixture of
INVENTION two or more of them.
The above polyphenols can be prepared by known methods
The following will describe the present invention in detail. but commercially available products may be purchased.
In the invention, a polyphenol is reacted in a solvent show Moreover, they may be prepared by synthesis. Furthermore,
ing alkalinity in the coexistence of oxygen molecules at a highly concentrated polyphenol fractions prepared from
reaction pH value of 6.5 or more to obtain a deodorant com plants can be employed.
position. In the invention, instead of the above polyphenols, a plant
First, the following will describe a polyphenol which is a extract can be also employed. The plant extract in this case is
raw material for preparing the deodorant composition of the 10 preferably a plant extract containing a polyphenol but con
invention. The polyphenol to be used in the invention means taining Substantially no amino acid. As the plant extract, one
a compound having two or more phenolic hydroxyl groups in prepared by a known method may be used and a commer
one molecule and a glycoside thereof is also included in the cially available one may be used.
polyphenol. The polyphenol to be used in the invention is not A polyphenol compound and a polyphenol-containing
particularly limited as far as it is a polyphenol capable of 15 plant extract containing Substantially no amino acid may be
achieving the desired object. used in combination.
Specific examples of the polyphenol include apigenin, api Moreover, in the invention, a deodorant composition can
genin glycosides, acacetin, isorhamnetin, isorhamnetingly be also obtained by reacting a polyphenol and an amino acid
cosides, isoquercitrin, epicatechin, epicatechin gallate, epi in an alkaline solvent in the coexistence of oxygen molecules
gallocatechin, epigallocatechin gallate, aesculetin, ethyl at a reaction pH value of 6.5 or more.
protocatechuate salt, elagic acid, catechol, Y-acid, catechin, The amino acid usable in the invention is not particularly
gardenin, gallocatechin, caffeic acid, caffeic esters, chloro limited as far as it is an amino acid capable of resulting in the
genic acid, kaempferol, kaempferol glycosides, quercetin, desired effect but, of amino acids, C.-amino acids are particu
quercetinglycosides, quercetagenin, genistin, genistinglyco larly preferred. The C-amino acid herein means an amino acid
side, gossypetin, gossypetin glycosides, gossypol, 4-dihy 25 wherein one amino group and one carboxyl group are bonded
droxyanthraquinone, 1,4-dihydroxynaphthalene, cyanidin, to one identical carbon atom. Examples of the C-amino acid
cyanidinglycosides, sinensetin, dioSmetin, dioSmetin glyco include glycine, alanine, Valine, leucine, isoleucine, glutamic
sides, 3,4'-diphenyldiol, sinapic acid, stearyl-?-(3,5-di-tert acid, aspartic acid, glutamine, asparagine, serine, threonine,
butyl-4-hydroxyphenyl)propionate, spinacene, tangeritin, lysine, hydroxylysine, arginine, histidine, cystine, methion
taxifolin, tannic acid, daphnetin, tyrosine, delphinidin, del 30 ine, phenylalanine, tyrosine, tryptophan, proline, 4-hydrox
phinidin glycosides, theaflavine, theaflavine monogallate, yproline, cysteine, theanine, amino acid salts (sodium
theaflavine bisgallate, tricetinidin, dopa, dopamine, maringe glutamate, sodium aspartate), and the like.
nin, naringin, nordihydroguairetic acid, noradrenaline, hyd Of these, particularly, glycine, alanine, glutamic acid,
roquinone, Vanillin, patchouletin, herbacetin, Vanillyl alco aspartic acid, lysine, arginine, histidine, serine, cystine,
hol, Vanitrope, Vanillin propylene glycol acetal, Vanillic acid, 35 methionine, cysteine, Sodium glutamate, Sodium aspartate,
bis(4-hydroxyphenyl)sulfonic acid, bisphenol A, pyrocat and tyrosine are preferred.
echol, Vitexin, 4,4'-biphenyldiol, 4-tert-butylcatechol, 2-tert These amino acids can be easily available by purchasing
butylhydroquinone, protocatechuic acid, phloroglucinol, commercially available products. Moreover, these amino
phenolic resins, procyanidin, prodelphinidin, phloretin, phlo acids may be used solely or as a mixture of two or more of
retinglycosides, fisetin, folin, fervasetin, fraxetin, phloridzin, 40 them. Furthermore, a plant extract containing an amino acid
paeonidin, paeonidin glycosides, pelargonidin, pelagugoni can be also employed.
din glycosides, petunidin, petunidin glycosides, hesperetin, In addition, the deodorant composition of the invention can
hesperidin, gallic acid, gallic esters (lauryl gallate, propyl be also obtained by employing a plant extract containing
gallate, butyl gallate), maniferin, malvidin, malvidinglyco Substantially no polyphenol and containing an amino acid
sides, myricetin, myricetin glycosides, 2,2'-methylenebis(4- 45 instead of an amino acid and a polyphenol in combination.
methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6- The “plant extract containing Substantially no polyphenol and
tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert containing an amino acid herein can be prepared by a known
butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), method but a commercially available product can be pur
methyl atrarate, 4-methylcatechol, 5-methylcatechol, chased. In this connection, it is also possible to use an amino
4-methoxycatechol, 5-methoxycatechol, methylcatechol-4- 50 acid and an amino acid-containing plant extract containing
carboxylic acid, 2-methylresorcinol, 5-methylresorcinol, Substantially no polyphenol in combination.
morin, limocitrin, limocitrin glycosides, limocitrol, luteolin, At obtaining the deodorant composition in the invention,
luteolin glycosides, luteolinidin, luteolinidin glycosides, examples of using a polyphenol and an amino acid in combi
rutin, resorcin, resveratrol, resorcinol, leukocyanidin, leuko nation also include an example of using an amino acid-con
delphinidin, and the like. 55 taining plant extract containing Substantially no polyphenol
Of these polyphenols, preferred are flavonoids such as and a polyphenol in combination, an example of using a
quercetin, epicatechin, and epigallocatechin and glycosides polyphenol-containing plant extract containing Substantially
thereof; polyphenols having an o-diphenol structure. Such as no amino acid and an amino acid in combination, and an
gallic acid, gallic esters, chlorogenic acid, caffeic acid, caf example of using a polyphenol-containing plant extract con
feic esters, tannic acid, pyrocatechol, nordihydroguairetic 60 taining Substantially no amino acid and an amino acid-con
acid, L-dopa, 4-methylcatechol. 5-methylcatechol, 4-meth taining plant extract containing Substantially no polyphenol
oxycatechol, and 5-methoxycatechol; and hydroquinone. in combination.
Particularly preferred are hydroquinone and the polyphenols The mixing ratio of the polyphenol to the amino acid in the
having an o-diphenol structure. In this connection, the deodorant composition can not be prescribed unconditionally
o-diphenol structure means a structure wherein two hydroxyl 65 since the ratio varies depending on the polyphenol to the
groups are directly Substituted on a benzene ring and the amino acid to be adopted but the polyphenol and the amino
hydroxyl groups are adjacent to each other. acid are preferably mixed in a ratio of 9:1 to 1:9, more pref
 US 9,358,191 B2
5 6
erably in a ratio of 3:1 to 1:3 by mol. In this connection, the nent, the reaction is carried out at a temperature of preferably
prescription is determined for the purpose of effectively uti 0° C. to 60° C., more preferably 0° C. to 40° C., further
lizing the polyphenol and the amino acid in the case that they preferably 0° C. to 25° C.
are used as raw materials, and the case that either of both In the invention, the polyphenol reacts within a short period
Substances is present in excess is not excluded. of time but from a practical viewpoint, the reaction may be
The deodorant composition of the invention can be pre carried out for preferably from several minutes (2 minutes) to
pared by reacting a polyphenol or a polyphenol and an amino about 24 hours, more preferably from about 10 minutes to
acid in a solvent showing alkalinity in the coexistence of about 9 hours, further preferably from 10 minutes to 7 hours.
oxygen molecules at a reaction pH value of 6.5 or more. At the reaction for preparing the above deodorant composi
The solvent showing alkalinity is a known one and is rep 10 tion, pressurization is not particularly necessary but pressure
resentatively an alkaline Substance-containing solvent may be applied.
wherein an alkaline Substance is dissolved in a solvent Such as Moreover, when the reaction is carried out in the coexist
ence of a metalion or a metal salt which releases a metalion
Water.
into the reaction system, a more excellent deodorant compo
The alkaline Substance is not particularly limited and spe 15 sition exhibiting an enhanced deodorizing activity and Stabil
cifically includes carbonate salts or hydrogen carbonate salts ity can be obtained.
Such as Sodium carbonate, potassium carbonate, sodium As a preferable metalion, there may be mentioned a copper
bicarbonate, ammonium carbonate, and guanidine carbonate; ion, a Zinc ion, a calcium ion, a magnesium ion, a silver ion,
borate salts such as potassium borate and Sodium borate; a tin ion, an aluminum ion, or a manganese ion.
silicate salts such as potassium silicate, sodium silicate No. 1, Examples of the compound which releases a metal ion
sodium silicate No. 2, sodium silicate No. 3, sodium ortho include the following: e.g., copper compounds such as copper
silicate, and Sodium metasilicate; sodium monohydrogen chloride, copper fluoride, copper Sulfate, copper nitrate, cop
phosphate, sodium sulfite, sodium hydroxide, calcium per hydroxide, copper citrate, copper gluconate, copper
hydroxide, potassium hydroxide, magnesium hydroxide, aspartate, copper glutamate, sodium copper chlorophyllin
ammonium hydroxide, sodium pyrophosphate, and potas 25 and copper chlorophyll; Zinc compounds such as Zinc chlo
sium pyrophosphate; and the like. ride, Zinc fluoride, Zinc sulfate, Zinc nitrate, Zinc hydroxide,
The solvent for dissolving one or two or more these alka Zinc citrate, Zinc gluconate, Zinc aspartate, Zinc glutamate,
line Substances includes water and various hydrous solvent as Zinc phosphate, and Zinc lactate; calcium compounds such as
preferable solvents. Moreover, so-called alkaline buffer solu calcium chloride, calcium hydroxide, calcium citrate, cal
tions using these alkaline Substances and acids may be also 30 cium gluconate, calcium L-glutamate, calcium carbonate,
employed. calcium lactate, calcium pantothenate, calcium dihydrogen
The above solvent usually show alkalinity and it is alkaline pyrophosphate, calcium propionate, calcium sulfate, trical
cium phosphate, calcium monohydrogen phosphate, calcium
before the reaction but sometimes shows weak acidity dihydrogen phosphate, and disodium calcium ethylenedi
depending on the Substance to be incorporated into the Sol 35 aminetetraacetate; magnesium compounds such as magne
vent and an added amount thereof. Namely, when the solvent sium chloride, magnesium sulfate, magnesium hydroxide,
before the reaction is necessarily alkaline and, at obtaining magnesium L-glutamate, magnesium oxide, and magnesium
the above deodorant composition, the pH of the solvent in the carbonate; silver compounds Such as silver oxide; tin com
reaction system after the start of the reaction is 6.5 or more, pounds such as tin chloride, tin acetate, and tin fluoride;
then a preferable result is obtained. In particular, the pH of the 40 aluminum compounds such as aluminum chloride, aluminum
reaction system is preferably in the range of 7 to 13, further hydroxide, aluminum acetate, aluminum borate, aluminum
preferably in the range of 8 to 13. When the pH in the reaction phosphate, and aluminum Sulfate; permanganese salts such as
system during the reaction is below 6.5, it is impossible to potassium permanganese, manganese compounds such as
afford a deodorant composition having a preferable deodor manganese Sulfate, and the like. In addition, titanium com
izing effect. 45 pounds such as titanium dioxide can be also employed.
In the invention, it is necessary to react the polyphenol in The addition amount of the metal ion varies depending on
the coexistence of oxygen molecules. As a conventional the situation of the reaction but it is preferable to add the ion
means for Supplying oxygen molecules into the reaction sys so that the concentration of the metalion in the reaction liquid
tem, there may be mentioned Supply of oxygen or air into the becomes 0.00001 mM to 100 mM and the concentration is
system utilizing an air pump (bubbling) or active stirring of 50 more preferably from 0.00005 mM to 10 mM, further pref
the system. The reaction in the coexistence of oxygen mol erably from 0.1 mM to 5 mM.
ecules means a reaction aiming at the acceleration of the Moreover, in the invention, after a deodorant composition
reaction of the polyphenol present in the reaction system by is obtained by reacting a polyphenol or a polyphenol and an
actively incorporating oxygen molecules into the reaction amino acid in an alkaline solvent in the coexistence of oxygen
liquid. In this case, the deodorant composition can be effi 55 molecules, a metalion may be added thereto to form a deodor
ciently obtained by making the oxygen Supplying amount ant composition.
into the reaction liquid 1 mg/L or more, preferably 2 mg/L or In the invention, at obtaining the deodorant composition by
more. The oxygen Supplying amount can be achieved by, for reacting a polyphenol and anamino acid in analkaline solvent
example, actively blowing oxygen gas, air, or a mixture in the coexistence of oxygen molecules, a plant extract con
thereof into the reaction system (bubbling) or it can be also 60 taining a polyphenol and an amino acid can be used instead of
achieved by stirring the reaction liquid under a reaction con the polyphenol and the amino acid. As the plant extract in this
dition that oxygen gas or air can constantly come into contact case, a plant extract containing a polyphenol and an amino
therewith. acid in a high concentration may be mentioned. As the plant
With regard to the temperature at the reaction, the inventive extracts, those prepared by known methods may be used or
product can be obtained at a temperature of 0° C. to a reflux 65 commercially available ones may be used.
temperature of the solvent but in order to avoid thermal For example, the deodorant composition of the invention
decomposition of the resulting deodorizing active compo can be also obtained by adding a plant extract containing a
 US 9,358,191 B2
7 8
polyphenol and an amino acid, i.e., an extract from at least fig, kiwi, prune, blueberry, blackberry, raspberry, cranberry,
one portion selected from leaves, stems, roots, fruits, and the coffee beans, cacao beans, grape seeds, grape fruits seeds,
like of a plant to a solvent showing alkalinity, adjusting the pecan nut, cashew nut, chestnut, coconut, peanut, walnut,
reaction liquid during the reaction to pH 6.5 or more, and green tea leaves, black tea leaves, oolong tea leaves, tobacco,
treating it at an oxygen Supplying amount of 1 mg/L or more 5 perilla leaves, garden thyme, Sage, lavender, spearmint, pep
at a reaction temperature of 0°C. to a refluxing temperature of permint, spotted thistle, hyssop, Sweet basil, marigold, dan
the solvent for a reaction time of several minutes to 24 hours. delion, artichoke, Matricaria chamomille, Agrimonia pilosa
Examples of the alkaline Substance and solvent in this case var. japonica, licorice, anise, yarrow, eucalyptus, wormwood,
include those described in the above and the composition is balm, Angelica pubescens, fenugreek, Capsicum annuum var.
obtained by operating the reaction under the same conditions 10 angulosum, fennel, red pepper, coriander seeds, caraway
as described above. In the case that the plant extract contain seeds, fennel seeds, ginger, horseradish, Origanum majo
ing a polyphenol and an amino acid is used instead of the rana, Origanum vulgare, mustard, parsley, pepper, Savory,
polyphenol and the amino acid, at least one selected from a tarragon, queen lily, wasabi, dill seeds, citrus fruits, and the
polyphenol-containing plant extract containing Substantially like. Two or more of these plant extracts may be used in
no amino acid, an amino acid-containing plant extract con 15 combination.
taining Substantially no polyphenol, a polyphenol, and an At the preparation of the deodorant composition of the
amino acid may be further used in combination. Examples of invention, additives already conventionally used may be
the plant extract will be shown below. coexisted in the reaction system.
Moreover, in the invention, at obtaining the deodorant Thus, there is obtained the colored compound which is an
composition by reacting a polyphenol and an amino acid in an active component of the deodorant composition of the inven
alkaline solvent in the coexistence of oxygen molecules at a tion. The color of the resulting reaction liquid widely varies
reaction pH value of 6.5 or more, a plant body containing a depending on the kind of the polyphenol as a starting Sub
polyphenol and an amino acid can be also used instead of the stance, the presence of an amino acid, the kind of the amino
polyphenol and the amino acid. The plant body in this case is acid, and the ratio thereof. Moreover, since the density of the
preferably one containing a polyphenol and an amino acid in 25 color also varies depending on the reaction time and pH, the
a high concentration. color cannot be unconditionally prescribed.
For example, the deodorant composition of the invention For example, when the case of chlorogenic acid is
can be also obtained by adding a plant body containing the described as an example, the color of the reaction liquid
polyphenol and the amino acid of the invention, i.e., at least which is paleyellow at the initial stage of the reaction changes
one portion selected from leaves, stems, roots, fruits, and the 30 into brown with time and finally into dark brown. In the case
like of a plant to a solvent showing alkalinity, adjusting the of quercetin, the color of the reaction liquid which is pale pink
reaction liquid during the reaction to pH 6.5 or more, and at the initial stage of the reaction increases in red with time
treating it at an oxygen Supplying amount of 1 mg/L or more and finally into deep wine red. In the case of gallic acid, the
at a reaction temperature of 0°C. to a refluxing temperature of color of the reaction liquid which is pale yellow at the initial
the solvent for a reaction time of several minutes to 24 hours. 35 stage of the reaction changes into greenish with time and
Examples of the alkaline substance and solvent include those finally into dark green. In the case of pyrocatechol, the color
described in the above and the composition is obtained by of the reaction liquid which is pale pink at the initial stage of
operating the reaction under the same conditions as described the reaction changes into brown with time and finally into
above. As the plant body, plants exemplified in the following dark brown.
plant extract can be used. In the case that the plant body 40 Moreover, in the case that glycine is selected as an amino
containing a polyphenol and an amino acid is used instead of acid and reacted, the reaction liquid with chlorogenic acid is
the polyphenol and the amino acid, at least one selected from green, the reaction liquid with (+)-catechin is red, the reaction
a polyphenol-containing plant extract containing Substan liquid with protocatechuic acid is red, the reaction liquid with
tially no amino acid, an amino acid-containing plant extract pyrocatechol is pale pink, the reaction liquid with aesculetin
containing Substantially no polyphenol, a plant extract con 45 is brown, the reaction liquid with hydroquinone is brown, the
taining a polyphenol and an amino acid, a polyphenol, and an reaction liquid with quercetin is red, and the reaction liquid
amino acid may be further used in combination. Herein, the with gallic acid is brown.
amount of the amino acid or polyphenol which is “substan With regard to the reaction with a polyphenol or a polyphe
tially not contained' is an amount imparting no influence to nol and an amino acid in most cases, the reaction liquid has a
the reaction and is an amount which is less than detection 50 pale color at the initial stage of the reaction but the color of the
limit when measured according to a generally known method. reaction liquid is darkened and finally tends to become a dark
Examples of the plant extract include extracts obtainable color. The time required for darkening the color of the reac
from aloe, anise seeds, elder, eleutherococcus, psyllium, tion liquid varies depending on the kind of the polyphenol, the
orange flower, allspice, oregano, Valerian, chamomile, capsi combination of the polyphenol and the amino acid, and the
cum pepper, cardamon, Cassia, garlic, caraway seeds, clove, 55 reaction conditions but is about several minutes after the start
cumin seeds, kola, coriander seeds, Rhus javanica, Saffron, of the reaction and sometimes about 20 minutes or 30 min
Zanthoxylum, juniper berry, cinnamon, ginger, star anise, St. utes.
Johns wart, celery seed, savory, Sesame, pieplant, tarragon, As mentioned above, the deodorant composition prepared
turmeric, thistle, Anethum graveolens, nutmeg, nettle, hibis in the invention contains the colored compound. The colored
cus, hamamelis, birch, basil, bitter orange, fennel, primrose, 60 compound acts a role as a deodorizing active component. The
fenugreek, verbena, Laurus nobilis, hop, boldo, horseradish, colored compounds have various chemical structures and, for
poppy seed, gallnut, marigold, marrow, marjoram, mustard, example, reaction products of polyphenols which are starting
Millefeuille, mint leaves, melissa, mace, lindane, Gentiana materials, polymeric products prepared from polyphenols,
scabra var. buergeri, rosehip, rosemary, Rosmarinus offici reaction products from polyphenols and amino acids, poly
nalis, Sunflower seeds, grape pericarp, apple, carrot leaves, 65 meric reaction products prepared from polyphenols and
banana, Strawberry, apricot, peach, plum, pineapple, pear, amino acids, oxides of polyphenols, oxides of the above
persimmon, cherry, papaya, mango, avocado, melon, loquat, reaction products and polymeric products, and further various
 US 9,358,191 B2
10
radicals such as a phenoxy radical which is one of oxidation collagen; oily gelating agents such as metal Soaps and diben
products of polyphenols also belong to the category of the Zylidene sorbitol. They can be used solely or in combination.
colored compounds of the invention. As a method for Supporting the deodorant composition of
The ratio of the colored compound contained in the deodor the invention on the carrier, there can be mentioned a method
ant composition of the invention is from 10 ppm to 100% by of attaching the deodorant composition in a solution state by
weight. means of coating, impregnation, spraying, or the like and
It is preferred that the molecular weight of the colored Subsequently drying (e.g., air-drying at 60°C. for 12 hours) as
compound in the resulting deodorant composition exceeds an example.
the molecular weight of the polyphenol before the reaction as 10
The deodorant composition of the invention may be used
a starting material or the sum of the molecular weights of the after capsulation by a known method using gelatin, gum
polyphenol and the amino acid, and is 10,000 or less. arabic, Sodium arginate, a cellulose derivative Such as ethyl
The molecular weight of the colored compound can be cellulose, polyvinyl alcohol, vinyl methyl ether-maleic anhy
measured by the following method. Namely, the deodorant dride copolymer, styrene-maleic anhydride copolymer, poly
composition prepared by one of the above various methods is 15 ethylene, polystyrene, paraffin wax, or the like.
concentrated by centrifugation and it is determined whether Moreover, particularly in the case that the deodorant com
the concentrate passes through or remains on a filtration position of the invention is used in a solution state, the reduc
membrane having a certain pores, whereby a corresponding tion of the amount of dissolved oxygen in the Solution as far
molecular weight is determined based on the pore size of the as possible remarkably enhances the storage stability of the
filtration membrane on which the concentrate remains. As the composition of the invention in the solution and thus the case
filtration membranes to be used, commercially available is convenient. A rough standard of the amount of dissolved
products may be used. oxygen convenient at storage is, for example, 0.0005% by
The deodorizing active component in the invention may be weight, more preferably 0.00015% by weight or less.
an oxide of a starting material obtained by the reaction of the As a method for the reduction of the amount of dissolved
starting material with oxygen molecules, and hence the range 25 oxygen in the solution as far as possible, a known method may
of the molecular weight of the deodorizing active component be employed, which specifically includes a method of storing
is expressed as above. the solution under a circumstance of reduced pressure, a
The thus obtained reaction liquid containing the deodoriz method of Subjecting the Solution to degas treatment, a
ing active component can be used as the deodorant composi method of replacement with nitrogen gas or argon gas, a
tion without further treatment. Alternatively, if necessary, by 30 method of treating it under an atmosphere of nitrogen gas or
a method of further concentrating the reaction liquid contain argon gas, and the like.
ing the deodorizing active component or the like method, a In the case that the deodorant composition is used in a solid
deodorant composition having a high content of the deodor state, when a compound having deliquescence or high hygro
izing active component can be obtained. Furthermore, a solid scopicity is present together with the deodorant composition,
deodorant composition can be obtained by removing liquid 35 the compound efficiently absorbs the moisture in the air and
components from the reaction liquid containing the deodor hence a reaction field suitable for the deodorant composition
izing active component by a known method such as a may be provided, so that the case is more preferred for exhib
vacuum-drying method or a freeze-drying method. Alterna iting the deodorizing effect of the deodorant composition.
tively, the liquid may be supported on any carrier Such as a As examples of the compound having deliquescence or
liquid, a solid, or a gel Substance to form a deodorant com 40 high hygroscopicity, salts and alkalis showing deliquescence
position. by the moisture in the air or showing a property of strongly
Preferred examples of the liquid include water, hydrous absorbing the moisture in the air are employed and particu
alcohols, lower alcohols (methanol, ethanol, butanol, pro larly, salts having deliquescence or high hygroscopicity are
panol, etc.), polyol-based organic solvents (ethylene glycol, practical.
propylene glycol, etc.), benzyl alcohol, glycerin, monoglyc 45 Specific examples include lithium chloride, sodium chlo
erides, diglycerides, animal and plant oils, essential oils, and ride, potassium chloride, magnesium chloride, ammonium
the like. magnesium chloride, Sodium magnesium chloride, potas
Preferred examples of the solid include porous carriers, sium magnesium chloride, manganese chloride, potassium
e.g., Sugars such as dextrin, cyclodextrin, glucose, lactose, manganese chloride, antimony chloride, antimony cobalt
and starch; plastic carriers such as plastic particles and foam 50 chloride, zinc chloride, iron chloride, bismuth chloride,
plastics; inorganic particles Such as silica gel particles, diato beryllium chloride, calcium bromide, zinc bromide, copper
maceous earth, activated clay, Vermiculite, alumina, Zeolite, bromide, iron bromide, cobalt bromide, cadmium bromide,
perlite, clay minerals, unglazed pottery, ceramics, metals, lithium iodide, Sodium iodide, magnesium iodide, calcium
glass, and active carbon; water-absorbable polymers; natural iodide, iron iodide, nickel iodide, Sodium nitrite, potassium
carriers such as buckwheat chaff, chaff, sawdust, and baked 55 nitrite, magnesium nitrite, ammonium nitrate, lithium nitrate,
products thereof fibrous carriers such as fibers, fiber aggre Sodium nitrate, calcium nitrate, beryllium nitrate, magnesium
gates, fiberbunch, non-woven fabrics, knitted goods, textiles, nitrate, manganese nitrate, cerium nitrate, ammonium cerium
pulp, paper, paper products (cardboards, honeycomb, etc.); nitrate, iron nitrate, copper nitrate, lithium chlorate, calcium
synthetic molecules Such as crown ethers, cryptands, cyclo chlorate, magnesium chlorate, Zinc chlorate, cadmium chlo
phanes, and carixarenes; and the like. The porous' herein 60 rate, cobalt chlorate, copper chlorate, potassium carbonate,
includes the case that the carrier itself is porous and the case lithium sulfate, ammonium Zinc sulfate, antimony Sulfate,
that numerous Voids are present between the carriers. iron Sulfate, ammonium cadmium sulfate, ammonium thio
Examples of the gel Substances include aqueous gelating Sulfate, potassium phosphate, ammonium phosphite, potas
agents such as carrageenin, carboxyvinyl polymers, sium phosphite, hydrazinium phosphite, sodium hypophos
crosslinked polyacrylic acid, hydroxyethyl cellulose, car 65 phite, potassium hypophosphite, sodium permanganate,
boxymethyl cellulose, sodium acrylate, agar, gelatin, pectin, calcium permanganate, strontium permanganate, magnesium
pharselan, Xanthan gum, locust bean gum, duran gum, and permanganate, Zinc permanganate, Sodium hydroxide, potas
 US 9,358,191 B2
11 12
sium hydroxide, and the like. These salts may be used solely The antibacterial agents include benzoic acid, Sodium ben
or two or more of them may be used in combination. Zoate, isopropyl p-hydroxybenzoate, isobutyl p-hydroxyben
The most Suitable amount of the compound having deli Zoate, ethyl p-hydroxybenzoate, methyl p-hydroxybenzoate,
quescence or high hygroscopicity to be co-present varies butyl p-hydroxybenzoate, propyl p-hydroxybenzoate,
depending on the kind of the compound, the environment to Sodium sulfite, sodium hyposulfite, potassium pyrosulfite,
be applied, and intended use and hence the amount is not Sorbic acid, potassium Sorbate, sodium dehydroacetate, thu
unconditionally determined but 0.1 to 10 weight equivalents japlicin, udo extract, storax extract, wild tansy extract, milt
to the deodorant composition may be mentioned as an protein extract, Zymolytic Job’s tears extract, and the like.
example. Examples of known deodorants include deodorants due to
In the invention, various additives commercially available 10
the desulfurizing action of iron Sulfates such as ferrous Sulfate
can be added to the deodorant composition obtained by the and iron chlorides; deodorants due to the chemical reaction of
above method. Examples of the additives include extenders, acidic agents, alkaline agents, oxidizing agents, and the like;
antioxidants, dyestuffs, known deodorizing materials,
enzymes for reducing malodor, Surfactants, flavors, fra deodorants due to the adding or condensing action of (meth)
grances, stabilizing agents, antibacterial agents, moisture 15 acrylate esters, maleate esters, and the like as adding agents or
absorbents (calcium chloride, highly water-absorbable poly glyoxal as a condensing agent; deodorants due to the ion
mers, etc.), excipients (lactose, etc.), and the like. exchanging action of amphoteric ion-exchange resins, cat
They can be mixed with the deodorant composition of the ionic ion-exchange resins, anionic ion-exchange resins, and
invention solely or as a combination of two or more of them the like; deodorants due to the chemical Substance-attaching
and thus a characteristic deodorant composition and deodor or adsorbing action of alkaline or acidic attaching active
ant can be prepared. Particularly, when an antibacterial agent carbon, mixtures of active carbon and a chemical reagent, and
is mixed to the deodorant composition, the deodorizing effect the like; deodorants due to the adsorbing action of porous
is synergistically enhanced and hence it becomes possible to adsorbents such as neutral active carbon, a fibrous carbon
prepare a more characteristic deodorant composition and deodorant, Zeolite, and active clay; deodorants due to the
deodorant by combining the agent with other additives to 25 enzymatic action of digestive enzymes or enzymes produced
exhibit performances of the additives. The mixing amounts of by mouth good bacterium LS-1 lactic acid bacterium, yeasts,
the above additives are not particularly limited as far as the soil bacteria, and the like or bacteria thereof; deodorants due
amounts are Such amounts that they can accomplish desired to the antiseptic or bactericidal action of chloramine T. para
purposes. bens, phenols, and the like; polyphenol deodorants such as
The extenders include Sugars, polysaccharides, processed 30
persimmon polyphenol, tea chatechin, rosemary extract,
starch, casein, gelatin, carboxymethyl cellulose (hereinafter oolong tea extract, tansy extract, white oak leave extract, and
referred to as CMC), lecithin, and the like. rice bran/soybean-firing extract; and the like. In addition,
As the antioxidants, there are known butylhydroxytoluene, there are also included cyclodextrin, champignon extract,
butylhydroxyanisole, citric acid, biofavoic acid, glutathione,
Selenium, licopene, VitaminA, vitamin E, and vitamin C, and 35 rooibos extract, sodium iron chlorophyllin, active carbon,
also pyrrolopyrrole derivatives, free radical Scavengers Zeolite, and the like.
obtainable form extracts of various plants, enzymes having Examples of the enzymes for reducing malodor include
antioxidant properties such as Superoxide dismutases and carbohydrases, lipases, proteases, phytases, and the like. By
glutathione peroxidases, and the like. mixing these enzymes in the deodorant composition, the
As the dyestuffs, dyes, lakes, organic synthetic dyestuffs 40 deodorizing effect can be enhanced.
(tar dyestuffs) such as organic pigments, natural dyestuffs, The Surfactants include nonion types (polyoxyethylene
inorganic pigments, and the like are known. Specifically, alkyl ethers, fatty acid alkylolamides, etc.), acylglutamic acid
there are known hibiscus dyestuff, huckleberry dyestuff, types, and the like. These surfactants are preferably used
plume dyestuff, laver dyestuff, duberry dyestuff, grape juice solely or as a combination of two or more of them. Examples
dyestuff, blackberry dyestuff, blueberry dyestuff, mulberry 45 of the polyoxyethylene alkyl ethers include polyoxyethylene
dyestuff, morello cherry dyestuff, red currant dyestuff, logan Stearyl, polyoxyethylene hardened castor oil, and the like.
berry dyestuff, paplica powder, malt extract, rutin, flavonoids, Examples of the fatty acid alkylolamides include coconut-oil
red cabbage dyestuff, red radish dyestuff, adzuki bean dye fatty acid diethanolamide. The acylglutamic acid types
stuff, turmeric dyestuff, olive tea, cowberry dyestuff, chlo include glutamate esters of Saturated and unsaturated fatty
rella dyestuff, saffron dyestuff, perilla dyestuff, strawberry 50 acids having 12 to 18 carbon atoms and coconut-oil fatty
dyestuff, chicory dyestuff, pecannut dyestuff, red rice malt acids, hardened coconut-oil fatty acids, palm-oil fatty acids,
dyestuff, safflower dyestuff, purple sweet potato dyestuff, lac hardened palm oil fatty acids, beef-tallow fatty acids, hard
dyestuff, Spirulina dyestuff, onion dyestuff, tamarind dye ened beef-tallow fatty acids, and the like which are mixtures
stuff, chili pepper dyestuff, gardenia dyestuff. Gardenia jas thereof, and specifically, include N-coconut-oil fatty acid
minoides dyestuff, sikon dyestuff, rosewood dyestuff, 55 acyl-L-glutamic triethanolamine, lauroyl-L-glutamic trietha
euphausiid dyestuff, orange dyestuff, carrot carotene, carmel, nolamine, Sodium N-coconut-oil fatty acid-acyl-L-
Sodium iron chlorophyllin, riboflavin, norbixin potassium, glutamate, Sodium N-lauroyl-L-glutamate, sodium
norbixin sodium, alamance, erythrocin, new coccin, phloxine N-myristoyl-L-glutamate, sodium N-coconut-oil fatty acid
B. rose bengal, acid red, cutoradin, Sunset yellow, first green, hardened tallow fatty acid-acyl-L-glutamate, potassium
brilliant blue, indigocarmine, lake red C, lithol red, 60 N-coconut-oil fatty acid-acyl-L-glutamate, and the like.
rhodamine, phloxine, indigo, ponceau, orange I, Sudan blue, Moreover, flavors and/or fragrances may be mixed with the
and the like. Inorganic pigments include mica, talc, calcium deodorant compositions. As a result, a strange odor charac
carbonate, kaolin, silicic anhydride, aluminum oxide, colco teristic to the substrate can be masked and further pleasant
thar, iron oxide, ultramarine, carbon black, titanium dioxide, aroma can be also imparted.
Zinc dioxide, mica, bismuth oxychloride, boron nitride, pho 65 The mixing amount of the flavors and/or fragrances varies
tochromic pigments, hybrid fine powder, synthetic mica, and depending on the polyphenol and amino acid to be adopted,
the like. the application target of the deodorant composition, the
 US 9,358,191 B2
13 14
method of using the same, and the like but is usually prefer linallyl, terpinyl, C.-methylpropionyl, 3-methylpropionyl,
ably from 0.001 to 500 equivalents to the deodorant compo etc.), heptanoate esters (allyl, ethyl, octyl, propyl, methyl,
sition by weight. etc.), heptynecarboxylate esters (allyl ethyl, propyl, methyl,
The flavor to be used in the invention includes synthetic etc.), myristate esters (isopropyl, ethyl, methyl, etc.), phe
aroma chemicals such as esters, alcohols, aldehydes, ketones, 5 nylglycidate esters (ethyl phenylglycidate, ethyl 3-meth
acetals, phenols, ethers, lactones, furans, hydrocarbons, and ylphenylglycidate, ethyl p-methyl-3-phenylglycidate, etc.),
acids, flavor materials of natural origin, and the like. 2-methylbutyrate esters (methyl, ethyl, octyl, phenylethyl,
Examples of the esters in the synthetic aroma chemicals to butyl, hexyl, benzyl, etc.), 3-methylbutyrate esters (methyl,
be used as the above flavor preferably include acrylate esters ethyl, etc.), butyrate esters (anisyl, amyl, allyl, isoamyl.
(methyl, ethyl, etc.), acetoacetate esters (methyl, ethyl, etc.), 10 methyl, ethyl, propyl, octyl, guanyl, linallyl, geranyl, cyclo
anisate esters (methyl, ethyl, etc.), benzoate esters (allyl, hexyl, citronellyl, cinnamyl, neryl, terpenyl, phenylpropyl.
isoamyl, ethyl, geranyl, linallyl, phenylethyl, hexyl, cis-3- 3-phenylethyl, butyl, hexyl, cis-3-hexenyl, trans-2-hexenyl,
hexenyl, benzyl, methyl, etc.), anthranilate esters (cinnamyl. benzyl, rhodinyl, etc.), hydroxybutyrate esters (3-hydroxy
cis-3-hexenyl, methyl, ethyl, linallyl, isobutyl, etc.), N-methy buyrate methyl, ethyl, or menthyl, etc.), and the like.
lanthranilate esters (methyl, ethyl, etc.), isovalerate ester 15 Examples of the alcohols to be used as the flavors in the
(amyl, allyl, isoamyl, isobutyl, isopropyl, ethyl, octyl, gera invention preferably include aliphatic alcohols (isoamyl alco
nyl, cyclohexyl, citronellyl, terpenyl, linallyl, cinnamyl, phe hol, isopulegol, 2-ethylhexanol, 1-octanol, 3-octanol,
nylethyl, butyl, propyl, hexyl, benzyl, methyl, rhodinyl, etc.), 1-octen-3-ol, 1-decanol. 1-dodecanol. 2.6-nonadienol,
isobutyrate esters (isoamyl, geranyl, citronellyl, terpenyl, nonanol, 2-nonanol, cis-6-nonenol, trans-2, cis-6-nona
cinnamyl, octyl, neryl, phenylethyl, phenylpropyl, phenoxy dienol, cis-3, cis-6-nonadienol, butanol, hexanol, cis-3-hex
ethyl, butyl, propyl, isopropyl, hexyl, benzyl, methyl, ethyl, enol, trans-2-hexenol. 1-undecanol, heptanol, 2-heptanol,
linallyl, rhodinyl, etc.), undecylenate esters (allyl, isoamyl. 3-methyl-1-pentanol, etc.), terpene alcohols (carveol,
butyl, ethyl, methyl, etc.), octanoate esters (allyl, isoamyl. borneol, isoborneol, carveol, piperitol, geraniol, C.- or B-san
ethyl, octyl, hexyl, butyl, methyl, linallyl, etc.), octenoate talol, citronellol, 4-thujanol, terpineol. 4-terpineol, nerol,
esters (methyl, ethyl, etc.), octynecarboxylate esters (methyl, 25 myrcenol, myrtenol, menthol, dihydromyrcenol, tetrahy
ethyl, etc.), caproate esters (allyl, amyl, isoamyl, methyl, dromyrcenol, nerolidol, hydroxycitronerol, farnesol, perilla
ethyl, isobutyl, propyl, hexyl, cis-3-hexenyl, trans-2-hexenyl, alcohol, rhodinol, linalool, etc.), aromatic alcohols (anise
linallyl, geranyl, cyclohexyl, etc.), hexenoate esters (methyl, alcohol, C.-amylcinnamic alcohol, isopropylbenzylcarbinol,
ethyl, etc.), Valerate esters (amyl, isopropyl, isobutyl, ethyl, carvacrol, cuminic alcohol, dimethylbenzylcarbinol, cin
cis-3-hexenyl, trans-2-hexenyl, cinnamyl, phenylethyl, 30 namic alcohol, phenylallyl alcohol, phenylethylcarbinol,
methyl, etc.), formate esters (anisyl, isoamyl, isopropyl. B-phenylethyl alcohol, 3-phenylpropyl alcohol, benzyl alco
ethyl, octyl, geranyl, citronellyl, cinnamyl, cyclohexyl, terpi hol, etc.), and the like.
nyl, phenylethyl, butyl, propyl, hexyl, cis-3-hexenyl, benzyl, Examples of the aldehydes to be used as the flavors in the
linallyl, rhodinyl, etc.), crotonate esters (isobutyl, ethyl, cyclo invention preferably include aliphatic aldehydes (acetalde
hexyl, etc.), cinnamate esters (allyl ethyl, methyl, isopropyl. 35 hyde, octanal, nonanal, decanal, undecanal. 2,6-dimethyl-5-
propyl, 3-phenylpropyl, benzyl, cyclohexyl, methyl, etc.), heptanal, 3.5.5-trimethylhexanal, cis-3, cis-6-nonadienal,
Succinate esters (monomenthyl, diethyl, dimethyl, etc.), trans-2, cis-6-nonadienal, Valeraldehyde, propanal, isopropa
acetate esters (anisyl, amyl, C.-amylcinnamyl, isoamyl, isobu nal, hexanal, trans-2-hexenal, cis-3-hexenal, 2-pentenal,
tyl, isopropyl, isopulegyl, isobornyl, isoeugenyl, eugenyl, dodecanal, tetradecanal, trans-4-decenal, trans-2-tridecenal,
2-ethylbutyl, ethyl, 3-octyl, carvyl, dihydrocarvyl, p-cresyl 40 trans-2-dodecenal, trans-2-undecenal, 2.4-hexadienal, cis-6-
o-cresyl, geranyl, C.- or B-Santalyl, cyclohexyl, cycloneryl, nonenal, trans-2-nonenal, 2-methylbutanal, etc.), aromatic
dihydrocuminyl, dimethylbenzylcarbinyl, cinnamyl, Styral aldehydes (anisaldehyde, C.-amylcinnamic aldehyde), C.-me
lyl, decyl, dodecyl, terpinyl, guanyl. neryl, nonyl, phenyl thylcinnamic aldehyde, cyclamen aldehyde, p-isopropylphe
ethyl, phenylpropyl, butyl, furfuryl, propyl, hexyl, cis-3-hex nylacetaldehyde, ethylvanillin, cuminaldehyde, salicylalde
enyl, trans-2-hexenyl, cis-3-nonenyl, cis-6-nonenyl, cis-3. 45 hyde, cinnamic aldehyde, o-, m- or p-tolylaldehyde, Vanillin,
cis-6-nonadienyl, 3-methyl-2-butenyl, menthyl, heptyl, ben piperonal, phenylacetaldehyde, heliotropin, benzaldehyde,
Zyl, bornyl, myrcenyl, dihydromyrcenyl, myrtenyl, methyl, 4-methyl-2-phenyl-2-pentenal, p-methoxycinnamic alde
2-methylbutyl, menthyl, linallyl, rhodinyl, etc.), Salicylate hyde, p-methoxybenzaldehyde, etc.), terpene aldehydes (ge
esters (allyl, isoamyl, phenyl, phenylethyl, benzyl, ethyl, ranial, citral, citronellal, C.-Sinensal, B-sinensal, perillalde
methyl, etc.), cyclohexylalkanoate esters (ethyl cyclohexy 50 hyde, hydroxycitronellal, tetrahydrocitral, myrtenal,
lacetate, allyl cyclohexylpropionate, allyl cyclohexylbu cyclocitral, isocyclocitral, citronellyloxyacetaldehyde, neral,
tyrate, allyl cyclohexylhexanoate, allyl cyclohexyldecanoate, C.-methylenecitronellal, myrac aldehyde, Vernaldehyde,
allyl cyclohexylvalerate, etc.), Stearate esters (ethyl, propyl. safranal, etc.), and the like.
butyl, etc.), sebacate esters (diethyl, dimethyl, etc.), Preferred examples of the ketones to be used as the flavors
decanoate esters (isoamyl, ethyl, butyl, methyl, etc.), dode 55 in the invention preferably include cyclic ketones (menthone,
canoate esters (isoamyl, ethyl, butyl, etc.), lactate esters isomenthone, carvone, dihydrocarvone, pulegone, piperi
(isoamyl, ethyl, butyl, etc.), nonanoate esters (ethyl, phenyl tone, 1-acetyl-3.3-dimethyl-1-cyclohexene, cis-jasmone, Cl-,
ethyl, methyl, etc.), nonenoate esters (allyl, ethyl, methyl, B- or Y-iron, ethylmaltol, cyclotene, dihydronootkatone, 3,4-
etc.), hydroxyhexanoate esters (ethyl, methyl, etc.), pheny dimethyl-1,2-cyclopentadione, Sotolone, Cl-, B-y- or Ö-dam
lacetate esters (isoamyl, isobutyl, ethyl, geranyl, citronellyl, 60 ascone, Cl-, 3- or Y-damascenone, nootkatone, 2-sec-butylcy
cis-3-hexenyl, methyl, etc.), phenoxyacetate esters (allyl, clohexanone, maltol, Cl-, 3- or Y-ionone, Cl-, 3- or
ethyl, methyl, etc.), furancarboxylate esters (ethyl furancar Y-methylionone, Cl-, 3- or Y-isomethylionone, furaneol, cam
boxylate, methyl furancarboxylate, hexyl furancarboxylate, phor, etc.), aromatic ketones (acetonaphthone, acetophenone,
isobutyl furanpropionate, etc.), propionate esters (anisyl, anisylideneacetone, raspberry ketone, p-methylacetophe
allyl, ethyl, amyl, isoamyl, propyl, butyl, isobutyl, isopropyl. 65 none, anisyllacetone, p-methoxyacetophenone, etc.), linear
benzyl, geranyl, cyclohexyl, citronellyl, cinnamyl, tetrahy ketones (diacetyl 2-nonanone, diacetyl, 2-heptanone, 2.3-
drofurfuryl, tricyclodecenyl, heptyl, bornyl, methyl, menthyl, heptanedione, 2-pentanone, methyl amyl ketone, methyl
 US 9,358,191 B2
15 16
nonyl ketone, B-methyl naphthyl ketone, methylheptanone, pyruvic acid, trans-2-methyl-2-pentenoic acid, 2-methyl-cis
3-heptanone, 4-heptanone, 3-octanone, 2.3-hexanedione, 3-pentenoic acid, 2-methyl-4-pentenoic acid, cyclohexan
2-undecanone, dimethyloctenone, 6-methyl-5-heptyn-3-one, ecarboxylic acid, and the like.
etc.), and the like. Furthermore, examples of the flavor materials of natural
Preferred examples of the acetals to be used as the flavors origin to be used as the flavors include anise, orange, lemon,
in the invention include acetaldehyde diethyl acetal, acetal lime, mandarin, petit grain, bergamot, lemon balm, grape
dehyde diamyl acetal, acetaldehyde dihexyl acetal, acetalde fruit, elemi, olibanum, lemon grass, neroli, marjoram,
hyde propylene glycol acetal, acetaldehyde ethyl cis-3-hex angelica root, star anise, basil, bay, calamus, chamomile,
enyl acetal, benzaldehyde glycerin acetal, benzaldehyde caraway, cardamom, Cassia, cinnamon, peppermint, spear
propylene glycol acetal, citral dimethyl acetal, citral diethyl 10 mint, mint, penny royal, pepper, perilla, cypress, oregano,
acetal, citral propylene glycol acetal, citral ethylene glycol cascarilla, ginger, parsley, pine needle, Sage, hyssop, tea tree,
acetal, phenylacetaldehyde dimethyl acetal, citronellyl mustard, horseradish, clarisage, clove, cognac, coriander,
methyl acetal, acetaldehyde phenylethyl propyl acetal, hexa estragon, eucalyptus, fennel, guaiac wood, dill, cajuput,
nal dimethyl acetal, hexanal dihexyl acetal, hexanal propy worm seed, pimento, juniper, fenugreek, garlic, laurel, mace,
lene glycol acetal, trans-2-hexenal diethyl acetal, trans-2- 15 mil, nutmeg, spruce, geranium, citronella, lavender, lavandin,
hexenal propylene glycol acetal, cis-3-hexenal diethyl acetal, palmarosa, rose, rosemary, Sandalwood, oak moth, cider
heptanal diethyl acetal, heptanal ethylene glycol acetal, octa wood, Vetiver, linaloe, bois de rose, patchouli, labdanum,
nal dimethyl acetal, nonanal dimethyl acetal, decanal dim cumin, thyme, ylang-ylang, birth, capsicum, celery, tolu bal
ethyl acetal, decanal diethyl acetal, 2-methylundecanal dim sam, djenne, inmortel, benzoin, jasmine, cassia, tuberose,
ethyl acetal, citronellal dimethyl acetal, ambersage mignonette, marigold, mimosa, opopanax, orris, Vanilla, lico
(manufactured by Givaudan), ethyl acetoacetate ethylene rice, and the like. The flavor components contained in these
glycol acetal, 2-phenylpropanal dimethyl acetal, and the like. flavor materials of natural origin can be also used.
Preferred examples of the phenols to be used as the flavors The fragrance to be used in the invention includes hydro
in the invention include eugenol, isoeugenol, 2-methoxy-4- carbons, alcohols, phenols, aldehydes and/or acetals, ketones
vinylphenol, thymol, carvacrol, guaiacol, chavicol, and the 25 and/or ketals, ethers, synthetic musks, acids, lactones, esters,
like. halogen-containing compounds, fragrance materials of natu
Preferred examples of the ethers to be used as the flavors in ral origin, and the like.
the invention include anethole, 1,4-cineole, 1,8-cineole, The hydrocarbons to be used as fragrances in the invention
dibenzyl ether, linalool oxide, limonene oxide, nerol oxide, are not particularly limited as far as they are volatile organic
rose oxide, methylisoeugenol, methyl chavicol, isoamylphe 30 compounds composed of carbon and hydrogen. Examples
nylethyl ether, B-naphthyl methyl ether, phenyl propyl ether, thereof include aliphatic hydrocarbons, alicyclic hydrocar
p-cresyl methyl ether, vanillyl butyl ether, C-terpinyl methyl bons, terpene hydrocarbons, aromatic hydrocarbons, and the
ether, citronellyl ethyl ether, geranyl ethyl ether, rose-furan, like. Preferred examples include 1,3,5-undecatriene,
theaspirane, decyl methyl ether, methyl phenylmethyl ether, p-cymene, C-pinene, C-phellandrene, B-caryophyllene,
and the like. 35 B-pinene, A-carene, allo-ocimene, Ocimene, dihy
Preferred examples of the lactones to be used as the flavors dromyrcene, dipentene, Sclarene, cedrene, terpinene, terpi
in the invention include Y- or 6-decalactone, Y-heptalactone, nolene, Valencene, bisabolene, farmesene, myrcene,
Y-nomalactone, y- or 6-hexylactone, y- or Ö-octalactone, Y- or limonene, longifolene, adamantane, isolongifolene, cam
Ö-undecalactone, 6-dodecalactone, 6-2-decenolactone, meth phene, guaiene, diphenyl, diphenylmethane, biphenyl, 3.7-
yllactone, 5-hydroxy-8-undecenenoic acid 6-lactone, jas 40 dimethyl-1,3,6-octatriene, 4-isopropyl-1-methyl-2-prope
mine lactone, menthalactone, dihydrocoumarin, octahydro nylbenzene, 7-methyl-3-methylene-1,6-octadiene,
coumarin, 6-methylcoumarin, and the like. p-ethylstyrene, C.-p-dimethylstyrene, isoprene, undecatriene,
Preferred examples of the furans to be used as the flavors in undecane, octadecadiene, octadecane, octadecene, octane,
the invention include furan, 2-methylfuran, 3-methylfuran, octene, cumene, Sabinene, cyclohexane, cyclohexene, cyclo
2-ethylfuran, 2,5-diethyltetrahydrofuran, 3-hydroxy-2-meth 45 pentadiene, dicyclopentadiene, styrene, decalin, decane, tet
yltetrahydrofuran, 2-(methoxymethyl)furan, 2,3-dihydrofu radecane, tetralin, dodecane, tridecane, tridecene, naphtha
ran, menthofuran, furfural, 5-methylfurfural, 3-(2-furyl)-2- lene, nonane, nonene, norbornane, norbornene, hexadecane,
methyl-2-propenal, 5-(hydroxymethyl)furfural, 2.5- hexane, heptadecadiene, heptadecane, heptadecene, heptane,
dimethyl-4-hydroxy-3(2H)-furanone (furaneol), 4,5- and pentadecane. Further preferred examples include 1,3,5-
dimethyl-3-hydroxy-2(5H)-furanone (sotolone), 2-ethyl-4- 50 undecatriene, p-cymene, C-pinene, C-phellandrene, B-caryo
hydroxy-5-methyl-3(2H)-furanone (homofuranol), 5-ethyl phyllene, B-pinene, A-carene, allo-ocimene, ocimene, dihy
3-hydroxy-4-methyl-2(5H)furanone (homosotolone), dromyrcene, dipentene, Sclarene, cedrene, terpinene,
3-methyl-1,2-cyclopentanedione (cyclotene), 205H)-fura terpinolene, Valencene, bisabolene, farnesene, myrcene,
none, 4-methyl-2(5H)-furanone, 5-methyl-2(5H)-furanone, limonene, longifolene, adamantane, isolongifolene, and cam
2-methyl-3(2H)-furanone, 5-methyl-3(2H)-furanone, 55 phene.
2-acetylfuranone, 2-acetyl-5-methylfuran, furfuryl alcohol, The alcohols to be used as fragrances in the invention are
methyl 2-furancarboxylate, ethyl 2-furancarboxylate, furfu not particularly limited as far as they are volatile organic
ryl acetate, and the like. compounds having a hydroxyl group. Examples thereof
Preferred examples of the hydrocarbons to be used as the include aliphatic alcohols, alicyclic alcohols, terpene alco
flavors in the invention include C.-bisabolene, B-caryophyl 60 hols, aromatic alcohols, and the like. Preferred examples
lene, p-cymene, terpinene, terpinolene, cadinene, farnesene, include 10-undecenol, 1-octen-3-ol, 2,6-nonadienol, 2-tert
limonene, Ocimene, myrcene, C.- or B-pinene, 1,3,5-undec butylcyclohexanol, 2-ethylhexanol, 2-heptanol, 3.5.5-trim
atriene, Valencene, and the like. ethylhexanol, 3-octanol, 3-phenylpropyl alcohol, L-menthol,
Moreover, preferred examples of the acids to be used as the n-decyl alcohol, C.-dimethylbenzyl alcohol, p-tert-butylcy
flavors in the invention include octanoic acid, nonanoic acid, 65 clohexanol, p-methyldimethylbenzylcarbinol, C.3,3-trim
decanoic acid, 2-decenoic acid, geranic acid, dodecanoic ethyl-2-norbornanemethanol, C.-n-amylcinnamic alcohol,
acid, myristic acid, Stearic acid, lactic acid, phenylacetic acid, C.-fenchyl alcohol, 3-phenylethyl alcohol, anise alcohol,
 US 9,358,191 B2
17 18
amber core, ambrinol, isononyl alcohol, isophytol, isopule examples thereof include 10-undecenol, 1-octen-3-ol, 2.6-
gol, isoborneol, ethyllinalool, octanol, carveol, geraniol, san nonadienol, 2-tert-butylcyclohexanol, 2-ethylhexanol,
talol, cis-3-hexen-1-ol, cis-6-nonenol, citronellol, dihydro-C.- 2-heptanol, 3.5.5-trimethylhexanol, 3-octanol, 3-phenylpro
terpineol. dihydrocitronellol, dihydromyrcenol, pyl alcohol, L-menthol, n-decyl alcohol, C.-dimethylbenzyl
dihydrolinalool, dimethylphenylethylcarbinol, dimethylben alcohol, p-tert-butylcyclohexanol, p-methyldimethylbenzyl
Zylcarbinol, cinnamic alcohol, styrally alcohol, cedrol, terpi carbinol, C.3.3-trimethyl-2-norbornanemethanol, C.-n-amyl
neol, terpinen-4-ol. Timberol, tetrahydrogeraniol, tetrahy cinnamic alcohol, C-fenchyl alcohol, B-phenylethyl alcohol,
dromyrcenol, tetrahydromugol, tetrahydrolinalool, nerol, anise alcohol, amber core, ambrinol, isononyl alcohol, iso
nerolidol, nonanol, nonyl alcohol, nopol, hydrotropyl alco phytol, isopulegol, isoborneol, ethyllinalool, octanol, car
hol, Bacdanol, patchouli alcohol, farnesol, phytol, phenyleth 10 Veol, geraniol, Santalol, cis-3-hexen-1-ol, cis-6-nonenol, cit
ylmethylethylcarbinol, phenoxyethyl alcohol, furfuryl alco ronellol, dihydro-C-terpineol. dihydrocitronellol,
hol, Vetivenol, perilla alcohol, benzyl alcohol, mayol, dihydromyrcenol, dihydrolinalool, dimethylphenylethyl
myrcenol, myrtenol, lavandulol, linalool, 1-(2.2,6-trimethyl carbinol, dimethylbenzylcarbinol, cinnamic alcohol, Styrally
cyclohexanyl)-hexan-3-ol, 1,1-dimethyl-3-phenylpropanol, alcohol, cedrol, terpineol, terpinen-4-ol. Timberol, tetrahy
1-decanol. 1-dodecanol. 1-nonen-3-ol, 1-heptanol, 1-penten 15 drogeraniol, tetrahydromyrcenol, tetrahydromugol, tetrahy
3-ol, 2,2-dimethyl-3-phenylpropanol. 2,4-dimethyl-3-cyclo drolinalool, nerol, nerolidol, nonanol, nonyl alcohol, nopol,
hexene-1-methanol. 2,4-dimethylbenzyl alcohol. 2.4-hexadi hydrotropyl alcohol, Bacdanol, patchouli alcohol, farnesol,
enol, 2.5.5-trimethyloctahydro-2-naphthol, 2,6- phytol, phenylethylmethylethylcarbinol, phenoxyethyl alco
dimethylheptan-2-ol. 2-isobutyl-4-hydroxy-4- hol, furfuryl alcohol, Vetivenol, perillaalcohol, benzyl alco
methyltetrahydropyran, 2-undecanol, 2-octanol, 2-nonanol, hol, myol, myrcenol, myrtenol, lavandulol, and linalool.
2-phenylpropyl alcohol, 2-methyl-3-buten-2-ol, 2-methyl-4- The phenols to be used as fragrances in the invention are
(2,2,3-trimethyl-3-cyclopentenyl)-2-butenol, 2-methyl-4-(2, not particularly limited as far as they are organic compounds
2,3-trimethyl-3-cyclopentenyl)-butanol, 2-methyloctanol, which are phenolic compounds or derivatives thereof and
2-methyldecanol, 2-methoxy-2-phenylethyl alcohol, 3.3- have aroma or pleasant odor, and examples thereof include
dimethyl-A2.f-norbornane-2-ethanol, 3,4,5,6,6-pentam 25 monovalent, divalent, or trivalent phenolic compounds,
ethyl-2-heptanol. 3,6-dimethyloctan-3-ol, 3,7-dimethyl-1- polyphenols, or ether derivatives thereof. Preferred examples
octanol. 3,7-dimethyl-7-methoxyoctan-2-ol, 3-thujanol, thereof include p-cresol, isoeugenol, estragol, eugenol, hino
3-dodecanol, 3-heptanol, 3-methyl-1-phenyl-3-pentanol, kithiol, benzylisoeugenol, benzyleugenol, methylisoeugenol,
3-methyl-2-buten-1-ol. 3-methyl-5-(2,2,3-trimethyl-3-cy methyleugenol, 2-methoxynaphthalene, 2,6-dimethoxyphe
clopentenyl)pentan-2-ol. 3-methyl-5-phenylpentanol, 3-me 30 nol, 4-ethylguaiacol, 4-methylguaiacol, 5-propenylguaetol,
thylpentanol, 4-isopropylcyclohexanol, 4-thujanol, 4-me B-naphthol isobutyl ether, p-allylphenol, p-ethylphenol,
thyl-3-decen-5-ol. 5-methyl-2-phenyl-2-hexanol, 6.8- isosafrol, ethylisoeugenol, catechol dimethyl ether, carvac
dimethyl-2-nonanol, 9-decenol, 9-decen-1-ol, E.G. rol, guaiacol, creosol, Safrol, dihydroeugenol, thymol, chavi
monobutyl ether, sec-undecylic alcohol, Sec-octyl alcohol, col, hydroquinone dimethyl ether, Vanitrope, bromelia, meth
sec-nonyl alcohol, C.C.p-trimethylphenylethyl alcohol, C.C.- 35 oxybenzene, resorcinol dimethyl ether, and shogaol.
dimethylphenylethyl alcohol, C.-isobutylphenylethyl alcohol, The aldehydes or acetals to be used as fragrances in the
C.-bisabolol, C-propylphenylethyl alcohol, B.Y-hexenol, invention are not particularly limited as far as they are volatile
B-caryophyllene alcohol, Y-4-dimethyl-3-cyclohexene-1- organic compounds having an aldehyde group or an acetal
propanol, allo-ocimenol, Ambestol, isocamphylcyclohex group in the molecule. Examples thereof include aliphatic
anol, isocyclogeraniol, isodihydrolavandulol, isobutylben 40 aldehydes or acetals, terpene aldehydes or acetals, aromatic
Zylcarbinol, undecanol, ethylene glycol, ethylene glycol aldehydes oracetals, and the like. Preferred examples include
monoethyl ether, ethylene glycol monobutyl ether, ethylene 10-undecenal, 2,4-dimethyl-4,4a,5.9b-tetrahydroindeno1,
glycol monopropyl ether, ethylene glycol monomethyl ether, 2d-1,3-dioxine, 2,4-decadienal, 2.6-nonadienal, 2-butyl-4.4.
ocimenol, Camekol DH. cuminalcohol, geranyllinalool, Sab 6-trimethyl-1,3-dioxane, 2-hexyl-5-methyl-1,3-dioxolane,
inene hydrate, diethylene glycol, diethylene glycol monoet 45 2-methylundecanal, 2-methylundecanal dimethyl acetal,
hyl ether, diethylene glycol monobutyl ether, diethylene gly 3-ethyl-2,4-dioxaspiro5.5undec-8-ene, 3-ethyl-8(9), 11
col monopropyl ether, diethylene glycol monomethyl ether, dimethyl-2,4-dioxaspiro5.5undec-8-ene, 3-propylbicyclo
cyclohexylethyl alcohol, cyclomethylene citronellol, cis-4- 2.2.1-hept-5-ene-2-carboxyaldehyde, 4-isopropyl-5,5-
hexen-1-ol, cis-p-isopropylcyclohexylmethanol, dihydrocar dimethyl-1,3-dioxane, 4-heptenal, 5-methyl-5-propyl-2-(1-
Veol, dipropylene glycol, dipropylene glycol monoethyl 50 methylbutyl)-1,3-dioxane, o-methoxycinnamic aldehyde,
ether, dipropylene glycol monobutyl ether, dipropylene gly o-methoxybenzaldehyde, p-tolylaldehyde, C.-n-hexylcin
col monopropyl ether, dipropylene glycol monomethyl ether, namic aldehyde, C-amylcinnamic aldehyde, acetaldehyde,
dimethyloctanol, dimethylvinylcarbinol, Sclareol, decahy acetaldehyde ethyllinallyl acetal, acetaldehyde diethyl acetal,
dro-3-naphthol, tetrahydroallo-ocimenol, trans-2-octanol, anisaldehyde, aldehyde C-10, aldehyde C-11, aldehyde C-12,
trans-2-hexenol, trans-3-hexen-1-ol, neopentyl glycol, 55 aldehyde C-6, aldehyde C-6 DEA, aldehyde C-6 DMA, alde
hydrocinnamic alcohol, Vanillyl alcohol, pinocarveol, hyde C-6 PG acetal, aldehyde C-8, aldehyde C-8 DEA, alde
butane-1,3-diol, butane-1,3-diol monoethyl ether, butane-1, hyde C-8 DMA, aldehyde C-9, aldehyde C-9 DEA, aldehyde
3-diol monobutyl ether, butane-1,3-diol monopropyl ether, C-9DMA, isocyclocitral, ethylvanillin, canthoxal, cucumber
butane-1,3-diol monomethyl ether, butane-2,3-diol, butane aldehyde, cumin aldehyde, geranial, cyclamen aldehyde, cis
2,3-diol monoethyl ether, butane-2,3-diol monobutyl ether, 60 6-nonenal, citral, citronellal, citronellyloxyacetaldehyde,
butane-2,3-diol monopropyl ether, butane-2,3-diol monom cinensal, Dupical, trans-2-hexenal, trans-2-hexenal diethyl
ethyl ether, butylene glycol, propylene glycol, propylene gly acetal, Triplal, neral, hydrotropaldehyde, Vanillin, hydroxy
col monoethyl ether, propylene glycol monobutyl ether, pro citronellal, phenylacetaldehyde, phenylacetaldehyde P.G.
pylene glycol monopropyl ether, propylene glycol acetal, phenylacetaldehyde dimethyl acetal, furfural, Floralo
monomethyl ether, hexamethylene glycol, hexylene glycol, 65 Zone, heliotropin, helional, perillaldehyde, bergamal, beltal
pentamethylene glycol, muguet alcohol, methyl 3-phenyl dehyde, bernaldehyde, benzaldehyde, homo-myrac alde
ethyl alcohol, and methyl sandeflor. Further preferred hyde, myrac aldehyde, melonal, lilal, lilial, 2.4.6-
 US 9,358,191 B2
19 20
triisopropyl-1,3,5-trioxane, 2.4-undecadienal, 2,4- beraldehyde, cumin aldehyde, geranial, cyclamen aldehyde,
octadienal, 2,4-dioxa-3-methyl-7,10-methanospiro5.5- cis-6-nonenal, citral, citronellal, citronellyloxyacetaldehyde,
undecane, 2,4-dodecadienal, 2.4-nonadienal, 2.4-hexadienal, cinensal, Dupical, trans-2-hexenal, trans-2-hexenal diethyl
2.4-heptadienal, 2.5,6-trimethyl-4-heptenal, 2,6,10-trim acetal, Triplal, neral, hydrotropaldehyde, Vanillin, hydroxy
ethyl-5.9-undecadienal, 2-methyl-3-(4-methylphenyl)-pro citronellal, phenylacetaldehyde, phenylacetaldehyde P.G.
panal, 2-methyl-4-(2,6,6-trimethyl-2-cyclohexenyl)-3-bute acetal, phenylacetaldehyde dimethyl acetal, furfural, Floralo
nal, 2-methylbutanal, 3-phenylpropionic aldehyde, Zone, heliotropin, helional, perillaldehyde, bergamal, beltal
3-phenylpropionic aldehyde dimethyl acetal, 3-methyl-5- dehyde, bernaldehyde, benzaldehyde, homo-myrac alde
phenylvaleraldehyde, 4-(2.2,6-trimethyl-2(1)-cyclohexane)- hyde, myrac aldehyde, melonal, lilal, and lilial.
2-methylbutanal, 4-(4-methyl-3-cyclohexen-1-ylidene)-pen 10 The ketones or ketals to be used as fragrances in the inven
tanal, 4-methyl-2-phenyl-2-pentenal, 5-(hydroxymethyl)-2- tion are not particularly limited as far as they are volatile
furfural, 5,9-dimethyl-4,9-decadienal, 5-methylfurfural, organic compounds having a ketone group or a ketal group in
n-valeraldehyde, p-tert-butylhydrocinnamic aldehyde, the molecule include aliphatic ketones or ketals, terpene
p-isobutyl-O-methylhydrocinnamic aldehyde, p-isopropyl ketones or ketals, aromatic ketones or ketals, and the like.
hydrotropaldehyde, p-methylhydrotropaldehyde, p-meth 15 Preferred examples include 2-sec-butylcyclohexanone,
ylphenylacetaldehyde, p-methylphenoxyacetaldehyde, 2-acetyl-3,3-dimethylnorbornane, 2-acetyl-5-methylfuran,
p-methoxybenzaldehyde, C.-n-amylcinnamic aldehyde 2-acetylfuran, 2-butyl-1,4-dioxaspiro4.4nonane, 2-hexyl
diethyl acetal, C-amylcinnamic aldehyde dimethyl acetal, cyclopentanone, 3-hydroxy-4,5-dimethyl-2-(5H)-furanone,
C-camphorenaldehyde, C.-methylcinnamic aldehyde, B-me 5-ethyl-3-hydroxy-4-methyl-25H-furanone, 6-methyl-3,5-
thylhydrocinnamic aldehyde, Y-n-hexylcinnamic aldehyde, heptadien-2-one, d-pulegone, L-carvone, o-tert-butylcyclo
acetaldehyde ethyl isoeugenyl acetal, acetaldehyde ethyl cis hexanone, p-tert-butylcyclohexanone, p-methylacetophe
3-hexenyl acetal, acetaldehyde ethyl phenylethyl acetal, none, p-methoxyacetophenone, C.-dinascone, C-fenchone,
acetaldehyde ethyl hexyl acetal, acetaldehyde citronellyl B-methylnaphthylketone, acetylcedrene, acetophenone, ani
ethyl acetal, acetaldehyde citronellyl methyl acetal, acetalde Sylacetone, allyl C-ionone, ionone, iso-E-Super, isojasmone,
hyde phenylethyl n-propyl acetal, aldehyde C-13, aldehyde 25 isodamascone, isolongifolanone, irone, ethyl isoamylketone,
C-14, aldehyde C-5, aldehyde C-7, aldehyde C-7 DEA, alde ethylmaltol, Cashmeran, carone, camphor, Koavone, cyclo
hyde C-7 DMA, isovaleraldehyde, octahydro-4,7-methano tene, cis-jasmone, dihydrocarvone, dihydrojasmone, diben
1H-indenecarboxyaldehyde, caryophyllenaldehyde, gerany Zylketone, cedorenone, Sotolone, damascone, damascenone,
loxyacetaldehyde, Safranal, Salicylaldehyde, cyclocitral, cis trimofix O. nootkatone, furaneol, plicatone, florex, vertfix,
3-hexenal, cis-3-hexenal diethyl acetal, cis-4-decenal, citral 30 Verbenone, benzophenone, maltol, methylionone, methylcy
PG acetal, citral diethyl acetal, citral dimethyl acetal, cit clopentenolone, methylheptenone, menthone, raspberry
ronellal EG acetal, dihydroindenyl-2,4-dioxane, dimethyloc ketone, 1-(4-methoxyphenyl)-1-penten-3-one, 1-(p-men
tanal, cinnamic aldehyde, decanal diethyl acetal, decanal then-6-yl)-1-propanone, 1-acetyl-3.3-dimethyl-1-cyclohex
dimethyl acetal, tetrahydrocitral, dodecanal dimethyl acetal, ene, 2-(1-cyclohexen-1-yl)cyclohexanone, 2.2.5.5-tetram
trans-2-undecenal, trans-2-decen-1-al, trans-2-dodecenal, 35 ethyl-4-isopropyl-1,3-dioxane, 2.2.5-trimethyl-5-
trans-2-tridecenal, trans-2-nonenal, trans-2-heptenal, trans pentylcyclopentanone, 2,3,5-trimethylcyclohexen-4-yl-1-
2-pentenal, trans-4-decenal, trimethylundecenal, trimethyl methyl ketone, 2.3-hexadione, 2.3-heptanedione, 2.3-
decadienal, hydrotropaldehyde E.G. acetal, hydrotropalde pentadione, 2,4-di-tert-butylcyclohexanone, 2.5.5-trimethyl
hyde dimethyl acetal, vanillin P.G. acetal, paraldehyde, 2-phenyl-1,3-dioxane, 2,6,10-trimethyl-1-acetyl-2.5.9-
hydroxycitronellal diethyl acetal, phenylacetaldehyde 2,3- 40 cyclododecatriene, 2.6,6-trimethyl-2-cyclohexene-1,4-
butylene glycol acetal, phenylacetaldehyde 2,4-dihydroxy-4- dione, 2-n-butylidene-35,5(3,3,5)-trimethylcyclohexanone,
methylpentane acetal, phenylacetaldehyde diisobutyl acetal, 2-n-heptylcycloheptanone, 2-acetonaphthone, 2-unde
phenoxyacetaldehyde, furfurylacrolein, heptanal E.G. acetal, canone, 2-octanone, 2-cyclopentylcyclopentanone, 2-tride
heliotropin diethyl acetal, heliotropin dimethyl acetal, ben canone, 2-nonanone, 2-hydroxy-6-isopropyl-3-methyl-2-cy
Zaldehyde PG acetal, benzaldehyde glyceryl acetal, benzal 45 clohexenone, 2-butanone, 2-heptanone,
dehyde diethyl acetal, benzaldehyde dimethyl acetal, formal 2-heptylcyclopentanone, 2-pentanone, 2-pentyl-2-cyclopen
dehyde cyclododecyl ethyl acetal, methyldecanal, tenone, 2-pentylcyclopentanone, 3.3-dimethylcyclohexyl
methylnonylacetaldehyde dimethyl acetal, methylvanillin, methyl ketone, 3,4-dimethyl-1,2-cyclopentadione, 3,4-hexa
methoxydicyclopentadienecarboxyaldehyde, and methoxy dione, 3,5-dimethyl-1,2-cyclopentadione, 3-acetyl-2,5-dim
citronellal. Further preferred examples include 10-undecenal, 50 ethylfuran, 3-octanone, 3-nonanone, 3-hydroxymethyl-2-
2,4-dimethyl-4,4a,5.9b-tetrahydroindeno1.2d-1,3-dioxine, nonanone, 3-hexanone, 3-heptanone, 3-hepten-2-one,
2,4-decadienal. 2.6-nonadienal, 2-butyl-4,4,6-trimethyl-1,3- 3-methyl-4-phenyl-3-buten-2-one, 3-methyl-5-(2,2,3-trim
dioxane, 2-hexyl-5-methyl-1,3-dioxolane, 2-methylundeca ethyl-3-cyclopentenyl)-3-penten-2-one, 3-methyl-5-propyl
nal, 2-methylundecanal dimethyl acetal, 3-ethyl-2,4-dioxas 2-cyclohexenone, 4-(4-hydroxy-3-methoxyphenyl)-2-bu
piro5.5undec-8-ene, 3-ethyl-8(9), 11-dimethyl-2,4- 55 tanone, 4-(4-methoxyphenyl)-3-buten-2-one, 4(5)-acetyl-7.
dioxaspiro5.5undec-8-ene, 3-propylbicyclo[2.2.1-hept-5- 7.9-(7.9.9)-trimethylbicyclo4.3.0nona-1-ene, 4,7-dihydro
ene-2-carboxyaldehyde, 4-isopropyl-5,5-dimethyl-1,3- 2-(3-pentanyl)-1,3-dioxepine, 4,7-dihydro-2-isoamyl-2-
dioxane, 4-heptenal, 5-methyl-5-propyl-2-(1-methylbutyl)- methyl-1,3-dioxiepine, 4-tert-amylcyclohexanone,
1,3-dioxane, o-methoxycinnamic aldehyde, 4-oxoisophorone, 4-cyclohexenyl-4-methyl-2-pentanone,
o-methoxybenzaldehyde, p-tolylaldehyde, C.-n-hexylcin 60 4-heptanone, 4-methyl-3-penten-2-one, 4-methyl-4-phenyl
namic aldehyde, C-amylcinnamic aldehyde, acetaldehyde, 2-pentanone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone,
acetaldehyde ethyllinallyl acetal, acetaldehyde diethyl acetal, 5-cyclohexadecen-1-one, 5-hydroxy-4-octanone, 5-phenyl
anisaldehyde, aldehyde C-10, aldehyde C-11, aldehyde C-12, 5-methyl-3-hexanone, 5-methyl-2,3-hexadione, 7-methyl-3,
aldehyde C-6, aldehyde C-6 DEA, aldehyde C-6 DMA, alde 5-dihydro-2H-benzodioxepin-3-one, p-hydroxyphenylbu
hyde C-6 PG acetal, aldehyde C-8, aldehyde C-8 DEA, alde 65 tanone, p-methoxyphenylacetone, C.-methylanisalacetone,
hyde C-8 DMA, aldehyde C-9, aldehyde C-9 DEA, aldehyde acetylisovaleryl, acetyl caryophyllene, acetyldimethyltet
C-9 DMA, isocyclocitral, ethylvanillin, kantokisal, cucum rahydrobenzindane, acetoin, acetoketal, acetophenone neo
 US 9,358,191 B2
21 22
pentyl glycol acetal, acetone, atrinone, anisylidenacetone, propylene glycol dimethyl ether. Further preferred examples
amylcyclopentanone, ethyl acetoacetate E.G. ketal, ethyl thereof include 14-cineol. 1,8-cineol, p-cresyl methyl ether,
acetoacetate propylene glycol acetal, oxocedrane, cryptone, B-caryophyllene oxide, B-naphthyl isobutyl ether, B-naphthyl
geranylacetone, diacetyl, diacetone alcohol, diosphenol, ethyl ether, B-naphthyl methyl ether, anethole, ambroxane,
cyclohexanone, cyclohexenone, cyclopentanone, cis-2-ac isoamyl phenylethyl ether, isobornyl methyl ether, grisalva,
etonyl-4-methyltetrahydropyran, dimethyloctenone, cyclamber, diphenyl oxide, cedrambar, cedryl methyl ether,
Zingerol, cedranone, vitalide, piperitenone, piperitone, pip teaspyran, nerol oxide, phenylethyl methyl ether, madroX,
eronylacetone, farnesylacetone, pseudoionone, butylidene linalool oxide, limetol, Rhubofix, rhouboflor, rose oxide, and
acetone, furfural acetone, propiophenone, heliotropylac rose furan.
etone, Verdoxane, benzylideneacetone, homofuraneol. 10 The synthetic musks to be used as fragrances in the inven
mesityl oxide, methyl C.-furyl ketone, methyl isopropyl tion are not particularly limited as far as they are organic
ketone, methyliritone, methylcedorilone, and methyltetrahy compounds having musk odor or musk-like odor and
drofuranone. Further preferred examples include 2-sec-bu examples thereof include 10-oxahexadecanolide, 11-Oxa
tylcyclohexanone, 2-acetyl-3,3-dimethylnorbornane, hexadecanolide, 12-oxahexadecanolide, ambrettolide,
2-acetyl-5-methylfuran, 2-acetylfuran, 2-butyl-1,4-dioxas 15 Ambreton, exaltolide, exaltone, Galaxolide, cyclohexade
piro4.4nonane, 2-hexylcyclopentanone, 3-hydroxy-4,5- canolide, cyclopentadecanolide, cyclopentadecanone,
dimethyl-2-(5H)-furanone, 5-ethyl-3-hydroxy-4-methyl-2 civetone, cerVolide, celestolide, Tonalide, fantolide, pen
5H-furanone, 6-methyl-3,5-heptadien-2-one, d-pulegone, tallide, formylethyltetramethyltetralin, muscone, versalide,
L-carvone, o-tert-butylcyclohexanone, p-tert-butylcyclohex and the like.
anone, p-methylacetophenone, p-methoxyacetophenone, The acids to be used as fragrances in the invention are not
C-dinascone, C.-fenchone, B-methylnaphthylketone, acetyl particularly limited as far as they are organic compounds
cedrene, acetophenone, anisyllacetone, allyl C-ionone, ion having a carboxyl group in the molecule and examples
one, iso E Super, isojasmone, isodamascone, isolongifol thereof include phenylacetic acid, 2-ethylbutyric acid, 2-eth
anone, irone, ethyl isoamylketone, ethylmaltol, Cashmeran, ylhexanoic acid, 2-decenoic acid, 2-hexenoic acid, 2-methyl
carone, camphor, Koavone, cyclotene, cis-jasmone, dihydro 25 2-pentenoic acid, 2-methylbutyric acid, 2-methylheptanoic
carvone, dihydrojasmone, dibenzyl ketone, cedorenone, acid, 4-pentenoic acid, 4-methylpentanoic acid, undecanoic
Sotolone, damascone, damascenone, trimofix O. nootkatone, acid, undecylenic acid, octanoic acid, oleic acid, geranic acid,
furaneol, plicatone, florex, vertfix, verbenone, benzophe cinnamic acid, Stearic acid, tiglic acid, decanoic acid, dode
none, maltol, methylionone, methylcyclopentenolone, meth canoic acid, tridecanoic acid, nonanoic acid, hydrocinnamic
ylheptenone, menthone, raspberry ketone. 30 acid, pyruvic acid, propionic acid, hexanoic acid, heptanoic
The ethers to be used as fragrances in the invention are not acid, myristic acid, lactic acid, linolic acid, linoleic acid,
particularly limited as far as they are volatile organic com levulinic acid, oxalic acid, glutalic acid, citric acid, succinic
pounds having an ether group in the molecule. Examples acid, tartaric acid, terephthalic acid, Vanillic acid, valine,
thereof include aliphatic ethers, terpene ethers, aromatic phytic acid, fumaric acid, benzoic acid, malic acid, maleic
ethers, and the like. Preferred examples include 14-cineol, 35 acid, malonic acid, and the like.
1,8-cineol. p-cresyl methyl ether, B-caryophyllene oxide, The lactones to be used as fragrances in the invention are
B-naphthyl isobutyl ether, B-naphthyl ethyl ether, B-naphthyl not particularly limited as far as they are organic compounds
methyl ether, anethole, ambroxane, isoamyl phenylethyl having a lactone group in the molecule and examples thereof
ether, isobornyl methyl ether, grisalva, cyclamber, diphenyl include aliphatic lactones, terpene lactones, aromatic lac
oxide, cedrambar, cedryl methyl ether, teaspyran, nerol 40 tones, and the like. Preferred examples thereof include 6-me
oxide, phenylethyl methyl ether, madrox, linalool oxide, thylcoumarin, C.-angelica lactone, Y-n-butyrolactone, Y-unde
limetol, Rhubofix, rhouboflor, rose oxide, rose furan, 13-ox calactone, Y-octalactone, y-decalactone, Y-nomalactone,
abicyclo10.3.0pentadecane, 1-methylcyclododecyl methyl Y-Valerolactone, Y-hexylactone, Y-heptalactone, 6-2-deceno
ether, 2.2,6-trimethyl-6-vinyltetrahydrofuran, 2.2-dimethyl lactone, Ö-undecalactone, Ö-octalactone, Ö-decalactone,
5-(1-methyl-1-propenyl)-tetrahydropyran, 2-ethylidene-6- 45 8-tetradecalactone, 6-dodecalactone, 6-tridecalactone,
isopropoxybicyclo2.2.1]heptane, 2-oxaspiro4.7dodecane, Ö-nonalactone, Ö-hexylactone, e-decalactone, e-dodecallac
2-butyl-4,6-dimethyldihydropyran, 2-methyl-2-butenylphe tone, aldehyde C-14 (peach), aldehyde C-18 (coconut),
nyl ethyl ether, 3,3,5-trimethylcyclohexyl ethyl ether, 3-ox whisky lactone, dihydrojasmone lactone, jasmine lactone,
abicyclo10.3.0-pentadec-6-ene, 4-allylanisole, 5-isoprope jasmolactone, methyly-decalactone, menthalactone, 4.6.6(4.
nyl-2-methyl-2-vinyltetrahydrofuran, 8.9-epoxycedrene, 50 4.6)-trimethyltetrahydropyran-2-one, 7-decene-1,4-lactone,
n-decyl vinyl ether, tert-butylhydroquinone dimethyl ether, octahydrocoumarin, dihydrocoumarin, dodecalactone, 3-n-
C.-cedrene epoxide, C-terpinyl methyl ether, allyl phenylethyl butylidenephthalide, 3-n-butylphthalide, 3-propylideneph
ether, isoamyl benzyl ether, isolongifolene epoxide, ethyl thalide, and 3-propylphthalide.
o-methoxybenzyl ether, Ocimene epoxide, geranyl ethyl The esters to be used as fragrances in the invention are not
ether, cyclodecenyl methyl ether, cyclohexyl ethyl ether, 55 particularly limited as far as they are volatile organic com
cyclohexyl phenylethyl ether, citroxide, citroneryl ethyl pounds having an ester group in the molecule and examples
ether, dibenzyl ether, juniparome, cedrol methyl ether, decyl thereof include aliphatic esters, terpene esters, aromatic
methyl ether, tricyclodecenyl methyl ether, trimethylcy esters, and the like. Preferred examples thereof include
clododecatriene epoxide, methylphenyl ethyl ether, methyl 1-ethynylcyclohexyl acetate, 1-octen-3-yl acetate, 2-ethyl
hexyl ether, methyl benzyl ether, limonene oxide, 1,2- 60 hexyl acetate, 2-phenoxyethyl isobutyrate, 2-phenoxyethyl
dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxy propionate, 3.5.5-trimethylhexyl acetate, 3,7-dimethylocta
2-tert-butylbenzene, ethylene glycol diethyl ether, ethylene nyl acetate, 3-phenylpropyl acetate, 9-decen-1-yl acetate,
glycol dibutyl ether, ethylene glycol dipropyl ether, ethylene L-menthyl acetate, L-menthyl propionate, o-tert-butylcyclo
glycol dimethyl ether, diethyl ether, diethylene glycol diethyl hexyl acetate, p-tert-butylcyclohexyl acetate, p-cresyl
ether, diethylene glycol dibutyl ether, diethylene glycol 65 acetate, p-cresyl isobutyrate, p-cresyl phenylacetate, acetyli
dipropyl ether, diethylene glycol dimethyl ether, dimethyl Soeugenol, acetyleugenol, anisyl acetate, aphermate, amyl
ether, tetrahydrofuran, propylene glycol diethyl ether, and acetate, amyl caprylate, amyl caproate, amyl salicylate, amyl
 US 9,358,191 B2
23 24
Valerate, amylbutyrate, amyl formate, allyl 2-ethylbutyrate, ethylbenzylcarbinyl propionate, jasmal, cinnamyl acetate,
allylamyl glycolate, allyl isovalerate, allyl octanoate, allyl cinnamyl isovalerate, cinnamyl isobutyrate, cinnamyl cin
caprylate, allyl caproate, allyl cyclohexylacetate, allyl cyclo namate, cinnamyl tiglate, cinnamylbutyrate, cinnamyl pro
hexyloxyacetate, allyl cyclohexylbutyrate, allyl cyclohexyl pionate, cinnamyl benzoate, cinnamyl formate, Styrallyl
propionate, allyl cinnamate, allyl phenoxyacetate, allyl acetate, styrallyl isobutyrate, styrallyl propionate, cedryl
butyrate, allyl heptanoate, allyl benzoate, aldehyde C-16 acetate, cedryl formate, terpinyl acetate, terpinyl isovalerate,
(strawberry), aldehyde C-19 (pineapple), aldehyde C-20 terpinyl isobutyrate, terpinyl butyrate, terpinyl propionate,
(raspberry), isoamyl acetate, isoamylangelate, isoamylisov terpinyl formate, decahydro-3-naphthyl formate, decyl
alerate, isoamyl isobutyrate, isoamyl undecylenate, isoamyl acetate, tetrahydrofurfuryl butyrate, tetrahydrogeranyl
octanoate, isoamyl salicylate, isoamyl cinnamate, isoamyl 10 acetate, tetrahydrofurfuryl acetate, tetrahydromugyl acetate,
decanoate, isoamyl dodecanoate, isoamylbutyrate, isoamyl tetrahydrolinallyl acetate, dodecyl acetate, trans-2-hexenyl
propionate, isoamyl hexanoate, isoamyl heptyne carbonate, acetate, trans-2-hexenyl butyrate, trans-2-hexenyl propi
isoamyl benzoate, isoamyl formate, isoamyl levulinate, onate, trans-2-hexenyl hexanoate, trans-decahydro-B-naph
isoeugenyl phenylacetate, isodihydrolavandulyl acetate, thyl acetate, trans-decahydro-3-naphthyl isobutyrate, triace
isobutyl acetate, isobutyl isovalerate, isobutyl isobutyrate, 15 tin, triethyl citrate, tricyclodecyl acetate, tricyclodecenyl
isobutyl salicylate, isobutyl cinnamate, isobutyl Valerate, acetate, tricyclodecenyl isobutyrate, tricyclodecenyl propi
isobutyl phenylacetate, isobutyl butyrate, isobutyl propi onate, neryl acetate, neryl isobutyrate, neryl butyrate, neryl
onate, isobutyl hexanoate, isobutyl benzoate, isopulegyl propionate, neryl formate, nonyl acetate, nopyl acetate,
acetate, isopropyl acetate, isopropyl isovalerate, isopropyl hydrotropic acetate, phenylethyl 2-methylbutyrate, phenyl
isobutyrate, isopropyl cinnamate, isopropyl decanoate, iso ethyl acetate, phenylethyl angelate, phenylethyl isovalerate,
propyl phenylacetate, isopropyl butyrate, isopropyl hex phenylethyl isobutyrate, phenylethyl caprylate, phenylethyl
anoate, isopropyl benzoate, isopropyl myristate, isobornyl salicylate, phenylethyl cinnamate, phenylethyl tiglate, phe
acetate, isobornyl propionate, Winter Green, ethyl 2-tert-bu nylethyl nonanoate, phenylethyl Valerate, phenylethyl piv
tylcyclohexyl carbonate, ethyl 2-ethylhexanoate, ethyl alate, phenylethyl phenylacetate, phenylethylbutyrate, phe
2-octenoate, ethyl 2-decenoate, ethyl 2-furoate, ethyl 2-hexy 25 nylethyl propionate, phenylethyl benzoate, phenylethyl
lacetoacetate, ethyl 2-benzylacetoacetate, ethyl 2-methylval formate, phenylethyl methacrylate, phenylethylmethylethyl
erate, ethyl 2-methylbutyrate, ethyl 3.5.5-trimethylhex carbinyl acetate, phenyl salicylate, fenchyl acetate, butyl
anoate, ethyl 3-hydroxybutyrate, ethyl 3-hydroxyhexanoate, acetate, butyl angelate, butyl isovalerate, butyl isobutyrate,
ethyl 3-hydroxy-3-phenylpropionate, ethyl 3-phenylglyci butyl octanoate, butyl salicylate, butyl decanoate, butyl dode
date, ethyl 3-phenylpropionate, ethyl o-methoxybenzoate, 30 canoate, butyl Valerate, butyl phenylacetate, butylbutyryllac
ethyl p-anisate, ethyl acetate, ethyl acetoacetate, ethyl isov tate, butylbutyrate, butyl propionate, butyl hexanoate, butyl
alerate, ethyl isobutyrate, ethyl octyne carbonate, ethyl ole levulinate, furfuryl acetate, prenyl acetate, prenyl angelate,
ate, ethyl caprinate, ethyl caprylate, ethyl caproate, ethyl prenyl benzoate, propyl acetate, propyl isovalerate, propyl
crotonate, ethyl geranate, ethyl safranate, ethyl salicylate, isobutyrate, propyl octanoate, propyl cinnamate, propyl
ethyl cyclogeraniate, ethyl cinnamate, ethyl Valerate, ethyl 35 trans-2, cis-4-decadienoate, propyl phenylacetate, propyl
phenylacetate, ethyl butyrate, ethyl propionate, ethyl hep butyrate, propyl propionate, propyl hexanoate, propyl hep
tanoate, ethyl heptyne carbonate, ethyl pelargonate, ethyl tanoate, propylbenzoate, propyl formate, hexyl 2-methylbu
benzoate, ethyl formate, ethyl myristate, ethyl methyl tyrate, hexyl acetate, hexyl isovalerate, hexyl isobutyrate,
p-tolylglycidate, ethyl methyl phenylglycidate, ethyl laurate, hexyl octanoate, hexyl salicylate, hexyltiglate, hexyl pheny
ethyl lactate, ethyl linallylacetate, ethyl levulinate, ethylene 40 lacetate, hexylbutyrate, hexyl propionate, hexyl hexanoate,
dodecanedioate, ethylene brassylate, eugenyl phenylacetate, hexyl benzoate, hexyl formate, veticol acetate, Vetiveryl
octyl acetate, octyl isovalerate, octyl isobutyrate, octyl acetate, heptyl acetate, heptyloctanoate, heptylbutyrate, hep
octanoate, octyl butyrate, octyl heptanoate, octyl formate, tylhexanoate, heliotropyl acetate, benzyl 2-methylbutyrate,
ocimenyl acetate, caryophyllen acetate, caryophyllen for benzyl acetate, benzyl isovalerate, benzyl isobutyrate, benzyl
mate, calyxol, carvyl acetate, guaiac acetate, cuminyl acetate, 45 caprylate, benzyl salicy alte, benzyl cinnamate, benzyltiglate,
geranyl acetate, geranyl isovalerate, geranyl isobutylate, benzyl dodecanoate, benzyl Valerate, benzyl phenylacetate,
geranyltiglate, geranyl phenylacetate, geranylbutyrate, gera benzylbutyrate, benzylpropionate, benzylhexanoate, benzyl
nyl propionate, geranylhexanoate, geranylbenzoate, geranyl benzoate, benzyl formate, pentyl salicylate, myraldyl acetate,
formate, coniferin, Santaryl acetate, diethyl adipate, diethyl myrcenyl acetate, myrtenyl acetate, methyl 1-methyl-3-cy
succinate, diethyl sebacate, diethyl tartrate, diethyl phthalate, 50 clohexenecarboxylate, methyl 2-nonenoate, methyl 2-fu
diethyl malonate, cyclohexyl acetate, cyclohexylisovalerate, roate, methyl 2-methylbutyrate, methyl 3-nonenoate, methyl
cyclohexylethyl acetate, cyclohexyl crotonate, cyclohexyl 9-undecenoate, methyl o-methoxybenzoate, methyl acetate,
butyrate, cis-3-hexenyl 2-methylbutyrate, cis-3-hexenyl methylatrarate, methylanisate, methyl angelate, methylisov
acetate, cis-3-hexenyl angelate, cis-3-hexenyl isovalerate, alerate, methyl isobutyrate, methyl isohexanoate, methyl
cis-3-hexenyl isobutyrate, cis-3-hexenyl caproate, cis-3-hex 55 octanoate, methyl octyne carbonate, methyl oleate, methyl
enyl salicylate, cis-3-hexenyl tiglate, cis-3-hexenyl Valerate, caprinate, methyl caprylate, methyl caproate, methyl geran
cis-3-hexenyl phenylacetate, cis-3-hexenyl butyrate, cis-3- ate, methyl salicylate, methyl cyclooctyl carbonate, methyl
hexenyl propionate, cis-3-hexenyl benzoate, cis-3-hexenyl cyclogeranate, methylcyclopentylideneacetate, methyldihy
formate, cis-3-hexenyl lactate, citryl acetate, citronellyl drojasmonate, methyl jasmonate, methyl cinnamate, methyl
acetate, citronellyl isovalerate, citronellyl isobutyrate, cit 60 decanoate, methyl decyne carbonate, methyl tetradecanoate,
ronellyl tiglate, citronellyl phenylacetate, citronellyl buty methyl dodecanoate, methyltrans-2-hexenoate, methyltrans
late, citronellyl propionate, citronellylhexanoate, citronellyl 3-hexenoate, methyl nonanoate, methyl hydroxyhexanoate,
formate, dihydrocarvyl acetate, dihydrocuminyl acetate, methyl Valerate, methyl phenylacetate, methyl phenylglyci
dihydroterpinyl acetate, dihydromyrcenyl acetate, dimethyl date, methylbutyrate, methyl heptanoate, methyl heptyne
Succinate, dimethylphenylethylcarbinyl acetate, dimethyl 65 carbonate, methyl pelargonate, methyl benzoate, methyl
phthalate, dimethylbenzylcarbinyl acetate, dimethylbenzyl myristate, methyl laurate, methyl lactate, lavandulyl acetate,
carbinyl isobutyrate, dimethylbenzylcarbinyl butyrate, dim linallyl acetate, linallyl isovalerate, linallyl isobutyrate, linallyl
 US 9,358,191 B2
25 26
octanoate, linallyl cinnamate, linallyl butyrate, linallyl propi date, ethyl 3-phenylpropionate, ethyl o-methoxybenzoate,
onate, linallyl hexanoate, linallyl benzoate, linallyl formate, ethyl p-anisate, ethyl acetate, ethyl acetoacetate, ethyl isov
rosamusk, rosephenone, rhodinyl acetate, rhodinyl isobu alerate, ethyl isobutyrate, ethyl octyne carbonate, ethyl ole
tyrate, rhodinyl phenylacetate, rhodinyl butyrate, rhodinyl ate, ethyl caprinate, ethyl caprylate, ethyl caproate, ethyl
propionate, rhodinyl formate, 1,3-dimethyl-3-butenyl isobu crotonate, ethyl geranate, ethyl safranate, ethyl salicylate,
tyrate, 1-acetoxy-2-sec-butyl-1-vinylcyclohexane, 1-cyclo ethyl cyclogeraniate, ethyl cinnamate, ethyl Valerate, ethyl
hex-1-ene isopropylacetate, 2,4-dimethyl-3-cyclohexylm phenylacetate, ethyl butyrate, ethyl propionate, ethyl hep
ethyl acetate, 2.4-hexadienyl isobutyrate, 2-methyl-2- tanoate, ethyl heptyne carbonate, ethyl pelargonate, ethyl
methylpentyl Valerate, 2-methylbutyl acetate, 2-methylbutyl benzoate, ethyl formate, ethyl myristate, ethyl methyl
isovalerate, 3-octyl acetate, 3-phenylpropyl isovalerate, 10 p-tolylglycidate, ethyl methyl phenylglycidate, ethyl laurate,
3-phenylpropyl isobutyrate, 3-phenylpropyl propionate, ethyl lactate, ethyl linallylacetate, ethyl levulinate, ethylene
3-methylpentyl angelate, 4-methylbenzyl acetate, 5-methyl dodecanedioate, ethylene brassylate, eugenyl phenylacetate,
3-butyltetrahydropyran-4-yl acetate, 6,10-dimethyl-5.9-un octyl acetate, octyl isovalerate, octyl isobutyrate, octyl
decatrien-2-yl acetate, 9-decen-1-yl propionate, E.G. diac octanoate, octyl butyrate, octyl heptanoate, octyl formate,
etate, E.G. monobutyl ether acetate, L-carvyl propionate, 15 ocimenyl acetate, caryophyllen acetate, caryophyllen for
L-perillyl acetate, L-bornyl propionate, L-menthyl isovaler mate, carvyl acetate, guaiac acetate, cuminyl acetate, geranyl
ate, L-menthyl phenylacetate, P.G. dibutyrate, P.G. dipropi acetate, geranyl isovalerate, geranyl isobutylate, geranyl
onate, p-cresyl caprylate, p-cresyl salicylate, C.-amylcin tiglate, geranyl phenylacetate, geranylbutyrate, geranyl pro
namyl acetate, acetylvanillin, anisyl propionate, anisyl pionate, geranyl hexanoate, geranyl benzoate, geranyl for
formate, isobutyl 2-furanpropionate, isobutyl angelate, mate, coniferin, Santaryl acetate, diethyl adipate, diethyl Suc
isobutyl crotonate, ethyl acrylate, ethyl citronellyl oxalate, cinate, diethyl sebacate, diethyl tartrate, diethyl phthalate,
ethyl Stearate, ethyl tiglate, ethyl decadienoate, ethyl dehy diethyl malonate, cyclohexyl acetate, cyclohexylisovalerate,
drocyclogeranate, ethyl dodecanoate, ethyl trans-2-hex cyclohexylethyl acetate, cyclohexyl crotonate, cyclohexyl
anoate, ethyl trans-3-hexanoate, ethyl nonanoate, ethyl butyrate, cis-3-hexenyl 2-methylbutyrate, cis-3-hexenyl
palmitate, ethyl Valerate, ethyl pyruvate, eugenyl formate, 25 acetate, cis-3-hexenyl angelate, cis-3-hexenyl isovalerate,
oxyoctalin formate, nerolidyl acetate, nonanediol-1,3-diac cis-3-hexenyl isobutyrate, cis-3-hexenyl caproate, cis-3-hex
etate, phenyl glycol diacetate, pseudolinallyl acetate, butyl enyl salicylate, cis-3-hexenyl tiglate, cis-3-hexenyl Valerate,
10-undecenoate, butyl stearate, butyl formate, butyl lactate, cis-3-hexenyl phenylacetate, cis-3-hexenyl butyrate, cis-3-
furfuryl Valerate, and propyl 2-furanacrylate. Further pre hexenyl propionate, cis-3-hexenyl benzoate, cis-3-hexenyl
ferred examples include 1-ethynylcyclohexyl acetate, 30 formate, cis-3-hexenyl lactate, citryl acetate, citronellyl
1-octen-3-yl acetate, 2-ethylhexyl acetate, 2-phenoxyethyl acetate, citronellyl isovalerate, citronellyl isobutyrate, cit
isobutyrate, 2-phenoxyethyl propionate, 3.5.5-trimethyl ronellyl tiglate, citronellyl phenylacetate, citronellyl buty
hexyl acetate, 3,7-dimethyloctanyl acetate, 3-phenylpropyl late, citronellyl propionate, citronellylhexanoate, citronellyl
acetate, 9-decen-1-yl acetate, L-menthyl acetate, L-menthyl formate, dihydrocarvyl acetate, dihydrocuminyl acetate,
propionate, o-tert-butylcyclohexyl acetate, p-tert-butylcyclo 35 dihydroterpinyl acetate, dihydromyrcenyl acetate, dimethyl
hexyl acetate, p-cresyl acetate, p-cresyl isobutyrate, p-cresyl Succinate, dimethylphenylethylcarbinyl acetate, dimethyl
phenylacetate, acetylisoeugenol, acetyleugenol, anisyl phthalate, dimethylbenzylcarbinyl acetate, dimethylbenzyl
acetate, aphermate, amyl acetate, amyl caprylate, amyl carbinyl isobutyrate, dimethylbenzylcarbinyl butyrate, dim
caproate, amyl salicylate, amyl Valerate, amylbutyrate, amyl ethylbenzylcarbinyl propionate, jasmal, cinnamyl acetate,
formate, allyl 2-ethylbutyrate, allylamylglycolate, allylisov 40 cinnamyl isovalerate, cinnamyl isobutyrate, cinnamyl cin
alerate, allyl octanoate, allyl caprylate, allyl caproate, allyl namate, cinnamyl tiglate, cinnamylbutyrate, cinnamyl pro
cyclohexylacetate, allyl cyclohexyloxyacetate, allyl cyclo pionate, cinnamyl benzoate, cinnamyl formate, Styrallyl
hexylbutyrate, allyl cyclohexylpropionate, allyl cinnamate, acetate, styrallyl isobutyrate, styrallyl propionate, cedryl
allyl phenoxyacetate, allyl butyrate, allyl heptanoate, allyl acetate, cedryl formate, terpinyl acetate, terpinyl isovalerate,
benzoate, aldehyde C-16 (strawberry), aldehyde C-19 (pine 45 terpinyl isobutyrate, terpinyl butyrate, terpinyl propionate,
apple), aldehyde C-20 (raspberry), isoamyl acetate, isoamyl terpinyl formate, decahydro-3-naphthyl formate, decyl
angelate, isoamyl isovalerate, isoamyl isobutyrate, isoamyl acetate, tetrahydrofurfuryl butyrate, tetrahydrogeranyl
undecylenate, isoamyl octanoate, isoamyl salicylate, isoamyl acetate, tetrahydrofurfuryl acetate, tetrahydromugyl acetate,
cinnamate, isoamyl decanoate, isoamyl dodecanoate, tetrahydrolinallyl acetate, dodecyl acetate, trans-2-hexenyl
isoamyl butyrate, isoamyl propionate, isoamyl hexanoate, 50 acetate, trans-2-hexenyl butyrate, trans-2-hexenyl propi
isoamyl heptyne carbonate, isoamylbenzoate, isoamyl for onate, trans-2-hexenyl hexanoate, trans-decahydro-B-naph
mate, isoamyl levulinate, isoeugenyl phenylacetate, isodihy thyl acetate, trans-decahydro-3-naphthyl isobutyrate, triace
drolavandulyl acetate, isobutyl acetate, isobutyl isovalerate, tin, triethyl citrate, tricyclodecyl acetate, tricyclodecenyl
isobutyl isobutyrate, isobutyl salicylate, isobutyl cinnamate, acetate, tricyclodecenyl isobutyrate, tricyclodecenyl propi
isobutyl Valerate, isobutyl phenylacetate, isobutylbutyrate, 55 onate, neryl acetate, neryl isobutyrate, neryl butyrate, neryl
isobutyl propionate, isobutyl hexanoate, isobutylbenzoate, propionate, neryl formate, nonyl acetate, nopyl acetate,
isopulegy1 acetate, isopropyl acetate, isopropyl isovalerate, hydrotropic acetate, phenylethyl 2-methylbutyrate, phenyl
isopropyl isobutyrate, isopropyl cinnamate, isopropyl ethyl acetate, phenylethyl angelate, phenylethyl isovalerate,
decanoate, isopropyl phenylacetate, isopropylbutyrate, iso phenylethyl isobutyrate, phenylethyl caprylate, phenylethyl
propyl hexanoate, isopropyl benzoate, isopropyl myristate, 60 salicylate, phenylethyl cinnamate, phenylethyl tiglate, phe
isobornyl acetate, isobornyl propionate, ethyl 2-tert-butylcy nylethyl nonanoate, phenylethyl Valerate, phenylethyl piv
clohexyl carbonate, ethyl 2-ethylhexanoate, ethyl alate, phenylethyl phenylacetate, phenylethylbutyrate, phe
2-octenoate, ethyl 2-decenoate, ethyl 2-furoate, ethyl 2-hexy nylethyl propionate, phenylethyl benzoate, phenylethyl
lacetoacetate, ethyl 2-benzylacetoacetate, ethyl 2-methylval formate, phenylethyl methacrylate, phenylethylmethylethyl
erate, ethyl 2-methylbutyrate, ethyl 3.5.5-trimethylhex 65 carbinyl acetate, phenyl salicylate, fenchyl acetate, butyl
anoate, ethyl 3-hydroxybutyrate, ethyl 3-hydroxyhexanoate, acetate, butyl angelate, butyl isovalerate, butyl isobutyrate,
ethyl 3-hydroxy-3-phenylpropionate, ethyl 3-phenylglyci butyl octanoate, butyl salicylate, butyl decanoate, butyl dode
 US 9,358,191 B2
27 28
canoate, butyl Valerate, butyl phenylacetate, butylbutyryllac tuberose absolute, tolu balsam oil, Diptheryx odorata oil,
tate, butylbutyrate, butyl propionate, butyl hexanoate, butyl nutmeg oil, narcissus absolute, neroli bigarado oil, Verbena
levulinate, furfuryl acetate, prenyl acetate, prenyl angelate, oil, violet leaves absolute, pine oil, basil oil, parsley seed oil,
prenyl benzoate, propyl acetate, propyl isovalerate, propyl patchouli oil, Vanilla oil, Vanilla resinoid, hyssop oil, bitter
isobutyrate, propyl octanoate, propyl cinnamate, propyl almond oil, bitter fennel oil, Hinoki oil, hiba oil, pimento
trans-2, cis-4-decadienoate, propyl phenylacetate, propyl berry oil, hyacinth absolute, petit-grain oil, buchu oil, bay oil,
butyrate, propyl propionate, propyl hexanoate, propyl hep petit-grain grass oil, petit-grain Paraguay oil, petit-grainber
tanoate, propylbenzoate, propyl formate, hexyl 2-methylbu gamot oil, petit-grain mandarin, petit-grain lemon oil, Vetiver
tyrate, hexyl acetate, hexyl isovalerate, hexyl isobutyrate, oil Java, Vetiver Bourbon, pennyroyal oil, pepper oil, pepper
hexyl octanoate, hexyl salicylate, hexyltiglate, hexyl pheny 10 mint oil, Peru balsam, Peru balsam oil, bergamot oil, benzoin
lacetate, hexylbutyrate, hexyl propionate, hexyl hexanoate, oil, benzoin resinoid, bois de rose oil, ho oil, horwood oil,
hexyl benzoate, hexyl formate, veticol acetate, Vetiveryl marjoram oil, mandarin oil, mimosa absolute, mill oil, musk
acetate, heptyl acetate, heptyloctanoate, heptylbutyrate, hep tonkintincture, mace oil, merrissa oil, eucalyptus oil, lime oil,
tylhexanoate, heliotropyl acetate, benzyl 2-methylbutyrate, lavandine oil, labdanum oil, lavender oil, rouX oil, lemon oil,
benzyl acetate, benzyl isovalerate, benzyl isobutyrate, benzyl 15 lemongrass oil, rose do mai, rose Bulgar oil, rosemary oil,
caprylate, benzyl salicy alte, benzyl cinnamate, benzyltiglate, Roman chamomile oil, laurel oil, and lovage oil. These natu
benzyl dodecanoate, benzyl Valerate, benzyl phenylacetate, ral materials can be used in various forms such as essential
benzylbutyrate, benzylpropionate, benzylhexanoate, benzyl oils, resinoids, balsams, absolutes, concretes, and tinctures.
benzoate, benzyl formate, pentyl salicylate, myraldyl acetate, The following show chemical names of the trade names
myrcenyl acetate, myrtenyl acetate, methyl 1-methyl-3-cy and general names in the above materials.
clohexenecarboxylate, methyl 2-nonenoate, methyl 2-fu Dupical (Quest): 4-(tricyclo[5.2.1.02.6 decylidene-8)buta
roate, methyl 2-methylbutyrate, methyl 3-nonenoate, methyl nal.
9-undecenoate, methyl o-methoxybenzoate, methyl acetate, Jasmal; 3-pentyltetrahydropyran-4-yl acetate.
methylatrarate, methylanisate, methyl angelate, methylisov Aphermate (IFF); O.3,3-trimethylcyclohexanemethyl for
alerate, methyl isobutyrate, methyl isohexanoate, methyl 25 mate.
octanoate, methyl octyne carbonate, methyl oleate, methyl Floralozon (IFF); p-ethyl-O.C.-dimethylhydrocinnamalde
caprinate, methyl caprylate, methyl caproate, methyl geran hyde.
ate, methyl salicylate, methyl cyclooctyl carbonate, methyl Cyclogalbanate (Dragoco); allyl cyclohexyloxyacetate.
cyclogeranate, methylcyclopentylideneacetate, methyl dihy Estragole; methyl chavicol.
drojasmonate, methyl jasmonate, methyl cinnamate, methyl 30 Rhubofix (Firmenich); an isomeric mixture of spiro 1,4-
decanoate, methyl decyne carbonate, methyl tetradecanoate, methanonaphthlene-2(1H), 2'-oxirane.3.4.4a.5.8.8a,-
methyl dodecanoate, methyltrans-2-hexanoate, methyltrans hexahydro-3',7-dimethyl (1) and spiro1.4-methanonaph
3-hexenoate, methyl nonanoate, methyl hydroxyhexanoate, thalene-(2H), 2'-oxiran).3.4.4a.5.8.8a-hexahydro-3',6-
methyl Valerate, methyl phenylacetate, methyl phenylglyci dimethyl (2).
date, methylbutyrate, methyl heptanoate, methyl heptyne 35 Triplal (IFF); dimethyl tetrahydrobenzaldehyde.
carbonate, methyl pelargonate, methyl benzoate, methyl Koavone (IFF): 4-methylene-3,5,6,6-tetramethyl-2-hep
myristate, methyl laurate, methyl lactate, lavandulyl acetate, tanone.
linallyl acetate, linallyl isovalerate, linallyl isobutyrate, linallyl Limetol; 2.2,6-trimethyl-6-vinyl tetrahydropyran.
octanoate, linallyl cinnamate, linallyl butyrate, linallyl propi Ambroxan (Henkel); decahydro-3a,6,6,9a-tetramethyl
onate, linallyl hexanoate, linallyl benzoate, linallyl formate, 40 naphtho2.1-bfuran.
rosamusk, rosephenone, rhodinyl acetate, rhodinyl isobu Damascone; C-damascone, B-damascone, y-damascone,
tyrate, rhodinyl phenylacetate, rhodinyl butyrate, rhodinyl Ö-damascone.
propionate, and rhodinyl formate. Damascenone; C-damascenone, 3-damascenone, y-dama
The halogen-containing compounds to be used as fra SCCOC.
grances in the invention are not particularly limited as far as 45 Ionone; C-ionone, B-ionone, Y-ionone.
they are harogenide having aroma or pleasant odor, and Methylionone; C.-n-methylionone, B-n-methylionone, Y-n-
examples thereof include p-dichlorobenzene and bromosty methylionone, C-iso-methylionone, B-iso-methylionone,
rol. Y-iso-methylionone.
The fragrance materials of natural origin to be used as Sandal: bacdanol (IFF); 2-ethyl-4-(2,2,3-trimethyl-3-cyclo
fragrances in the invention are not particularly limited and 50 penten-1-yl)-2-buten-1-ol.
examples thereof include almond oil, anise oil, abies-far oil, Brahamanol (Dragoco); 2-methyl-4-(2,2,3-trimethyl-3-cy
amyris oil, angelica oil, ambergris tincture, amber sage, clopenten-1-yl)butanol,
ambret seed oil, ylang-ylang oil, incense oil, wintergreen oil, Madranol (Dragoco); B-2,2,3-tetramethyl-3-Cyclopentenyl
elemi oil, oak moth absolute, oak moth essence, oak moth oil, 2-butenol,
opoponax oil, orris absolute, orange oil, orange flower abso 55 Sandalore (Givaudan): 3-methyl-5-(2,2,3-trimethylcyclo
lute, cascarilla oil, castoreum resinoid, cassia china oil, cas pent-3-en-1-yl)-pentan-2-ol.
sia absolute, cassia oil, canangajava oil, chamomile oil blue, 3.3-dimethyl-5-(2,2,3-trimethylcyclopenten-1-yl)-pent-4-
chamomile oil, Calamus oil, cardamom oil, galbanum oil, en-2-ol.
caraway oil, guaiac wood oil, guaiac oil, cumin oil, clove Methyl sandeflor (TPC): 2-methyl-1-(methylbicyclo[2.2.1-
boulbon oil, clove oil, costus oil, copaibabalsam, copaiba oil, 60 hept-5-en-2-yl)-penten-3-ol,
coriander oil, cypress oil, Sandalwood oil, cystlabdanum oil, Sandeol (MS), and the like.
ceder wood oil, citronella oil, civet absolute, jasmine abso Musk: Cashmeran (IFF); 1,2,3,5,6,7-hexahydro-1,1,2,3,3-
lute, juniper berry oil, camphor oil, jonquille absolute, ginger pentamethyl-4H-inden-4-one,
oil, ginger grass oil, cinnamon Ceylon oil, Sweet fennel oil, Galaxolide (IFF); 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexam
styrax oil, spike lavender oil, spearmint oil, Sage oil, sage 65 ethyl cyclopenta-Y-2-benzopyran,
clary oil, geranium oil, geranium grass oil, geranium Bour Tonalid (PFW); 6-acetyl-1,1,2,4,4,7-hexamethyl tetrahydro
bon oil, celery oil, thyme oil, tarragon oil, tangerine oil, naphthalene,
 US 9,358,191 B2
29 30
phantolid; 5-acetyl-1,1,2,3,3,6-hexamethyl indan, tary goods such as diapers, pads, sanitary napkins, sheets,
versalide; 7-acetyl-1,1,4,4-tetramethyl-6-ethyl-1,2,3,4-tet towels, and wet tissues; household cleaning products, foot
rahydro-naphthalene, wear cupboard spray, sheets in shoes, raw garbage spray, air
exaltolide; oxacyclohexadecan-2-one, cleaner and air conditioner, deodorizer, filters for air blower
exaltone, cyclopentadecanone, and air discharger, deodorants for refrigerator, deodorants for
oxalide; 10-oxahexadecanolide, cloths, deodorant for drawers, closets, and ambry, room or car
12-oxahexadecanolide, ethylenebrassylate, deodorants, toilet deodorants, deodorants for textile products,
celestolide (IFF): 4-acetyl-6-tert-butyl-1,1-dimethylindan, cloths (underwear and Socks), car sheets, deodorant fibers,
Traseolide (Quest); 5-aceytl-3-isopropyl-1,1,2,6-tetramethyl deodorants for factories and industrial wastes, and other vari
ous deodorants.
indan, 10
In the case that the deodorant composition of the invention
ethylenedodecanedioate, 5-cyclohexadecen-1-one, and the is incorporated in the above products or goods, the amount is
like. not unconditionally prescribed depending on the kind, apply
Iso-E-Super (IFF): 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6, ing environment, application, and use method of the products
7-tetramethyl-naphthalene. or goods but it is preferable to incorporate it usually in an
Timberol (Dragoco): 1-(2.2,6-trimethylcyclohexan-1-yl)- 15
amount of 0.001 to 100% by weight based on the products or
hexan-3-ol. goods.
Irone; C-irone, B-irone, Y-irone. At deodorization of malodor using the deodorant compo
C.-Dynascone (Firmenich): 1-(5,5-dimethylcyclohexen-1- sition of the invention, a known method can be applied. For
yl)-4-penten-1-one. example, when a solid matter, gel matter, or liquid matter of
Furthermore, in addition to the above flavors and fra the deodorant composition of the invention is applied by a
grances, use can be made of flavors and fragrances described method of directly spraying, sprinkling, wiping, immersing,
in “Nippon niokeru Shokuhin Koryo Kagoubutsu no Siyou or placing the composition to the site or place where a mal
Jittai Chosa” (2000" Kosei Kagaku Kenkyu Hokokusho, odor component is present or the site or place where possible
Nihon Koryo Kogyokai, published on March, 2001), “Gosei generation of a malodor component may be predicted, it is
koryo-Kgaku to Shohin Chisiki' (published on Mar. 6, 25 possible to eliminate the malodor or prevent the generation
1996, written by Motoichi Indoh, The Chemical Daily Co., thereof. Moreover, the deodorant composition of the inven
Ltd.), “Perfume and Flavor Chemicals (Aroma Chemicals) 1, tion may be applied by a spraying method.
2” (Steffen Arctender (1969)). The present invention provides the deodorant composition
These flavors and fragrances may be used solely or as exhibiting an excellent deodorizing effect on various malodor
mixtures of two or more of them. 30
components. The deodorant composition of the invention is
As these substances, commercially available Substances excellent in the deodorizing effect on malodor components
Such as Sulfur compounds Such as methyl mercaptan, hydro
can be also used. Moreover, as a single substance, a synthetic gen Sulfide, and dimethylsulfide and lower fatty acids such as
Substance or Substance which purified from a natural material butyric acid and isovaleric acid among malodor components,
Such as a plant may be used. The essential oils, resinoids, and also is excellent in the deodorizing effect on amine mal
balsams, absolutes, concretes, tinctures, and the like can be 35
odor components such as ammonia which are alkaline. Fur
also prepared by known methods. thermore, the method for preparing the deodorant composi
The deodorant composition of the invention is effective for tion is relatively simple. Moreover, once the deodorant
elimination or reduction of a wide range of odors. composition is prepared, it has an advantage that the deodor
Specifically, it is effective for elimination or reduction of ant performance is maintained even after the deodorant com
various odors including odors felt in daily life. Such as bad 40 position is stored for a long time. Therefore, the composition
breath (halitosis), body odor, odor in refrigerator, odor of can be said to be a remarkably excellent deodorant composi
feces and urine of human, animals, and birds, body odor, and tion.
odor of raw garbage, and malodors in factories and industrial EXAMPLES
Wastes.
Moreover, the deodorant composition of the invention is 45
The following will describe the invention more specifically
excellent in the deodorizing effect on Sulfur compounds Such with reference to Examples but the invention is by no means
as methyl mercaptan, hydrogen Sulfide, and dimethylsulfide; limited thereto.
nitrogenous compounds Such as ammonia, urea, indole, ska
tole, and amines; and lower fatty acids such as butyric acid. Example 1
Among them, the deodorant composition of the invention is 50
particularly excellent in the deodorizing effect on sulfur com Preparation of Deodorant Composition
pounds Such as methyl mercaptan, hydrogen Sulfide, and
dimethylsulfide. A deodorant composition was obtained by adding 1 mmol
Furthermore, the deodorant composition of the invention of each polyphenol described in Table 1 to the inside of a
can be incorporated into the following products or goods to 55 stirring vessel containing 50 mL of a 0.05MNaCO solution
exhibit the deodorizing performance. Specifically, the prod (pH 11.2) and stirring the whole at 25°C. under conditions
ucts or goods include oral care products such as mouthwash, that air could freely flow and the surface of the reaction liquid
toothpaste, chewing gum, tablets, hard candy, soft candy, could thoroughly come into contact with the air or allowing it
capsules, and oral spray; articles for pets and animals includ to stand after the stirring under the same conditions. The
ing dog, cat, rabbit, hamster, and parakeet, Such as cat sand, 60 stirring time and standing time are shown in Table 1.
cat sleeping straw, and sheet; detergents such as laundry
detergents, kitchen detergents, bathroom detergents, carpet Example 2
detergents, and toilet detergents; cosmetics such as Soap,
body shampoo, hand Soap, lotion, skin toner, antiperspirant, Deodorizing Effect on Methyl Mercaptain
foot deodorant spray, and foot powder, hair care products 65
Such as shampoo, conditioner, hair rinse, hair coloring agents, Into a 50 mL vial were placed 2 mL of the deodorant
permanent-wave agents, wax, hair spray, and mousse; sani composition of Example 1 and 4 LL of a 15% aqueous solu
 US 9,358,191 B2
31
tion of methyl mercaptain (Tokyo Kasei Kogyo Co., Ltd.) and TABLE 2
the vial was capped with Parafilm, followed by stirring at 25°
C. After 10 minutes, 50 mL of the head space gas in the vial Monophenols 1 hour 2 hours 3 hours 4 hours 1 day 5 days
was passed through a gas detecting tube (manufactured by p-Counaric -8.3 -8.3 -8.3 -8.3 O.O O.O
Gastech Corporation) to measure the concentration of Sulfur 5 acid
Ferulic acid -8.3 -8.3 O.O O.O 13.3 2O.O
compounds, which remained in the gas and were malodor
components, and a deodorization rate was calculated accord
ing to the following expression. The results are shown in In any of p-coumaric acid and ferulic acid, it was suggested
Table 1. that the deodorization rate was low and the yield efficiency of
10
deodorizing effective components was extremely low.
Deodorization rate (%)=100x{1-(A/B)
In the above expression, A means the measured concentra Example 3
tion of the malodor components and B means the concentra 15
tion of the malodor components measured in the control. Preparation of Deodorant Composition
The control was prepared by adding a 0.05M NaCO,
solution (pH 11.2) instead of the addition of 2 mL of the
deodorant composition of Example 1. One mmol of chlorogenic acid was added to the inside of a
stirring vessel containing 50 mL of a 0.05MNaCO solution
The time in the table shows a period of time from the start (pH 11.2) and the whole was stirred at 25°C. for 3 hours under
of stirring for the preparation of the deodorant composition to conditions that air could freely flow and the surface of the
the end of the preparation of the deodorant composition. The reaction liquid could thoroughly come into contact with the
1 hour, 2 hours, and 3 hours mean the stirring time at the air. Then, the reaction liquid was freeze-dried to obtain 460
preparation of the deodorant composition. The deodorant 25 mg of an ocher powdered deodorant composition.
compositions after 4 hours are compositions which have been
allowed to stand after 3 hours of stirring. The same shall apply
to the following tables except Table 18. Example 4
TABLE 1. 30 Deodorizing Effect on Methyl Mercaptain
5 8
Polyphenols 1 hour 2 hours 3 hours 4 hours 1 day days days The deodorizing effect of the deodorant composition of
Pyrocatechol 78.3 1OO.O 1OOO 1OOO 100.O 1OOO 10O.O Example 3 was measured in the same manner as in Example
Chlorogenic 1OOO 1OO.O 1OOO 100.0 100.0 100.O 86.7 2 except that a solution obtained by dissolving 20 mg of the
acid 35 deodorant composition of Example 3 in 2 mL of water was
(+)-Catechin 2SO 66.7 83.3 91.7 1 OOO 10O.O 63.3
Quercetin 1OOO 1OO.O 1OOO 1OOO 100.O 85.0 - used instead of 2 mL of the deodorant composition of
Gallic acid 1OOO 1OO.O 1OOO 1OOO 100.O 1OOO 10O.O Example 1. As a result, the deodorization rate was found to be
100%.
In the table, the numerals mean deodorization rates (%) and — means that the case is not
measured (the same shall apply hereinafter), 40
Comparative Example 3
Comparative Example 1
Preparation of Deodorant Composition
45
Preparation of Deodorant Composition Using A deodorant composition was obtained by adding 1 mmol
Monophenol of chlorogenic acid to the inside of a stirring vessel containing
50 mL of a 0.05M NaCO, solution (pH 11.2), from which
Adeodorant composition was obtained in the same manner dissolved oxygen had been removed by ultrasonification
as in Example 1 except that each monophenol described in 50 under vacuum with a vacuum pump, and stirring the whole at
Table 2 was used instead of the polyphenol described in Table 25°C. under a nitrogen gas atmosphere or allowing it to stand
1. after the stirring under the same conditions. The stirring time
and standing time are shown in Table 3. The deodorant com
position was yellow.
Comparative Example 2 55
Comparative Example 4
Deodorizing Effect of Deodorant Composition Using
Monophenol on Methyl Mercaptain Deodorizing Effect on Methyl Mercaptain
60
The deodorizing effect of the deodorant composition of The deodorizing effect of the deodorant composition of
Comparative Example 1 was measured in the same manner as Comparative Example 3 was measured in the same manner as
in Example 2 except that 2 mL of each deodorant composition in Example 2 except that 2 mL of the deodorant composition
described in Comparative Example 1 was used instead of 2 described in Comparative Example 3 was used instead of 2
mL of the deodorant composition of Example 1, and the 65 mL of the deodorant composition of Example 1, and the
deodorization rate was calculated. The results are shown in deodorization rate was calculated. The results are shown in
Table 2. Table 3.
 US 9,358,191 B2
34
TABLE 3 Example 6
3 7
1 hour 2 hours hours hours 24 hours
Deodorizing Effect on Methyl Mercaptain

Deodorant composition of 16.7 8.3 8.3 8.3 8.3 The deodorizing effect of the deodorant composition of
Comparative Example 3 Example 5 was measured in the same manner as in Example
2 except that 2 mL of the deodorant composition described in
10
Example 5 was used instead of 2 mL of the deodorant com
In the case that the deodorant composition was prepared position of Example 1, and the deodorization rate was calcu
without Supplying oxygen molecules, it was suggested that lated. The results are shown in Table 5.
TABLE 5
1 2 3 4 1
hour hours hours hours day 3 days 7 days 15 days 19 days 27 days
1OOO 1OOO 10O.O 100.O 1OOO 100.0 1OOO 100.0 1OOO 100.0
66.7 1OOO 10O.O 100.O 1OOO 100.0 1OO.O 73.3 66.7 53.3
SO.O - 53.3 68.3 - 81.7 85.0 SO.O SO.O
66.7 53.3 71.7 86.7 1OOO SO.O 8.3 8.3
1OOO 1OOO 10O.O 100.O 1OOO 100.0 1OOO 100.0 1OOO 100.0
83.3 76.7 76.7 81.7 40.O
1OOO 1OOO 10O.O 100.O 1OOO 100.0 1OOO 100.0 1OOO 100.0
1OOO 1OOO 10O.O 100.O 1OOO 100.0 1OOO 100.0 1OOO 100.0
1OOO 1OOO 10O.O 100.O 1OOO 100.0 1OOO 100.0 1OOO 100.0

In the table, A means pyrocatechol, B means chlorogenic acid, C means protocatechuic acid, D means
(+)-catechin, Emeans quercetin, Fmeans aesculetin, Gmeans gallic acid, Hmeans hydroquinone, and Imeans
tannic acid.

the deodorization rates in any reaction times were extremely Comparative Example 5
low and the yield efficiency of a deodorizing effective com 30
ponent was extremely low. Preparation of Deodorant Composition Using
Monophenol
Example 5
35 Adeodorant composition was obtained in the same manner
Preparation of Deodorant Composition as in Example 5 except that 1 mmol of each monophenol
described in Table 6 was used instead of 1 mmol of the
Adeodorant composition was obtained by adding 1 mmol polyphenol described in Table 4.
of each polyphenol described in Table 4 and 1 mmol of
40
glycine to the inside of a reaction vessel containing 50 mL of
a 0.05M NaCO, solution (pH 11.2) and stirring it at 25°C. The color tones of the resulting deodorant compositions
under a condition that it can thoroughly come into contact (results on third day) are as shown in Table 6.
with the air or allowing it to stand after the stirring under the
same conditions. The stirring time and standing time are TABLE 6
45
shown in Table 5.
Color tone of deodorant composition
The color tones of the resulting deodorant compositions Monophenols (reaction liquid)
(results on third day) are as shown in Table 4.
50 p-Counaric acid None
TABLE 4 Ferulic acid Pale yellow

Color tone of deodorant composition

Polyphenols (reaction liquid)
55
Chlorogenic acid Green
Comparative Example 6
(+)-Catechin Red
Protocatechuic acid Red Deodorizing Effect of Deodorant Composition Using
Pyrocatechol Pale pink Monophenol on Methyl Mercaptain
60
Aesculetin Brown
Hydroquinone Brown The deodorizing effect of the deodorant composition of
Quercetin Red Comparative Example 5 was measured in the same manner as
Gallic acid Deep green in Example 2 except that 2 mL of each deodorant composition
Tannic acid Ocher 65 described in Comparative Example 5 was used instead of 2
mL of the deodorant composition of Example 1, and the
deodorization rate was calculated.
 US 9,358,191 B2
The results are shown in Table 7.
TABLE 7
3 4 1 3 7 15 19 27
1 hour 2 hours hours hours day days days days days days
p- 33.3 33.3 O.O. O.O. O.O. O.O. O.O. O.O. O.O. O.O
Coumaric
acid
Ferulic O.O 8.3 8.3 8.3 O.O O.O O.O O.O O.O O.O
acid

Example 7 TABLE 8-continued

Preparation of Deodorant Composition 15 Amino acid Color tone pH Material odor
Arg Dark green 9.8 Slight odor
Adeodorant composition was obtained in the same manner His Dark green 9.3 No odor
as in Example 5 except that 1 mmol of chlorogenic acid and Ser Reddish brown 9.2 Almost no odor
1 1 of h idd ibed in Table 8 d Thr Reddish brown 9.2 Slight odor
immol of eacnamino acid described in lable 8 were used. 2O Met Dark green 9.2 Odor
The color tones of the resulting deodorant compositions Cys-Cys Dark green 9.1 Slight odor
are as shown in Table 8. Also, the pH of each reaction liquid Phe Dark green 9.3 Odor
and evaluation on the odor derived from each deodorizing Tyr Dark green Almost no odor
ial d ibed Trp Dark brown Odor
material Were described. Pro Dark brown Odor
Glu-Na Dark green Almost no odor
TABLE 8 25 Asp-Na Dark green Almost no odor
In the table, the color, pH, and odor show those of the reaction liquid after 3 days from the
Amino acid Color tone pH Material odor start of the reaction for the preparation of each deodorant composition,
Gly Dark green 9.3 Slight odor
Ala Dark green 9.4 Slight odor
Wall Dark green 9.6 Slight odor 30 Example 8
Leu Blackish green 9.4 Slight odor
Ile Dark green 9.4 Slight odor Deodorizing Effect on Methyl Mercaptain
Glu Dark green 9.0 Slight odor
Gln
ASn Dark green
Dark green 92
9.1 Slight odor
Slight odor The deodorization rate of each deodorant composition of
Asp Dark green 8.7 Slight odor as Example 7 was measured in the same manner as in Example
Lys Dark green 9.7 Bean odor 2 except that 2 mL of each deodorant composition of Example
7 was used. The results are shown in Table 9.
TABLE 9

Amino 10 30
acid minutes minutes 1 hour 2 hours 3 hours 24 hours 7 days 132 days
Gly 56.7 56.7 1OO.O OO.O OO.O OO.O OO.O 33.3
Ala 98.3 1OOO 1OO.O OO.O OO.O OO.O OO.O 2SO
Wall 1OOO 1OOO 1OO.O OO.O OO.O OO.O OO.O O
Leu 1OOO 1OOO 1OO.O OO.O OO.O OO.O OO.O O
Ile 98.3 1OOO 1OO.O OO.O OO.O OO.O OO.O O
Glu 97.5 98.3 1OO.O OO.O OO.O OO.O OO.O SO.O
Gln 46.7 SO.O 66.7 83.3 91.7 OO.O OO.O O
ASn 417 66.7 73.3 90.0 OO.O OO.O OO.O 8.3
Asp 16.7 16.7 36.7 6S.O 68.3 68.3 75.0 2SO
Lys 1OOO 1OOO 1OO.O OO.O OO.O OO.O OO.O SO.O
Arg 1OOO 1OOO 1OO.O OO.O OO.O OO.O OO.O 33.3
His 68.3 8S.O 91.7 OO.O OO.O OO.O OO.O 33.3
Ser 65.7 81.7 91.7 OO.O OO.O OO.O OO.O 8.3
Thr 6SO 81.7 91.7 OO.O OO.O OO.O OO.O O
Met 450 78.3 91.7 91.7 OO.O OO.O OO.O 28.3
Cys- 95.0 98.3 1OO.O OO.O OO.O OO.O OO.O 91.7
Cys
Phe 75.0 8S.O 1OO.O OO.O OO.O OO.O OO.O 36.7
Tyr 6SO 56.7 78.3 86.7 96.7 OO.O OO.O 53.3
Trp 53.3 36.7 75.O 91.7 OO.O OO.O OO.O 33.3
Pro 1OOO 1OOO 1OO.O OO.O OO.O OO.O OO.O O
Glu-Na. 83.3 83.3 90.0 91.7 66.7 O
Asp- 98.3 98.3 OO.O OO.O 66.7 O
Na
 US 9,358,191 B2
37
Example 9 TABLE 10-continued
1 hour 3 hours 24 hours 4 days 36 days
Preparation of Deodorant Composition Grape seed 1OO.O 1OOO 1OO.O 1OOO 1OOO
extract
One mmol of chlorogenic acid and 1 mmol of glycine were Coffee raw bean extract; polyphenol content 45% by weight
placed in a reaction vessel and 50 mL of a 0.05M NaCO, Green tea extract; polyphenol content 30% by weight
solution (pH 11.2) was added thereto. The whole was stirred Apple extract; polyphenol content 60% by weight
at 25°C. for 3 hours under a condition that it could come into Rosemary extract; polyphenol content 50% by weight
10 Peppermint extract; polyphenol content 32% by weight
contact with air. Then, the product was freeze-dried to obtain Spearmint extract; polyphenol content 33% by weight
535 mg of a dark green powdered deodorant composition. Grape pericarp extract; polyphenol content 90% by weight
Grape seed extract; polyphenol content 40% by weight

Example 10 The polyphenol contents were calculated in terms of chlo

15 rogenic acid in the cases of the coffee raw bean extract, apple
Deodorizing Effect on Methyl Mercaptain extract, rosemary extract, peppermint extract, and spearmint
extract. In the case of the green tea extract, the content was
calculated in terms of catechin. In the cases of the grape
The deodorization rate was measured in the same manner pericarp extract and grape seed extract, the contents were
as in Example 2 except that 28 mg of the powdered deodorant adopted following manufacturers indications.
composition of Example 9 was used instead of the deodorant Preparation of Coffee Raw Bean Extract:
composition of Example 1 and 2 mL of distilled water was Coffee raw beans were extracted under stirring at 90 to 95°
further added. C. for 2 hours with adding 10 weight equivalents of water.
As a result, the deodorization rate was found to be 100%. After filtration, the filtrate was concentrated by removing the
25 solvent under reduced pressure to obtain a coffee raw bean
extract (yield based on coffee raw beans: about 16.8%).
Example 11 Preparation of Green Tea Extract:
Green tea was extracted under stirring at 90 to 95°C. for 2
hours with adding 20 weight equivalents of water. After fil
Preparation of Deodorant Composition 30 tration, the filtrate was concentrated by removing the solvent
under reduced pressure to obtain a green tea extract (yield
In a reaction vessel was placed 50 mL of a 0.05MNaCO based on green tea: about 25.7%).
Solution (pH 11.2), and then each plant extract (an extract Apple extract: manufactured by Nikka Whisky K.K.
containing a polyphenol and an amino acid) described in Preparation of Rosemary Extract:
Table 10 was added thereto so that the polyphenol content 35 Dry rosemary was extracted under stirring at 45 to 50° C.
becomes 1 mmol. The whole was stirred at 25° C. under a for 2 hours with adding 20 weight equivalents of 30% hydrous
condition that it could come into contact with air or stirred ethanol. After filtration, the filtrate was concentrated by
under the same conditions and then allowed to stand to obtain removing the solvent under reduced pressure to obtain a
a deodorant composition. The stirring time and the standing rosemary extract (yield based on dry rosemary: about 15.4%).
time are shown in Table 10. 40 Preparation of Peppermint Extract:
Dry peppermint after oil components had been removed by
Example 12 steam distillation treatment was extracted under stirring at 90
to 95°C. for 2 hours with adding 10 weight equivalents of
water. After filtration, the filtrate was concentrated by remov
Deodorizing Effect on Methyl Mercaptain 45 ing the solvent under reduced pressure to obtain a peppermint
extract (yield based on dry peppermint: about 17.8%).
The deodorization rate was measured in the same manner Preparation of Spearmint Extract:
as in Example 2 using each deodorant composition of Dry spearmint after oil components had been removed by
Example 11 was used. The results are shown in Table 10. steam distillation treatment was extracted under stirring at 90
50 to 95°C. for 2 hours with adding 10 weight equivalents of
TABLE 10 water. After filtration, the filtrate was concentrated by remov
ing the solvent under reduced pressure to obtain a spearmint
1 hour 3 hours 24 hours 4 days 36 days extract (yield based on dry spearmint: about 15.8%).
Coffee raw 1OO.O 1OOO 1OOO 1OOO 1OOO
Grape pericarp extract: manufactured by Polyphenolics
bean extract
55 Grape seed extract: manufactured by Polyphenolics
Green tea 1OO.O 1OOO 1OOO 1OOO 1OOO
extract Example 13
Apple 1OO.O 1OOO 1OOO 1OOO 1OOO
extract
Rosemary 1OO.O 1OOO 1OOO 1OOO 1OOO
Dried pericarp of apples (a variety of Fuji) was pulverized
extract
60 into powder by a mill to obtain an apple powder. To 80 g of the
Peppermint 1OO.O 1OOO 1OOO 1OOO 1OOO powder was added 800 mL of a 50 mM sodium carbonate
extract
Spearmint 1OO.O 1OOO 1OOO 1OOO 1OOO
solution, and the whole was vigorously stirred at 40°C. for 3
extract
hours in a state that it could come into contact with air (the pH
Grape 1OO.O 1OOO 1OOO 1OOO 1OOO of the reaction solution was 7.6). After the reaction liquid was
pericarp 65 filtered, the filtrate was dried under reduced pressure to obtain
extract 81.6 g of a deodorant composition powder (102% based on
dried pericarp).
 US 9,358,191 B2
39 40
Example 14 TABLE 11-continued
Deodorant composition Color tone of solution Deodorization rate
To 80 g of dry tea leaves of green tea was added 1600 mL
of a 50 mM sodium carbonate solution, and the whole was Example 17 red 100%
vigorously stirred at 30°C. for 1 hour in a state that it could (derived from grape
pericarp)
come into contact with air (the pH of the reaction solution was
8.7). After the reaction liquid was filtered, the filtrate was
freeze-dried under reduced pressure to obtain 51.8 g of a
deodorant composition powder (64% based on dried tea 10 Example 19 and Comparative Example 7
leaves).
Example 15 In a reaction vessel, 1 mmol of gallic acid, 1 mmol of
Sodium glutamate, and each of NaCO aqueous solutions
A hundred grams of dried leaves and stems of perilla after 15
having various concentrations described in Table 12 or each
oil parts had been removed by steam distillation treatment of NaOH adueous Solutions having various concentrations
were pulverized by a mill. Thereto was added 20 weight described in Table 13 were mixed. The whole was stirred at
equivalents of a 50 mM sodium carbonate solution (pH 11.2). room temperature under a condition that air could come into
and the whole was vigorously stirred and extracted at 25°C. contact therewith or stirred under the same conditions and
for 3 hours in a state that it could come into contact with air then allowed to stand to prepare a deodorant composition.
(the pH of the reaction solution was 8.5). After the reaction The stirring time and the standing time were shown in Tables
liquid was filtered, the filtrate was freeze-dried to obtain 25.8 12 and 13.
g of a deodorant composition powder (25.8% based on dried Using each of the above deodorant composition, the
perilla). deodorization rate was measured in the same manner in
25 Example 2. In the control corresponding to B in the expres
Example 16 sion of Example 2, each of alkaline solvents having various
concentrations described in Tables 12 and 13 was added
To 100 g of coffee raw beans was added 10 weight equiva instead of the deodorant composition.
lents of a 50 mM sodium carbonate solution (pH 11.2), and The results are shown in Tables 12 and 13.
the whole was vigorously stirred at 15° C. for 3 hours in a state 30
that it could come into contact with air (the pH of the reaction TABLE 12
solution was 7.8). After the reaction liquid was filtered, the
filtrate was freeze-dried to obtain 17.3 g of a deodorant com pH of pH of
position powder (17.3% based on coffee raw beans). reaction alkaline
35
Na2CO liquid solution
Example 17 aqueous 3 1 3 5 2O 28 during before
Solution hours day days days days days reaction reaction
To 100 g of dried pericarp of grapes was added 10 weight 1M
SOO mM
1OOO
1OOO
100.0
100.0
100.0
1 OOO
1 OOO
100.0
100.0
100.0
100.0
1OOO
10.7
10.6
11.6
11.5
equivalents of a 50 mM sodium carbonate solution (pH 11.2). 100 mM 1OOO 100.0 1 OOO 100.0 100.0 100.0 9.9 11.4
and the whole was vigorously stirred at 15° C. for 3 hours in 40 50 mM 1OOO 100.0 1 OOO 100.0 100.0 100.0 9.O 11.4
a state that it could come into contact with air (the pH of the 25 mM 1OOO 100.0 100.0 100.0 85.0 S6.7 8.0 11.4
reaction solution was 7.3). After the reaction liquid was fil 10 mM
1 mM
O
O
O
O
2S.O
O
2SO
O
36.7
O
16.7
O
6.0
4-5
11.1
10.9
tered, the filtrate was freeze-dried to obtain 15.4 g of a deodor
ant composition powder (15.4% based on dried pericarp of
grapes). 45
TABLE 13
Example 18
pH of pH of
The deodorization rate was measured in the same manner reaction alkaline
NaOH liquid solution
as in Example 2 except that a solution obtained by dissolving 50 aqueous 3 3 5 14 21 during before
40 mg of each deodorant composition powder obtained in Solution hours 1 day days days days days reaction reaction
Examples 13 to 17 in 2 mL of water was used instead of the 1M 1OOO 100.0 1 OOO 100.0 100.0 100.0 12.9 13.5
deodorant composition of Example 1. The results are shown SOO mM 1OOO 100.0 1 OOO 100.0 100.0 100.0 12.8 13.4
in Table 11. 100 mM 1OOO 100.0 1 OOO 100.0 100.0 1OOO 10.1 12.8
50 mM 1OOO 100.0 1 OOO 100.0 100.0 100.0 8.0 12.5
55 25 mM
TABLE 11 1OOO 100.0 100.0 10O.O SO.O SO.O 7.0 12.2
10 mM O O O O O O 4.6 11.8
Deodorant composition Color tone of solution Deodorization rate 1 mM O O O O O O 4.6 10.7

Example 13 red 100%

(derived from apple
pericarp) 60 The pH of the reaction liquid was measured after 3 days
Example 14 red 100% from the start of the reaction (stirring).
(derived from green tea) In any alkaline solvents, the deodorant compositions pre
Example 15 red 100% pared at pH of the reaction liquid of 6.5 or higher during the
(derived from perilla)
Example 16 green 100% reaction exhibited an excellent deodorizing effect but the
(derived from coffee raw 65 deodorant compositions prepared at pH of the reaction liquid
bean) of 6.0 or lower during the reaction exhibited a low deodor
ization rate.
 US 9,358,191 B2
41 42
Example 20 and Comparative Example 8 mL of a 0.05M sodium carbonate solution (pH 11.2), and the
whole was stirred at each temperature described in Table 15
Preparation of Deodorant Compositions with continuously supplying air and the concentration of
dissolved oxygen in the reaction liquid was measured with
To a reaction vessel in which 50 mL of the following 5 time. Moreover, in the case of 100 mL of a 0.05M sodium
alkaline solvent, alkaline buffer solvent, or neutral buffer carbonate solution (pH 11.2) without adding gallic acid and
Solvent were added 1 mmol of chlorogenic acid and 1 mmol Sodium glutamate, the concentration of dissolved oxygen in
of glycine, and the whole was stirred at 25°C. or stirred at 25° the reaction liquid was measured with time in the same man
C. and then allowed to stand, whereby a deodorant composi 10
ner. The results are shown in Table 15.
tion was obtained. The stirring time and the standing time are The concentration of dissolved oxygen in the reaction liq
shown in Table 14. uid was measured using a dissolved oxygen measuring appa
(A) 0.05M NaHCO, solution (pH 8.3) ratus (manufactured by TOA Electric K.K., oxygen electrode:
(B) 0.05M NaHCO/NaCO, solution (pH 9.1) OE-2102) at 23.4°C. and 42.4° C. and using a Ponal Kit for
(C) 0.05M NaHCO/NaCO, solution (pH 10.0) 15 measuring dissolved oxygen (manufactured by Dojindo
(D) 0.05M NaCO, solution (pH 11.2) Laboratories) at 60° C. and 80°C., and in boiling water.
(E) 0.05M NaHPO/NaH2PO solution (pH 6.5) With regard to the case after 3 hours of stirring at each
temperature, as in Example 2, a deodorizing activity test was
Example 21 conducted. The results are shown in Table 16.
Deodorizing Effect on Methyl Mercaptain TABLE 1.5
Using each deodorant composition of Example 20, the Solvent alone (+)Gallic acid + Glu-Na
deodorizing effect of Example 20 was measured in the same stirring time stirring time
manner in Example 2. In the control corresponding to B in the 25 Reaction O 10 3 O 10 3
expression of Example 2, each of (A) to (E) solvents was temperature min min hir min min hir
added instead of the deodorant composition. 23.4° C. 3.7 7.8 7.8 O O O
The results are shown in Table 14. 42.4° C. 3.2 5.2 5.2 O O O
60.0° C. 2.5 2.0 2.0 O O O
30 80.0° C.
TABLE 1.4 O.S 1.5 1.5 O O O
Boiling O.S O.S O.S O O O
pH of pH of temperature
reaction alkaline
liquid solution
3 4 6 8 24 during before Amount of Dissolved Oxygen in the Reaction Liquid (mg/L)
hours hours hours hours hours reaction reaction In the case of the solvent alone, at the measured tempera
35
(A) 16.7 2SO 75.O 83.3 83.3 6.5 8.3 tures except boiling temperature, the amount of dissolved
(B) 33.3 71.7 1OO.O 1OOO 1OO.O 9.0 9.1 oxygen reached equilibrium within 10 minutes of stirring but
(C) SO.O 81.7 1OO.O 1OOO 1OO.O 1O.O 1O.O the amount decreased as the temperature was elevated. In the
(D) 91.4 1OOO 1OO.O 1OOO 1OO.O 9.3 11.2
(E) O.O O.O O.O O.O O.O 6.5 6.5 case that gallic acid and Sodium glutamate were added and
40 reacted, the amount of dissolved oxygen in the reaction liquid
In the tables, (A), (B), (C), (D), and (E) represent deodorant compositions prepared using a was 0 at any time. From these results, it is revealed that gallic
0.05MNaHCO, solution (pH 8.3), a 0.05M NaHCO/Na2CO, solution (pH 9.1), a 0.05M
NaHCO/Na2CO3 solution (pH 10.0), a 0.05M Na2CO3 solution (pH 11.2), and a 0.05M
Na2HPO/NaH2PO4 solution (pH 6.5), respectively,
acid and Sodium glutamate rapidly consume dissolved oxy
gen when they are dissolved in an alkaline solvent and Sub
In the case that chlorogenic acid and glycine were added to sequently continue to consume it.
the buffer solution of pH 6.5 and reacted, the pH of the 45
reaction liquid during the reaction was maintained at pH 6.5 TABLE 16
and no deodorizing effect was observed at any reaction times.
On the other hand, even when the pH of the reaction liquid Reaction Deodorization rate at
during the reaction was 6.5, a deodorizing effect was temperature 3 hours stirring (%)
observed and a deodorant composition was formed in the case 50 23.4° C. 100
that the solvent before the reaction was alkaline and the pH 42.4° C.
60.0° C.
100
100
became 6.5 as a result of the reaction with the addition of 80.0° C. 100
chlorogenic acid and glycine. Boiling 25
From Examples 19, 20, and 21, it is suggested that the temperature
formation of the deodorant composition does not depend on 55
the kind and concentration of the alkaline solvent and the pH As a result of the deodorizing activity test at 3 hours of
of the alkaline solvent before the reaction but it is an impor stirring with adding gallic acid and sodium glutamate, the
tant factor to make the pH of the reaction liquid during the deodorization rate was 100% in all cases at the reaction tem
reaction 6.5 or higher by using the alkaline solvent with the
pH of 7.0 or higher. 60 perature other than boiling temperature but the deodorization
rate was 25% in the case that the reaction was carried out at
Example 22 boiling temperature.
From the above results, it is suggested that the yield effi
Influence of Oxygen Supplying Amount ciency of the deodorizing effective component considerably
65 decreases at the amount of dissolved oxygen in the case that
One mmol of gallic acid and 1 mmol of sodium glutamate the reaction was carried out at boiling temperature (0.5
were added to the inside of the reaction vessel containing 100 mg/L).
 US 9,358,191 B2
43 44
Example 23 of 10,000, a strong deodorizing activity was observed on the
filtrate but no deodorizing effect was observed on the filtra
Measurement of Molecular Weight tion residual liquid. Based on the results, it is suggested that
the molecular weight of the active component in the deodor
One mmol of tannic acid and 1 mmol of sodium glutamate 5 ant composition should be 10,000 or less.
were added to the inside of a stirring vessel containing 50 mL
of a 0.05M sodium carbonate solution (pH 11.2). The whole Example 24
was stirred at 25°C. for 3 hours under a condition that it could
come into contact with air and then allowed to stand to obtain
10
Reaction Temperature and Reaction Time at
a deodorant composition. Preparation of Deodorant Composition
One mmol of gallic acid and 1 mmol of glycine were added
to the inside of a stirring vessel containing 50 mL of a 0.05M One mmol of gallic acid and 1 mmol of sodium glutamate
sodium carbonate solution (pH 11.2). The whole was stirred were added to the inside of a reaction vessel containing 50 mL
at 25°C. for 3 hours under a condition that it could come into of a 0.05M sodium carbonate solution (pH 11.2). The whole
15
contact with air and then allowed to stand to obtain a deodor was continued to stir at each temperature for each period of
ant composition. time described in Table 18 under a condition that it could
Two grams of each resulting deodorant composition was come into contact with air. Two milliliters of the reaction
subjected to centrifugal membrane filtration at 3,000 rpm for liquid was sampled with time and the deodorizing activity
1 hour. In the centrifugal membrane filtration, two kinds of was measured according to Example 2.
filtration membranes were used, which were a filtration mem The results are shown in Table 18
brane whose separating molecular weight was 3,000 and a
filtration membrane whose separating molecular weight was TABLE 1.8
10,000. In the filtration of separating molecular weight of
3,000, substances having a molecular weight of 3,000 or less Stirring
25 time Reaction temperature
were separated as the filtrate and Substances having a molecu
lar weight of more than 3,000 were separated as the filtration (Hr) 5° C. 25° C. 40° C. 50° C. 60° C. 70° C. 80° C.
residue. In the filtration of separating molecular weight of O 100 100 100 1OO 100 1OO 100
10,000, substances having a molecular weight of 10,000 or 1 100 100 100 1OO 100 1OO 100
less were separated as the filtrate and Substances having a 30 2 100 100 100 1OO 100 1OO 100
molecular weight of more than 10,000 were separated as the 3 100 100 100 1OO 100 1OO 100
filtration residue. 4 100 100 100 1OO 100 1OO 55
5 100 100 100 1OO 100 1OO O
After the centrifugal membrane filtration, a deodorizing 6 100 100 100 1OO 100 1OO O
activity test was conducted on the filtrate and the filtration 7 100 100 100 1OO 100 55 O
residue as in Example 2 to measure the deodorization rate. In 35
8 100 8O 75 75 25 O O
this connection, the liquid obtained by dissolving the filtra 9
24
100
70
70
<10
63
O<
63
O<
O<
O
tion residue in 2 g of water was referred to as a filtration
residual liquid. The numerals in the table mean deodorization rates.
The results are shown in Table 17. Moreover, — means no measurement,
Filtration membrane for molecular weight 3,000 separation:
Centricon (registered trademark) YM-3 (manufactured by 40 With regard to the relation between the reaction (stifling)
Millipore, for cutting molecular weight 3,000) temperature and the deodorizing activity, it is revealed that
Filtration membrane for molecular weight 10,000 separation: the deodorizing activity decreases as the reaction temperature
Centricon (registered trademark) YM-10 (manufactured by is elevated. Particularly at a high temperature of 70° C. or
Millipore, for cutting molecular weight 10,000) higher, the deodorizing activity decreased when the stirring
45 time was a long time. Therefore, the reaction temperature at
TABLE 17 which the yield efficiency of the deodorizing effective com
ponent is high is in the range of up to 60° C. The reaction
Filtration for Filtration for (stirring) time is preferably about 7 hours. Moreover, at the
cutting molecular cutting molecular reaction temperature of 80° C., the time up to 3 hours is
weight 3,000 weight 10,000 50 suitable for the formation of the deodorizing effective com
(Tannic acid x Glu-Na) ponent, wherein the deodorization rate of 100% is main
tained.
Filtration residual liquid 100 O
Filtrate 100 1OO
(Gallic acid x Gly) Example 25
55
Filtration residual liquid 100 O Influence of Metal Ion
Filtrate 100 1OO

The numerals in the table mean deodorization rates (%). In a reaction vessel, 1 mmol of chlorogenic acid, 1 mmol of
sodium glutamate, 50 mL of a 50 mM NaCO aqueous
The same results were obtained in the cases of both of the 60 solution, and 0.25 mmol of each of various metal salts
deodorant composition derived from tannic acid and sodium described in Table 19 were mixed. The whole was stirred at
glutamate and the deodorant composition derived from gallic room temperature under a condition that it could come into
acid and glycine. Namely, in the case of the centrifugal filtra contact with air or stirred under the same conditions and then
tion apparatus for cutting molecular weight of 3,000, a strong allowed to stand to prepare a deodorant composition. The
deodorizing activity was observed on both of the filtrate and 65 stirring time and the standing time were shown in Table 19.
the filtration residual liquid. However, in the case of the Moreover, “no addition' in the table means a deodorant com
centrifugal filtration apparatus for cutting molecular weight position prepared without adding any metal salt.
 US 9,358,191 B2
45 46
Using the above deodorant composition, the deodorization of a 0.05M sodium carbonate solution (pH 11.2). The whole
rate was measured in the same manner in Example 2. The was stirred at 25°C. for 3 hours under a condition that it could
results are shown in Table 19. come into contact with air. Then, the reaction liquid was
freeze-dried to obtain a deodorant composition powder. The
TABLE 19 powder was dissolved in water to obtain a deodorant compo
Deodori- Deodori sition solution.
Various zation zation A deodorant composition Solution having a deodorant
metal rate after 3 rate after 48
salts hours (%) days (%) pH Color tone composition concentration of 10.00 mg/mL was prepared and
10 tests for the deodorizing effect of the deodorant composition
No 1OO.O 4S.O 7.8 Dark green -> black green Solution on methyl mercaptan, ammonia, and isovaleric acid
addition
CaCl2 96.7 83.3 8.0 Green -> black green was conducted.
MgCl2 1OO.O 1OOO 8.1 Dark green -> dark green Deodorization Test on Methyl Mercaptain
CuCl2 1OO.O 1OOO 8.5 Dark green -> dark brown
MnSO 1OO.O 1OOO 8.7 Dark bluegreen -> dark
bluegreen 15 The test was conducted in the same manner as in Example
2.
ZnCl2 1OO.O 1OOO 8.5 Dark green -> dark green
Deodorization Test on Ammonia
The pH in the table was a result observed after 3 days from the start of the reaction (stirring).
The color tone showed results observed after 3 days and 48 days from the start of the reaction
(stirring),
Into a 50 mL vial was placed 2 mL of the deodorant com
position, and 5 uL of a 2.8% ammonia water was added
In the case that a metal ion was added, durability of the thereto. Then, the vial was capped with Parafilm, followed by
deodorizing activity was observed as compared with the con stirring at 25°C. for 10 minutes. Thereafter, 50 mL of the head
trol (no addition of metal salt). Moreover, the deodorant com space gas in the vial was passed through a gas detecting tube
positions to which MgCl, ZnCl2 or MnSO was added also (manufactured by Gastech Corporation) to measure the con
exhibited an excellent effect on the stability of the color tone. 25 centration of the malodor component which remained in the
Example 26 gas, and a deodorization rate was calculated according to the
expression shown in Example 2.
Influence of Concentration of Metal Ion
Deodorization Test on Isovaleric Acid
In a reaction vessel, 1 mmol of chlorogenic acid, 1 mmol of 30
Into a 50 mL vial was placed 2 mL of the deodorant com
sodium glutamate, 45 mL of a 50 mM NaCO aqueous position, and 40 uL of isovaleric acid was added thereto.
Solution, and 5 mL of each of various concentrations of an Then, the vial was capped with Parafilm, followed by stirring
MgCl, aqueous solution described in Table 20 were mixed. at 25°C. for 10 minutes. Thereafter, 50 mL of the head space
The whole was stirred at room temperature under a condition gas in the vial was passed through a gas detecting tube (manu
that it could come into contact with air or stirred under the
same conditions and then allowed to stand to prepare a 35 factured by Gastech Corporation) to measure the concentra
deodorant composition. The stirring time and the standing tion of the malodor component which remained in the gas,
time were shown in Table 20. Moreover, “no addition' in the and a deodorization rate was calculated according to the
table means a deodorant composition prepared without add expression shown in Example 2.
ing the MgCl2 aqueous solution. As a result, the deodorization rates for methyl mercaptan,
Using the above deodorant composition, the deodorization 40 ammonia, and isovaleric acid were found to be 100(%),
rate was measured in the same manner in Example 2. The 80(%), and 100(%), respectively.
results are shown in Table 20.
From this fact, it was revealed that the deodorant compo
TABLE 20 sition of the invention provides an excellent deodorizing
45 effect on methyl mercaptan, ammonia, and isovaleric acid
Concentration of MgCl2
aqueous solution 3 hours 13 days 47 days pH
and is a multipurpose deodorant composition capable of also
providing an excellent deodorizing effect on malodor com
No addition 1OOO 83.3 46.7 7.9 ponents exhibiting alkalinity.
50 mM 80.0 1OO.O 1OOO 7.4
5 mM 1OOO 1OO.O 1OOO 8.9
50
O.5 mM
O.05 mM
1OOO
1OOO
1OO.O
1OO.O
66.7
55.0
9.0
9.0
Example 28
O.OOS mM 1OOO 1OO.O 6.3.3 9.1
O.OOOS mM 1OOO 1OO.O 6.3.3 9.1
Deodorizing Effect on Methyl Mercaptain and
Concentration of Deodorant Composition
The pH was measured after 3 days from the start of the 55
reaction (stirring).
Even in the case that a 0.0005 mM MgClaqueous solution One mmol of gallic acid and 1 mmol of sodium glutamate
was added, the deodorization rates after 13 days and 47 days were added to the inside of a reaction vessel containing 50 mL
were higher than the case of no addition and hence durability of a 0.05M sodium carbonate solution (pH 11.2). The whole
of the activity was enhanced by the addition of MgCl, 60
was stirred at 25°C. for 3 hours under a condition that it could
Example 27 come into contact with air. Then, the reaction liquid was
freeze-dried to obtain a deodorant composition powder. The
Deodorizing Effect on Each Malodor and powder was dissolved in water to obtain a deodorant compo
Concentration of Deodorant Composition sition solution having each concentration shown in Table 21.
65 The test for the deodorizing effect of the deodorant com
One mmol of gallic acid and 1 mmol of sodium glutamate position Solution having each concentration on methyl mer
were added to the inside of a reaction vessel containing 50 mL captain was conducted.
 US 9,358,191 B2
47 48
Deodorization Test on Methyl Mercaptain Example 30
The test was conducted in the same manner as in Example
2. Urine Odor Suppressing Effect
The results are shown in Table 21.
Twenty mmol of gallic acid, 20 mmol of sodium glutamate,
TABLE 21 and 1,000 mL of a 50M sodium carbonate solution were
mixed and the whole was stirred at room temperature for 3
Deodorization rate (% hours under a condition that it could come into contact with
Concentration of deodorant Malodor component 10
air. Thereafter, the reaction liquid was dried and concentrated
composition (mg/ml) Methyl mercaptain by freeze drying. The dried product was grinded to obtain 9.6
1O.OO 100
g of a deodorant composition powder.
S.OO 100 About /2 (10 g) of the urine absorber of a paper diaper
2.50 100 (Lifely Urine Pad Supper: manufactured by Unicharm Cor
1.25
O.63
100
100 15 poration) was placed in a 500 mL paper cup and 0.5g of the
O.31 100 above deodorant composition powder was added onto top.
O.15 63 Then, 100 mL of human urine was added and the cup was
capped with a double structure of Saran-Wrap (trade name)
and aluminum foil. Sensory evaluation for odor after standing
With regard to the deodorizing effect on methyl mercaptan, at 34°C. for 3 hours, 6 hours, or 24 hours was conducted by
the deodorization rate was 100% even when the concentration
of the deodorant composition was 0.31 mg/mL and thus an four panelists. The evaluation was conducted on the follow
excellent deodorizing effect was exhibited. Furthermore, the ing items in terms of Score evaluation and evaluation results
deodorizing effect was observed even at the concentration of were shown as an average of scores of four panelists.
0.15 mg/mL. The case that the deodorant composition powder was not
25 added was adopted as a blank. The results are shown in FIGS.
1 and 2.
Example 29 Evaluation Items and Evaluation Scores
Deodorizing effect on urine odor;
Deodorizing Effect on Isovaleric Acid and 30
1: nearly no urine odor is felt
Concentration of Deodorant Composition 2: slight urine odor is felt
: a little bit urine odor is felt
: a little urine odor is felt
One mmol of gallic acid and 1 mmol of sodium glutamate : considerable urine odor is felt
were added to the inside of a reaction vessel containing 50 mL : strong urine odor is felt
of a 0.05M sodium carbonate solution (pH 11.2). The whole 35
Overall odor intensity (odor intensity over the whole system
was stirred at 25°C. for 3 hours under a condition that it could
come into contact with air. Then, the reaction liquid was including urine odor, odor of the urine absorber of the
freeze-dried to obtain a deodorant composition powder. The paper diaper itself, and the like);
powder was dissolved in water to obtain a deodorant compo : no odor is felt
sition Solution having each concentration shown in Table 22. 40 : odor is slightly felt with effort
: odor is felt without effort
The test for the deodorizing effect of the deodorant com : odor is evidently felt
position solution having each concentration onisovaleric acid
was conducted. : odor is strongly felt
: odor is impatiently strongly felt
Deodorization Test on Isovaleric Acid 45
Into a 50 mL vial was placed 2 mL of the deodorant com Example 31
position, and 40 uL of isovaleric acid was added thereto.
Then, the vial was capped with Parafilm, followed by stirring Urine Odor Suppressing Effect
at 25°C. for 10 minutes. Thereafter, 50 mL of the head space
gas in the vial was passed through a gas detecting tube (manu 50 Twenty mmol of gallic acid and 1,000 mL of a 50M sodium
factured by Gastech Corporation) to measure the concentra carbonate aqueous solution were mixed and the whole was
tion of the malodor component which remained in the gas, stirred at room temperature for 3 hours under a condition that
and a deodorization rate was calculated according to the it could come into contact with air. Thereafter, the reaction
expression shown in Example 2. liquid was dried and concentrated by freeze drying. The dried
The results are shown in Table 22. 55
product was ground to obtain 5.8 g of a deodorant composi
tion powder.
TABLE 22 The application method to the paper diaper and sensory
Deodorization rate (% evaluation were conducted in the same manner as in Example
60
30. The results are shown in FIGS. 1 and 2.
Concentration of deodorant Malodor component From FIGS. 1 and 2, the paper diaper to which the deodor
composition (mg/ml) ISOValeric acid
ant composition of the invention had been added exhibited
1O.OO
S.OO
100
100
that the score obtained after 24 hours of standing were about
the same as the score obtained after 3 hours and thus the
2.50 100
1.25 90 65 generation of urine odor was remarkably suppressed and also
the odor intensity over the whole system was weak, so that a
strong deodorizing effect was attained.
 US 9,358,191 B2
49 50
Example 32 powder. The components of the following formulation were
mixed and a tooth paste was obtained in a usual manner.
Mouthwash
TABLE 25
One mmol of gallic acid and 1 mmol of sodium glutamate 5
Composition of tooth paste
were added to the inside of a reaction vessel containing 50 mL
of a 0.05MNaCO solution (pH 11.2). The whole was stirred Component % by weight
at 25°C. for 3 hours under a condition that it could come into
Dicalcium phosphate 1O.OO
contact with air. Then, the reaction liquid was freeze-dried 10
Sodium laurylsulfate 2.OO
and allowed to stand to obtain a deodorant composition pow Carboxymethyl cellulose sodium
Saccharin Sodium
OSO
O.O2
der. The components of the following formulation were Sodium benzoate 1O.OO
mixed and a mouthwash was obtained in a usual manner. Deodorant composition of the invention O.10
Glycerin Balance
TABLE 23 15 Total 1OOOO
Composition of mouthwash
Component % by weight Deodorization Test
Ethyl alcohol 10.00 In order to evaluate the effect of eliminating bad breath in
Polyoxyethylene hydrogenated castor oil 2.00 the case that the deodorant composition was used in the tooth
Saccharin sodium O.O2 paste, the following method was adopted.
Glycerin 10.00 After mouths were well rinsed with water, test subjects
Sodium benzoate O.OS
Deodorant composition of the invention 2.00 kept 10 mL of a 50 ppm solution of sodium methyl mercaptain
Purified water Balance in their mouths for 1 minute and then spat out the solution.
25 Immediately, a breath was trapped into a 5 L plastic bag.
Total 100.00 Subsequently, they cleaned their teeth for 2 minutes with the
tooth paste prepared in the above. Immediately, a breath was
Deodorization Test trapped into a 5 L plastic bag.
A garlic extract solution was prepared from 4 g of garlic The breath after tooth cleaning in the plastic bag was sub
and 1 L of water. Ten milliliters of the resulting garlic extract 30 jected to sensory evaluation by four panelists based on the
solution was injected into a 50 mL bottle, and 1 mL of the following evaluation standard in comparison with the breath
above mouthwash was further added thereto, followed by before tooth cleaning in the plastic bag. The results are shown
mixing. Subsequently, the whole was shaken at 34° C. for 3 in Table 26 as an average of scores of the four panelists.
minutes. Sensory evaluation was conducted on the resulting Evaluation Standard Scores
mixture by five expert panelists according to the following 35 1 point) no methyl mercaptain is felt
evaluation standard. The results were shown as an average of 2 points) methyl mercaptain is slightly felt
scores of five panelists. 3 points) methyl mercaptain is felt to Some extent
The results are shown in Table 24. 4 points) methyl mercaptain is evidently slightly felt
Evaluation Standard Scores 40 5 points) methyl mercaptain is strongly felt
1 point) no garlic odor is felt 6 points) methyl mercaptain is intensely felt
2 points) garlic odor is slightly felt
3 points) garlic odor is felt to Some extent TABLE 26
4 points) garlic odor is evidently slightly felt Evaluation
5 points) garlic odor is strongly felt 45 average score
6 points) garlic odor is intensely felt
Toothpaste containing 1.O
TABLE 24 inventive product
Control (1) 6.O
Evaluation Control (2) 4.5
50
average score In the table, the control (1) shows the case of the breath from the subjects who did not clean
their teeth and the control (2) shows the case that a tooth paste prepared without adding the
Mouthwash containing 1.O inventive product is used,
inventive product
Control 6.O

In the table, the control shows the result at the time when a mouthwash prepared without 55
Example 34
adding the inventive product was used,
Tablet
Example 33
In a reaction vessel was placed 50 mL of a 0.05M NaCO
Tooth Paste 60 Solution (pH 11.2), and a peppermint extract was added
thereto so that the polyphenol content became 1 mmol in
One mmol of tannic acid and 1 mmol of glycine were added terms of chlorogenic acid. The whole was stirred at 25°C. for
to the inside of a reaction vessel containing 50 mL of a 0.05M 3 hours under a condition that it could come into contact with
NaCO solution (pH 11.2). The whole was stirred at 25°C. air. Then, the reaction liquid was freeze-dried to obtain a
for 3 hours under a condition that it could come into contact 65 deodorant composition powder. The components of the fol
with air. Then, the reaction liquid was concentrated to dryness lowing formulation were mixed and a tablet was obtained in
under reduced pressure to obtain a deodorant composition a usual manner.
 US 9,358,191 B2
51 52
TABLE 27 Deodorization Test
In order to evaluate the effect of eliminating bad breath in
Composition of tablet the case that a chewing gum containing the above deodorant
Component % by weight composition was used, the following method was adopted.
After mouths were well rinsed with water, test subjects
Starch 97.5 kept 10 mL of a 50 ppm solution of sodium methyl mercaptain
Sucrose fatty acid ester O.S in their mouths for 1 minute and then spat out the solution.
Deodorant composition of the invention 2.0 Immediately, a breath was trapped into a 5 L plastic bag.
Total 1OOOO Subsequently, they continued to chew the chewing gum
10 prepared in the above for 10 minutes. Immediately, a breath
was trapped into a 5 L plastic bag.
Deodorization Test The breath after continued chewing of the gum trapped in
In order to evaluate the effect of eliminating bad breath in the plastic bag was Subjected to sensory evaluation by four
the case that the deodorant composition was incorporated into panelists based on the same evaluation standard as in the case
the tablet, the following method was adopted. 15 of the tooth paste in comparison with the breath before chew
After mouths were well rinsed with water, test subjects ing of the gum trapped in the plastic bag. The results are
kept 10 mL of a 50ppm solution of sodium methyl mercaptain shown in Table 30 as an average of scores of the four panelists.
in their mouths for 1 minute and then spat out the solution.
Immediately, a breath was trapped into a 5 L plastic bag. TABLE 30
Subsequently, they ate the tablet prepared in the above for 10
minutes. Immediately, a breath was trapped into a 5 L plastic Evaluation
bag. average score
The breath after tablet eating trapped in the plastic bag was Inventive product 1.3
Subjected to sensory evaluation by four panelists based on the Control (1) 6.0
same evaluation standard as in the case of the tooth paste in 25
Control (2) 4.3
comparison with the breath before tablet eating trapped in the In the table, the control (1) shows the case of the breath from the subjects who did not chew
plastic bag. The results are shown in Table 28 as an average of the gum and the control (2) shows the case that a chewing gum prepared without adding the
inventive product is chewed.
scores of the four panelists.
TABLE 28 30 Example 36
Evaluation
average score
Antiperspirant
Tablet containing 1.3 One mmol of chlorogenic acid and 1 mmol of Sodium
inventive composition glutamate were added to the inside of a reaction vessel con
Control (1) 6.O 35
Control (2) 4.8 taining 50 mL of a 0.05M NaCO, solution (pH 11.2). The
whole was stirred at 25°C. for 3 hours under a condition that
In the table, the control (1) shows the case of the breath from the subjects who did not eat the
tablet and the control (2) shows the case that a tablet prepared without adding the inventive
it could come into contact with air. Then, the reaction liquid
product is used. was freeze-dried to obtain a deodorant composition powder.
40 A predetermined amount of the components of the following
Example 35 formulation was heated to obtain a homogeneous highly vis
cous solution. Then, the solution was cast into a mold and
Chewing Gum cooled to obtain an antiperspirant stick containing the
deodorant composition.
In a reaction vessel was placed 50 mL of a 0.05MNaCO, 45
TABLE 31
Solution (pH 11.2), and a grape pericarp extract was added
thereto so that the polyphenol content became 1 mmol in Composition of antiperSpirant Stick
terms of catechin. The whole was stirred at 25°C. for 3 hours
under a condition that it could come into contact with air. Component % by weight
Then, the reaction liquid was freeze-dried to obtain a deodor 50
PEG-7 glyceryl cocoate 2.0
ant composition powder. The components of the following Hydrogenated oil S.O
formulation were mixed and a chewing gum was obtained in Mirystyl myristate 1S.O
a usual manner. Cyclomethicone 33.0
Stearyl alcohol 2O.O
Stearyl isononenoate 3.0
TABLE 29 55 aluminum chlorohydrate 2O.O
Deodorant composition of the invention 2.0
Composition of chewing gun
Total 1OO.O
Component % by weight
Gum base 21.0 60 Deodorization Test
Sugar powder 63.9
Corn starch 12.5 To 5 mL of a 0.25% butyric acid aqueous solution was
Acidifying agent O6 added 2 g of shavings of the above antiperspirant stick, and
Deodorant composition of the invention 2.0 the whole was mixed at room temperature. After 10 minutes,
Total 1OOO
the mixture was subjected to sensory evaluation by five expert
65 panelists based on the following evaluation standard. The
results are shown as an average of scores of the five panelists
in Table 32.
 US 9,358,191 B2
53 54
For comparison, using an antiperspirant stick containing TABLE 34
no deodorant composition, sensory evaluation was conducted
in the same manner as above. Evaluation
average score
Evaluation Standard Score
1 point) nobutyric acid odor is felt 5 Powdery detergent containing inventive product 1.2
2 points) butyric acid odor is slightly felt Control 4.2
3 points) butyric acid odor is felt to some extent
4 points) butyric acid odor is evidently slightly felt
5 points) butyric acid odor is strongly felt Example 38
6 points) butyric acid odor is intensely felt 10
Shampoo
TABLE 32
Evaluation One mmol of gallic acid and 1 mmol of sodium glutamate
average score 15
were added to the inside of a reaction vessel containing 50 mL
Antiperspirant containing inventive product 1.6
of a 0.05MNaCO, solution (pH 11.2). The whole was stirred
at 25°C. for 3 hours under a condition that it could come into
Control 6.0
contact with air. Then, the reaction liquid was freeze-dried to
In the table, the control shows the case of the antiperspirant containing no inventive product, obtain a deodorant composition powder. The components of
the following formulation were mixed and a shampoo was
obtained in a usual manner.
Example 37
TABLE 35
Powdery Detergent
Composition of shampoo
25
One mmol of gallic acid was added to the inside of a Component % by weight
reaction vessel containing 50 mL of a 0.05M NaCO solu
tion (pH 11.2). The whole was stirred at 25°C. for 3 hours Sodium laurylsulfate 40.OO
under a condition that it could come into contact with air. Sodium cocoamphoacetate 1O.OO
Cocoamide DEA 2.OO
Then, the reaction liquid was freeze-dried to obtain a deodor 30
Butylene glycol 2.OO
ant composition powder. The components of the following Citric acid O.35
formulation were mixed and a powdery detergent was Sodium chloride O.10
obtained in a usual manner. Methylparaben O.20
Propylparaben O.10
EDTA tetrasodium O.10
TABLE 33 Green floral fragrance O.SO
35 Deodorant composition of the invention 2.OO
Composition of powdery detergent Purified water Balance

Component % by weight Total 100.00

Sodium laurylsulfate, Sodium stearylsulfate 1S.O

Sodium carbonate
Sodium metasilicate
1S.O
13.0
40 Deodorization Test
Sodium citrate 1S.O
In order to evaluate the effect of eliminating permanent
Carboxymethyl cellulose 2.0 wave odor using the shampoo containing the deodorant com
Sodium sulfate 38.0 position, the following method was adopted.
Deodorant composition of the invention 2.0 A tress of false hair for test (1.8 g) was immersed in 50 mL
Total 1OOO
45 of a permanent wave first Solution (obtained by adjusting a
6% thioglycolic acid aqueous solution to pH 9.3 with ammo
nia water) for 30 minutes. After the attached first solution was
Deodorization Test wiped off with paper, the tress was washed with 100 mL of
One of socks worn for a whole day was immersed in water water and then immersed in 50 mL of a permanent wave
containing the powdery detergent (0.5% by weight) contain 50 second solution (5% potassium bromate aqueous solution)
ing the deodorant composition prepared in the above, and it for 20 minutes. After the attached second solution was wiped
was washed at room temperature for 5 minutes and rinsed. off with paper, the tress was immersed in 1000 mL of water
The remaining one of the Socks was immersed in water con containing the shampoo (1% by weight) prepared in the above
taining a powdery detergent (0.5% by weight) prepared with for 5 minutes. After the attached water containing the sham
out adding the deodorant composition of the invention, and it 55 poo was wiped off with paper, the tress was washed with 100
was washed at room temperature for 5 minutes at the same mL of water and then the attached water was wiped off with
time and rinsed (control). The Socks were subjected to sen paper. The tress was subjected to sensory evaluation by four
sory evaluation by five expert panelists according to the fol panelists according to the following evaluation standard. The
lowing evaluation standard. The results are shown as an aver results are shown as an average of scores of the four panelists
age of scores of the five panelists in Table 34. 60 in Table 36.
Evaluation Standard Score Evaluation Standard Score
1 point) no typical stuffy odor is felt 1 point) no permanent wave odor is felt
2 points) typical stuffy odor is slightly felt 2 points) permanent wave odor is slightly felt
3 points) typical stuffy odor is felt to some extent 3 points) permanent wave odor is felt to some extent
4 points) typical stuffy odor is evidently slightly felt 65 4 points) permanent wave odor is evidently slightly felt
5 points) typical stuffy odor is strongly felt 5 points) permanent wave odor is strongly felt
6 points) typical stuffy odor is intensely felt 6 points) permanent wave odor is intensely felt
 US 9,358,191 B2
55 56
TABLE 36 Deodorization Test
Into a 100 mL vial were placed 10 mL of a physiological
Evaluation malodor and 50 mg of the above deodorant composition, and
average score then the vial was capped with Parafilm, followed by shaking
Shampoo containing inventive product 1.5 at 25°C. for 10 minutes. Then, sensory evaluation was con
Control 5.3 ducted by seven panelists according to the following evalua
In the table, the control shows the case thatashampoo prepared without adding the inventive
tion standard. The results are shown as an average of scores of
product is used. the seven panelists in Table 38.
As comparison, an analyte of the malodor alone was
10 shaken and Subjected to sensory evaluation.
Example 39 Sensory Evaluation Standard
1 point) no malodor is felt
Deodorizing Effect on Human Feces and Urine 2 points) malodor is slightly felt
3 points) malodor is felt to some extent
One mmol of chlorogenic acid was added to the inside of a 4 points) malodor is evidently slightly felt
15 5 points) malodor is strongly felt
reaction vessel containing 50 mL of a 0.05M sodium carbon 6 points) malodor is intensely felt
ate solution (pH 11.2). The whole was stirred at 25°C. for 3
hours under a condition that it could come into contact with
TABLE 38
air. Then, the reaction liquid was freeze-dried to obtain a
deodorant composition powder. Evaluation
Deodorization Test average score
Into a 100 mL vial were placed 10 mL of urine of an adult Case that inventive product is added 1.4
male and 20 mg of the above deodorant composition, and then Malodor alone 6.O
the vial was capped with Parafilm (manufactured by Ameri
can National Can), followed by shaking at 25° C. for 10 25
minutes. Moreover, into a 100 mL vial were placed 10 mL of Example 41
urine of an adult male, 20 mg of the above deodorant com
position, and 10 LIL of lavender fragrance (manufactured by Deodorizing Effect on Feces and Urine of Livestock
Takasago International Corporation), and then the vial was
capped with Parafilm, followed by shaking at 25°C. for 10 30 One mmol of chlorogenic acid and 1 mmol of Sodium
minutes. glutamate were added to the inside of a reaction vessel con
The inside of the vial was subjected to sensory evaluation taining 50 mL of a 0.05M NaCO, solution (pH 11.2). The
whole was stirred at 25°C. for 3 hours under a condition that
by seven panelists according to the following evaluation stan it could come into contact with air, and then allowed to stand
dard. The results are shown as an average of scores of the 35 to obtain a deodorant composition.
seven panelists in Table 37. Deodorization Test
As comparison, an analyte of the urine alone and an analyte Into a 100 mL vial were placed 10 mL of a liquid separated
wherein 10 uL of lavender fragrance (manufactured by from feces and urine of livestock and 1 mL of the above
Takasago International Corporation) was added to the urine deodorant composition, and then the vial was capped with
were also tested. Parafilm, followed by shaking at 25°C. for 10 minutes. Then,
40
Sensory Evaluation Standard sensory evaluation was conducted by seven panelists accord
1 point) no malodor is felt ing to the following evaluation standard. The results are
2 points) malodor is slightly felt shown as an average of scores of the seven panelists in Table
3 points) malodor is felt to some extent 39.
4 points) malodor is evidently slightly felt As control, an analyte obtained by culturing the feces and
45
5 points) malodor is strongly felt urine of livestock alone was used.
6 points) malodor is intensely felt Sensory Evaluation Standard
1 point) no feces and urine odor is felt
TABLE 37 2 points) feces and urine odor is slightly felt
3 points) feces and urine odor is felt to some extent
Evaluation 50 4 points) feces and urine odor is evidently slightly felt
average score 5 points) feces and urine odor is strongly felt
Urine + inventive product 1.3 6 points) feces and urine odor is intensely felt
Urine + inventive product + lavender fragrance 1.O
Urine alone 6.O TABLE 39
Urine + lavender fragrance 4.7 55
Evaluation
average score

Example 40 Case that inventive product is added 1.3

Separated liquid of feces and urine of livestock alone 6.0
Deodorizing Effect on Physiological Odor 60

One mmol of tannic acid and 1 mmol of sodium glutamate Example 42

were added to the inside of a reaction vessel containing 50 mL
of a 0.05MNaCO solution (pH 11.2). The whole was stirred Deodorizing Effect on Fish Odor
at 25°C. for 3 hours under a condition that it could come into 65
contact with air. Then, the reaction liquid was freeze-dried to In a reaction vessel was placed 50 mL of a 0.05M NaCO
obtain a deodorant composition powder. Solution (pH 11.2), and a green tea extract was added thereto
 US 9,358,191 B2
57 58
so that the polyphenol content became 1 mmol in terms of TABLE 41
catechin. The whole was stirred at 25°C. for 3 hours under a
condition that it could come into contact with air and then Evaluation
allowed to stand to obtain a deodorant composition. average score Comment
5 Inventive 2.4 Odor intrinsic to vegetable and the like was
Deodorization Test product observed butputrid odor characteristic to
To 5 L of water was added 5 mL of the deodorant compo raw garbage was hardly observed.
sition prepared in the above, and the whole was thoroughly Control 5.8 Intense putrid odor characteristic to raw
mixed. In the mixture, a pan after Sardine had been cooked garbage was observed.
was immersed. Under room temperature, after 10 minutes 10
had been passed, the pan was taken out and the Solution
containing the deodorant composition was washed away with Example 44
water. Then, the presence of odor on the pan Surface and the
degree thereof were evaluated in a sensory manner by five Deodorizing Effect in Toilet
expert panelists based on the following evaluation standard. 15
The results are shown as an average of scores of the five In a reaction vessel was placed 50 mL of a 0.05MNaCO,
panelists in Table 40. Solution (pH 11.2), and an apple pericarp extract was added
Evaluation Standard Score thereto so that the polyphenol content became 1 mmol in
1 point) no fish odor is felt terms of chlorogenic acid. The whole was stirred at 25°C. for
2 points) fish odor is slightly felt 3 hours under a condition that it could come into contact with
3 points) fish odor is felt to some extent air. Then, the reaction liquid was freeze-dried to obtain a
4 points) fish odor is evidently slightly felt deodorant composition powder.
Deodorization Test
5 points) fish odor is strongly felt Two grams of the inventive product was spread on the
6 points) fish odor is intensely felt 25
water sump of a toilet bowl and then feces were eliminated by
five panelists. After the elimination, the odor in the toilet was
TABLE 40 evaluated in a sensory manner according to the sensory evalu
ation standard. The results are shown in Table 42.
Evaluation
average score 30
Sensory Evaluation Standard
1 point) no excrement odor is felt
Case that inventive product is added
Control
1.4
6.0
2 points) excrement odor is slightly felt
3 points) excrement odor is felt to some extent
In the table, the control shows the result of the test without adding the deodorant composition 4 points) excrement odor is evidently slightly felt
of the invention.
35
5 points) excrement odor is strongly felt to the same degree as
in the usual case.
Example 43 TABLE 42
Evaluation
Deodorizing Effect on Raw Garbage 40 average score Comment
One mmol of tannic acid was added to the inside of a
Inventive 1.4 Excrement odor was hardly felt and
product excrement odor was remarkably suppressed
reaction vessel containing 50 mL of a 0.05M NaCO solu as compared with the usual case using no
tion (pH 11.2). The whole was stirred at 25°C. for 3 hours inventive product.
under a condition that it could come into contact with air and 45
then allowed to stand to obtain a deodorant composition.
Deodorization Test Example 45
One kilograms of so-called raw garbage composed of veg
etable garbage, fish garbage, meat garbage, and the like was Deodorizing Effect on Malodor Gas
50
placed in a plastic bucket fitted with a cap and 50 mL of an
aqueous solution obtained by ten times dilution of the deodor One mmol of gallic acid and 1 mmol of glycine were added
ant composition prepared in the above with water was to the inside of a reaction vessel containing 50 mL of a 0.05M
sprayed thereonto, followed by capping the bucket. As a NaCO solution (pH 11.2). The whole was stirred at 25°C.
control, 50 mL of water was sprayed onto 1 kg of the same raw for 3 hours under a condition that it could come into contact
garbage. After 3 days standing at room temperature, sensory 55 with air and then allowed to stand to obtain a deodorant
evaluation was conducted by five panelists according to the composition.
predetermined evaluation standard. The results are shown as Deodorization Test
an average of scores of the five panelists in Table 41. Into a 4 L odorless bag. 4L of air was included by means of
Sensory Evaluation Standard an air pump. Each malodor gas (ammonia, trimethylamine,
60 hydrogen Sulfide, or methyl mercaptan) was injected there
1 point) no raw garbage odor is felt into by an injection Syringe to regulate a gas concentration.
2 points) raw garbage odor is slightly felt The bag was set at a test apparatus of closed circulation
3 points) raw garbage odor is felt to Some extent system fitted with an air pump and the air pump was worked
at an air amount of about 1000 mL/minute. One milliliter of
4 points) raw garbage odor is evidently slightly felt 65 the above deodorant composition was supported on an absor
5 points) raw garbage odor is strongly felt bent cotton (0.2 g) and the cotton was set at the discharging
6 points) raw garbage odor is intensely felt side of the air pump. After 2 hours of working, the remaining
 US 9,358,191 B2
59 60
amount of the malodor gas in the system was measured using capsules, and oral spray; articles for pets and animals includ
a dedicated gas detecting tube (Gastech Corporation) and a ing dog, cat, rabbit, hamster, and parakeet, such as cat sand,
deodorization rate was calculated according to the following cat sleeping straw, and sheet; detergents such as laundry
expression. detergents, kitchen detergents, bathroom detergents, carpet
As a comparative example, an absorbent cotton impreg- 5 detergents, and toilet detergents; cosmetics such as Soap,
nated with 1 mL of a 20 mM aqueous solution of gallic acid body shampoo, hand Soap, lotion, skin toner, antiperspirant,
was set at the discharging side of the air pump, instead of the foot deodorant spray, and foot powder, hair care products
absorbent cotton on which the above deodorant composition Such as shampoo, conditioner, hair rinse, hair coloring agents,
was supported. Then, the test was conducted similarly and the permanent-wave agents, wax, hair spray, and mousse; sani
deodorization rate was calculated. 10 tary goods such as diapers, pads, sanitary napkins, sheets,
The results are shown in Table 43. towels, and wet tissues; household cleaning products, foot
Deodorization rate (%)=100x{1-(A/B) wear cupboard spray, sheets in shoes, raw garbage spray, air
cleaner and air conditioner, deodorizer, filters for air blower
In the above expression, A means the measured concentra and air discharger, deodorants for refrigerator, deodorants for
tion of the malodor components and B means the concentra- 15 cloths, deodorant for drawers, closets, and ambry, room or car
tion of the malodor components measured in the control. The deodorants, toilet deodorants, deodorants for textile products,
control is the case that an absorbent cotton was impregnated cloths (underwear and Socks), car sheets, deodorant fibers,
with 1 mL of water instead of 1 mL of the above deodorant deodorants for factories and industrial wastes, and other vari
composition. ous deodorants.
2O
TABLE 43 BRIEF DESCRIPTION OF DRAWINGS
Deodorization rate (%
FIG. 1 is a drawing illustrating a deodorizing effect of the
Initial Deodorant Gallic acid deodorant composition of the invention on a paper diaper.
concentration composition of the aqueous 25 FIG. 2 is a drawing illustrating a deodorizing effect of the
Malodor gas (ppm) invention Solution deodorant composition of the invention on a paper diaper, the
Ammonia 60 effect being different from the above.
Trimethylamine 130
Methyl mercaptain 100 The invention claimed is:
Hydrogen sulfide 120 30 1. A deodorant composition comprising, as an active com
ponent, a colored compound obtained by reacting a plant
The deodorant composition of the invention exhibits the extract and/or a plant body containing a polyphenol and an
deodorizing effect on various malodor components including amino acid in a solvent showing alkalinity in the coexistence
amine malodor components such as ammonia and trimethy of oxygen molecules at a reaction pH value of 6.5 or more,
lamine, Sulfur compounds Such as methyl mercaptain and 35 wherein the plan extract and/or the plant body is selected
hydrogen Sulfide, and the like. from the group consisting of coffee raw bean, green tea,
Industrial Applicability apple, rosemary, peppermint, spearmint, grape pericarp,
The deodorant composition of the invention is effective for grape seed and leaves and the stem of perilla;
elimination or reduction of a wide range of odors. Specifi the polyphenol is selected from the group consisting of
cally, it is effective for elimination or reduction of various 40 chlorogenic acid, (+)-catechin, protocatechuic acid,
odors including odors felt in daily life, such as bad breath pyrocatechol, aesculetin, hydroquinone, quercetin, gal
(halitosis), body odor, odor in refrigerator, odor of feces and lic acid and tannic acid, and
urine of human, animals, and birds, body odor, and odor of the amino acid is selected from the group consisting of
raw garbage, and malodors in factories and industrial wastes. glycine, alanine, Valine, leucine, isoleucine, glutamic
Moreover, the deodorant composition of the invention is 45 acid, glutamine, asparagine, aspartic acid, lysine, argin
excellent in the deodorizing effect on Sulfur compounds Such ine, histidine, serine, threonine, methionine, cystine,
as methyl mercaptan, hydrogen Sulfide, and dimethylsulfide; phenylalanine, tyrosine, tryptophan, proline, Sodium
nitrogenous compounds Such as ammonia, urea, indole, ska glutamate and sodium aspartate.
2. The deodorant composition according to claim 1,
tole, and amines; and lower fatty acids such as butyric acid. wherein
Among them, the deodorant composition of the invention is 50 the concentration of oxygen molecule during the
particularly excellent in the deodorizing effect on sulfur com reaction is 1 mg/L or more.
3. The deodorant composition according to claim 1,
pounds Such as methyl mercaptan, hydrogen Sulfide, and
dimethylsulfide. wherein the reacting is conducted at a temperature in the
Furthermore, the deodorant composition of the invention range of 0 to 60° C.
can be incorporated into the following products or goods to 55 4. The deodorant composition according to claim 1,
exhibit the deodorizing performance. Specifically, the prod wherein the reacting is conducted in the presence of an added
ucts or goods include oral care products such as mouthwash, metalion.
toothpaste, chewing gum, tablets, hard candy, soft candy,