US008217 132B2

(12) United States Patent (10) Patent No.: US 8,217,132 B2

Sato et al. (45) Date of Patent: Jul. 10, 2012

(54) SILICONE RUBBER COMPOSITION 5,405,896 A * 4/1995 Fujiki et al. ................... 524/265
5,418,065 A * 5/1995 Fujiki et al. ... ... 428,451
5,610,218 A * 3/1997 Funk et al. ..... ... 524/413
(75) Inventors: El St. sy (May
suka, Kumamoto (JP); Masashi
5,623,028 A * 4/1997 Fitzgerald etal
5,792,812 A * 8/1998 Fujiki et al. ........
525/474
525/105
Kudo, Kanagawa (JP) 5,824,736 A * 10/1998 Kobayashi et al. ........... 524/588
5,866,653 A * 2/1999 Matsushita et al. ........... 524/731
(73) Assignee: NOK Corporation, Tokyo (JP) 6,127.503 A * 10/2000 Fujioka et al. .................. 528, 15
6,130,272 A * 10/2000 Dopp et al. ........ 523,212
(*) Notice: Subject to any disclaimer, the term of this 6,162,854. A * 12/2000 Meguriya et al. ............. 524/437
6,284,861 B1* 9/2001 Takuman et al. ...... . 528,31
patent is extended or adjusted under 35 6,303,675 B1 * 10/2001 Kobayashi et al. ... 524/263
U.S.C. 154(b) by 57 days. 6,369,155 B1 * 4/2002 Takita ................ ... 524,588
6,890,662 B2 * 5/2005 Yaginuma et al. . ... 428.447
(21) Appl. No.: 12/308.913 7,271,215 B2* 9/2007 Ikeno et al. ........ ... 524,588
7,288,322 B2 * 10/2007 Bosshammer ..... ... 428.447
2001/0034403 A1* 10, 2001 Takuman et al. .. ... 524,588
(22) PCT Filed: Jun. 15, 2007 2002/0016412 A1 2/2002 Hirai et al. ..... 525/100
2002/0077.440 A1* 6/2002 Baba et al. ...................... 528, 10
(86). PCT No.: PCT/UP2007/062098 2003/005.5157 A1* 3/2003 Wolfer et al. ................. 524,588
2004/0235994 A1 11/2004 Okamoto et al.
S371 (c)(1),
(2), (4) Date: Dec. 29, 2008 FOREIGN PATENT DOCUMENTS
CN 1314435 A 9, 2001
(87) PCT Pub. No.: WO2008/001625 JP 63-2187.64 9, 1988
JP 05-017688 1, 1993
PCT Pub. Date: Jan. 3, 2008 JP 06-287.304 10, 1994
JP 2003-0283O2 1, 2003
(65) Prior Publication Data JP 2004-076870 3, 2004
WO WO 2008/O13319 1, 2008
US 2009/0326122 A1 Dec. 31, 2009
OTHER PUBLICATIONS
(30) Foreign Application Priority Data European Search Report from corresponding European Application
Jun. 27, 2006 (JP) ................................. 2006-176247 No. 07745353.8 dated Mar. 24, 2010, 3 pages.
(51) Int. Cl. * cited by examiner
C08G 77/20 (2006.01)
C08G 77/04 (2006.01) Primary Examiner — Robert S. Loewe
C08G 77/08 (2006.01) (74) Attorney, Agent, or Firm — Brinks Hofer Gilson &
Lione
C08G 77/24 (2006.01)
(52) U.S. Cl. ................. 528/36; 528/10; 528/24; 528/32 (57) ABSTRACT
(58) Field of Classification Search ................... 524/588 A silicone rubber composition, which comprises 100 parts by
See application file for complete search history. weight of a vinyl group-introduced methylfluoroalkylvinyl
(56) References Cited based silicone rubber obtained by copolymerization of a dim
ethylsiloxane copolymerization unit as the main component
U.S. PATENT DOCUMENTS with 5-50% by mole of a methylfluoroalkylsiloxane copoly
3,642,685 A * 2/1972 Matherly ...................... 524/785 merization unit, and 0.2-8 parts by weight of an organic
3,836,623 A * 9/1974 Matherly ...................... 264/267 peroxide. When silica is used as a filler, it is desirable to use
4,029,629 A * 6/1977 Jeram ........................... 523,203 a surfactant for silica, and water at the same time. The present
4,101,499 A * 7/1978 Herzig .......................... 524,731 silicone rubber composition can give distinguished low-tem
4,355,121 A * 10, 1982 Evans ........................... 523,213 perature characteristics and blister resistance, and thus can be
4.454.288 A 6, 1984 Lee et al. ...................... 524,588
4,529,774. A * 7/1985 Evans et al. ... 523/217 used for seal materials directed to high-pressure hydrogen gas
4,585,848 A * 4, 1986 Evans et al. ...... 528, 15 storage tanks, for example, to storage under 70 MPa, and
4,649,005 A * 3/1987 Kobayashi et al. . . . 264,101 particularly as Suitable Vulcanization-molding materials for
4,766,191 A * 8/1988 Gvozdic et al. ...... ... 528, 14 O-rings, packings, gaskets, oil seals, valves, etc. High-pres
4,785,047 A * 1 1/1988 Jensen ............. 524,714 Sure gases for storage are not limited only to hydrogen gas,
5,008,305 A * 4, 1991 Kennan et al. ... 523,212
5,057,151 A * 10/1991 Schuster et al. ... 106.2 but also to oxygen gas, nitrogen gas, helium gas, etc. likewise.
5,110,845 A * 5/1992 Gray et al. ... 523,211
5,399,602 A * 3/1995 Matsushita et al. ........... 524/267 5 Claims, No Drawings
 US 8,217,132 B2
1. 2
SILICONE RUBBER COMPOSITION Patent Literature 2: JP-A-2004-76870
Silicone rubber is also known as rubber having distin
RELATED APPLICATIONS guished low-temperature characteristics, where polydimeth
ylsiloxane having a small amount of vinyl groups as cross
The present application is a 35 U.S.C. S371 national stage 5 linkable groups, most typical silicone rubber, has a low
filing of International Patent Application No. PCT/JP2007/ temperature resistance downto about -55°C., and thus has no
062098, filed Jun. 15, 2007, to which priority is claimed under satisfactory low-temperature characteristics, whereas meth
35 U.S.C. S 120 and through which priority is claimed under ylfluoroalkylvinyl-based silicone rubber has an effective low
35 U.S.C. S 119 to Japanese Priority Patent Application No. temperature resistance down to about -70° C., but has a
10
problem of blister occurrence when subjected to abrupt pres
2006-176247, filed Jun. 27, 2006. Sure reduction.
TECHNICAL FIELD
The present applicants have so far proposed a silicone
rubber composition, which comprises: (a) diorganopolysi
loxane copolymer comprising (i) about 5 to about 40% by
The present invention relates to a silicone rubber compo mole of (CFCH2CH2)(R)SiO, and (ii) about 95 to about
sition, and more particularly to a silicone rubber composition 15
60% by mole of RSiO, as unit formulae, where R is
for Suitable use to Vulcanization-molding materials, etc. of methyl, ethyl, vinyl or phenyl group, (b) diatomaceous earth,
seal materials for high-pressure gas, particularly high-pres (c) finely powdery silica, (d) titanium oxide and carbonate or
Sure hydrogen gas. oxide of Mn., Zn, Mg, Ca or Fe, (e) graphite, (f) fluororesin,
BACKGROUND ART
(g) carbon black, and (h) an organic peroxide, which is dis
closed to have distinguished heat resistance and oil resis
tance, and to be applicable effectively to mold seal materials.
Due to recentenergy problems such as possible exhaustion Patent Literature 3: JP No. 2,049,956
petroleum resources, etc., efficient fuel cells have been now It is further disclosed therein that in the afore-mentioned
brought into the limelight. The fuel cell is a system of gener unit (i), a (CFCH2CH2)(CH)SiO unit and a (CFCHCH)
ating electricity by reaction of hydrogen with oxygen, where 25
(CHs)SiO unit can be used as preferable copolymerization
how to store hydrogen is a problem. Up to now, how to store units, and in the unit (ii), a (CF)2SiO unit can be used so, and
hydrogen under high-pressure, how to store hydrogen by the copolymer molecule chain terminals may be blocked by a
adsorption onto a metal, how to reform hydrocarbon to triorganosilyl group, etc. Such as a trimethylsilyl group, a
recover hydrogen, etc. have been proposed. Storage of hydro dimethylvinylsilyl group, a methylvinylphenylsilyl group,
gen gas under high-pressure must take a tank storage form. 30
etc. It is stated that Vulcanization-molding products of the
Now, tanks capable of withstanding a hydrogen gas storage composition can be effectively applied to various packings,
pressure of about 35 MPa are generally used, but cannot sealing materials, etc. in the field relating to machines and
satisfy a sufficient mileage when the fuel cells are to be transporting machinery, but no mention has been made
mounted on automobiles. Thus, storage under much higher therein as to application to high-pressure gas sealing materi
pressure, for example, about 70 MPa, has been now under 35
als requiring good low-temperature characteristics and blister
study. Seals are indispensable for storage of hydrogen gas in resistance.
a tank, and now metallic seals, EPDM rubber seals, etc. have
been proposed, but in the present situation the metallic Seals DISCLOSURE OF THE INVENTION
have a poor maintainability, whereas the EPDM rubber seals
have a poor reliability. 40
Problem to be Solved by the Invention
Functions generally required for a high-pressure gas seal
are an unbreakability due to pressure increases or pressure The object of the present invention is to provide a rubber
reduction (no occurrence of blisters) and a maintainability of composition for Suitable use as Vulcanization-molding mate
rubbery elasticity even if exposed to extremely low tempera rials for seal materials, etc. of high-pressure hydrogen gas
tures by adiabatic expansion due to an abrupt pressure reduc 45 storage tank, for example, to storage under 70 MPa, having
tion. For example, it is known that CNG (compressed natural distinguished low-temperature characteristics and blister
gas: about 20 MPa) known as a high-pressure fuel gas under resistance.
goes a temperature decrease down to about -60° C. by adia
batic expansion when Subjected to abrupt pressure reduction. Means for Solving the Problem
In view of this fact, it seems necessary that the rubbery elas 50
ticity must be maintained even at-60° C. or lower, because The object of the present invention can be attained by a
the hydrogen gas is stored under higher pressure than that of silicone rubber composition, which comprises 100 parts by
CNG. However, EPDM as now mainly used can maintain a weight of vinyl group-introduced methylfluoroalkylvinyl
satisfactory rubbery elasticity down to about -50° C., and based silicone rubber obtained by copolymerization of dim
thus has unsatisfactory low-temperature characteristics. 55 ethylsiloxane copolymerization units as the main component
Seal materials in a tight seal structure capable of Sustaining with 5-50 mol.% of methylfluoroalkylsiloxane copolymer
tight sealing of high-pressure gases such as high-pressure ization units, and 0.2-8 parts by weight of an organic peroX
hydrogen gas, etc., so far used, include, for example, butyl ide. Introduction of vinyl groups to the silicone rubber can be
rubber, fluororubber, hydrogenated nitrile rubber, tetrafluo carried out generally by copolymerization of the silicone
roethylene-perfluoro(alkyl vinyl ether) copolymer, etc., as 60 rubber with 0.1-5 mol. 9% of methylvinylsiloxane. When
disclosed in the following Patent Literatures 1 and 2. How silica is used as a filler, it is preferable to use a surfactant for
ever, these rubber materials for forming seal materials are not the silica, and water together.
preferable, because of deterioration of sealability at low tem
peratures. Furthermore, at least butyl rubber, fluororubber, Effect of the Invention
and hydrogenated nitrile rubber have a problem of blister 65
occurrence, when Subjected to abrupt pressure reduction. Homopolymer of methylvinylsiloxane or methylfluoro
Patent Literature 1: JP-A-2003-28302 alkylvinylsiloxane cannot satisfy both of the necessary low
 US 8,217,132 B2
3 4
temperature characteristics and blister resistance at the same 2,5-di(benzoylperoxy)hexane, t-butylperoxy benzoate,
time, whereas the present silicone rubber composition com t-butylperoxyisopropyl carbonate, n-butyl-4,4-di(t-butylper
prising the copolymer of the methylvinylsiloxane and meth oxy) Valerate, etc.
ylfluoroalkylvinylsiloxane can give such distinguished low The organic peroxide can be used in a proportion of 0.2-8
temperature characteristics as to allow use even at -80° C. parts by weight, preferably 1-5 parts by weight, on the basis of
and also a distinguished blister resistance at the same time. 100 parts by weight of silicone rubber. When the organic
Owing to distinguished low-temperature characteristics and peroxide is used in a proportion of less than 0.2 parts by
blister resistance, the present silicone rubber composition can weight, any satisfactory cross-linking density cannot be
be used as a Suitable seal material for high-pressure hydrogen obtained, whereas in a proportion of more than 8 parts by
gas storage tanks, for example, to storage under 70 MPa, and 10 weight, foaming will take place, resulting in a failure to obtain
specifically as Suitable Vulcanization-molding materials for O Vulcanization products or if obtained the rubbery elasticity or
rings, packings, gaskets, oil seals, valves, etc. The high-pres elongation will be lowered.
Sure gas to be stored includes not only a hydrogen gas, but The silicone rubber composition can further contain, if
also, e.g. an oxygen gas, a nitrogen gas, a helium gas, etc. The required, besides the foregoing essential components, a rein
15 forcing agent such as carbon black, silica, etc., a filler Such as
present invention is directed to application to a high-pressure talc, clay, graphite, calcium silicate, etc., a processing aid
gas under 1 MPa or higher as a measure of the pressure Such as Stearic acid, palmitic acid, paraffin wax, etc., an acid
resistance, and a distinguished pressure-resistant sealability acceptor Such as Zinc oxide, magnesium oxide, etc., an anti
can be attained particularly under 35 MPa or higher, as set oxidant, a plasticizer, etc.. So far used generally as rubber
forth in the storage tank specification, for example, under the compounding agents, appropriately.
service conditions of 70 MPa, as mentioned above. Silica can be used as a reinforcing agent in a proportion of
When silica is also used as a filler, it is preferable to use a not more than 120 parts by weight, preferably about 50 to
Surfactant for the silica, and water together. Simultaneous use about 120 parts by weight, on the basis of 100 parts by weight
of water is effective for further prevention of blister occur of methylfluoroalkylvinyl-based silicone rubber. When silica
CC. 25 is used, it is desirable to use together with not more than about
12 parts by weight, preferably about 2 to about 8 parts by
BEST MODES FOR CARRYING OUT THE weight, of a Surfactant such as hexamethylsilaZane, etc. on the
INVENTION basis of 100 parts by weight of silica, where the blisters will
be hard to occur by using not more than about 50 wt.%.
The methylfluoroalkylvinyl-based silicone rubber for use 30
preferably about 10 to about 30 wt.% of water on the basis of
in the present invention is a silicone rubber, which comprises the weight of the Surfactant at the same time.
dimethylsiloxane copolymerization units as the main compo The present composition can be prepared by kneading
nent, a methylfluoroalkylsiloxane copolymerization units, for through a kneader Such as intermix, kneader, Banbury mixer,
example, Y.Y.Y-trifluoropropylmethylsiloxane (CFCHCH) etc. or open rolls, etc., and Vulcanization-molding can be
(CH)SiO copolymerization unit, (5-50 mol. %, preferably 35 carried out generally by heating at about 150° to about 200°
20-40 mol.%, based on 100 mol.% of total), copolymerized C. for about 3 to about 60 minutes through an injection
with the former copolymerization units, and further a small molding machine, a compression molding machine, a Vulca
amount (about 0.1 to about 5 mol.%, preferably about 0.5 to nization press, etc., and if required, oven heating (secondary
about 3 mol.%, and about 1 mol.% in Examples and Com Vulcanization) can be carried out by heating at about 150° to
parative Examples, based on 100 mol.% of total) of a vinyl 40 about 250° C. for about 1 to about 24 hours.
group as a cross-linkable group, derived from methylvinylsi
loxane (CH=CH)(CH)SiO copolymerization units, etc. So EXAMPLES
long as the copolymerization proportion of the methylfluoro
alkylsiloxane copolymerization units is within 5-50 mol.%. The present invention will be described in detail below,
the methylfluoroalkylvinyl-based silicone rubber can have a 45 referring to Examples.
glass transition temperature Tg of -80° to -120°C., and can
be used at extremely low-temperatures without any blister Example 1
occurrence even if Subjected to abrupt pressure reduction,
whereas when the copolymerization proportion of the meth
ylfluoroalkylsiloxane copolymerization units is outside the 50
above-defined range, the resulting silicone rubber has a glass
transition temperature Tg of about -70° C. at the lowest, and Parts by weight
cannot always be used at extremely low-temperatures, where Methylfluoroalkylvinyl-based silicone rubber 100
the blister resistance is often not satisfactory. As the silicone (copolymerization proportion of Y.Y.Y-
rubber having a copolymer composition as set forth above, 55 trifluoropropylmethylsiloxane copolymerization
commercially available products such as X-30-7811U, etc. of units: 30 mol.%)
Silica 70
Shin-Etsu Silicone products, can be practically used as such. HexamethyldisilaZane 5
The methylfluoroalkylvinyl-based silicone rubber can be (Surfactant for silica compounding)
Vulcanized (cross-linked) by an organic peroxide. Any Distilled water 1
2,5-dimethyl-2,5-di(t-butylperoxy) hexane 2
organic peroxide can be used without any particular restric 60
tion, so long as it can be generally used in rubber, and
includes, for example, benzoyl peroxide, p-chlorobenzoyl The foregoing components were kneaded through a kneader
peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, and open rolls, and the resulting kneading product was press
t-butyl cumyl peroxide, dicumyl peroxide, 1,1-di(t-butylper Vulcanized at 170° C. for 20 minutes, and oven Vulcanized
oxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-bu 65 (secondary Vulcanization) at 200° C. for 4 hours to produce
tylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hex Vulcanized sheets (150 mmx 150 mmx2 mm) and G25 size
ine-3,1,3-di(t-butylperoxyisopropyl)-benzene, 2,5-dimethyl rings (inner diameter: 24.4 mm, wire diameter: 3.1 mm).
 US 8,217,132 B2
5 6
The resulting Vulcanizates were subjected to determination unit is 70 mol.%, was used as the silicone rubber, while the
of the following items: amount of silica was changed to 60 parts by weight.
Normal state physical properties: according to JIS K6253
and K6251 corresponding to ASTM D2240 and D412 Comparative Example 4
Low-temperature characteristics: TR test according to JIS
K6261 corresponding to ASTM D1329, and determina In Example 1, the amount of organic peroxide was changed
tion of glass transition temperature to 0.1 part by weight. At the stage of just prepared compound
Blister test: Visual determination of blister occurrence or (unVulcanizated State), foaming took place, resulting in fail
not by placing the test samples into a hydrogen gas ure to conduct molding.
atmosphere or helium gas atmosphere under 70 MPa at 10
25°C. for 5 hours, followed by pressure reduction down Comparative Example 5
to the normal atmospheric pressure within 5 Second
In Example 1, the amount of organic peroxide was changed
Example 2 to 10 parts by weight. The Vulcanization sheet underwent
15 foaming, resulting in failure to conduct molding.
In Example 1, the same amount of methylfluoroalkylvinyl Results obtained in the foregoing Examples and Compara
based silicone rubber, a copolymerization proportion of tive Examples (excluding Comparative Examples 4 and 5) are
whose Y.Y.Y-trifluoropropylmethylsiloxane copolymerization shown in the following Table.
TABLE
tem of determination Comp. Comp. Comp.
evaluation Ex. 1 Ex. 2 Ex. 3 Ex. 1 Ex. 2 Ex. 3

Normal state physical properties

Hardness (Duro A) 70 70 71 71 69 70
Tensile strength (MPa) 8.2O 8.53 8.44 8.78 10.3 8.69
Elongation at break (%) 250 270 240 220 250 250
Low-temp. Characteristics
TR-10 ( C.) <-85 -80 -68 -50 -63 -57
Glass transition temp. Tg (C.) -120 -98 -80 -61 -70 -72
Blister test
Blister generation
H2 None None None None Yes None
He None None None None Yes None

is 50 mol. 96, was used as the silicone rubber, while the It can be seen from the foregoing results that all the
amount of silica was changed to 70 parts by weight. Examples are satisfactory in both of the low-temperature
characteristics and blister test, whereas Comparative
Example 3 40 Examples 1 and 3 are not satisfactory in the low-temperature
characteristics and Comparative Example 2 is not satisfactory
In Example 1, the same amount of methylfluoroalkylvinyl in the blister resistance.
based silicone rubber, a copolymerization proportion of
whose Y.Y.Y-trifluoropropylmethylsiloxane is 10 mol.%, was The invention claimed is:
45
used as the silicone rubber, while the amount of silica was 1. A silicone rubber composition that is used as a Vulcani
changed to 90 parts by weight, and neither hexamethyldisi Zation-molding material for a high-pressure gas seal material,
lazane nor distilled water was used.
which silicon rubber composition comprises 100 parts by
Comparative Example 1 weight of vinyl group-introduced methylfluoroalkylvinyl
50 based silicone rubber obtained by copolymerization of dim
In Example 1, the same amount of methylvinylsiloxane ethylsiloxane copolymerization units as the main component
homopolymerization silicone rubber (KE971-U, a product of with 5-50 mol.% of a methylfluoroalkylsiloxane copolymer
Shin-Etsu Silicone product) was used as the silicone rubber, ization unit, and 0.5-5% by mole of methylvinylsiloxane
while the amount of silica was changed to 95 parts by weight. copolymerization unit, 50-120 parts by weight of silica as a
55 reinforcing agent, 2-12 parts by weight of hexamethyldisila
Comparative Example 2 Zane as a Surfactant for compounding the silica on the basis of
100 parts by weight of the silica, 10-30% by weight of water
In Example 1, the same amount of methylfluoroalkylvinyl on the basis of the weight of the Surfactant for compounding
siloxane homopolymerization silicone rubber (FE271-U, a the silica, and 0.2-8 parts by weight of an organic peroxide
Shin-Etsu Silicone product) was used as the silicone rubber, 60 selected from benzoyl peroxide, p-chlorobenzoyl peroxide,
while the amount of silica was changed to 40 parts by weight. 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, t-butyl
cumyl peroxide, dicumyl peroxide, 1,1-di(t-butylperoxy)-3,
Comparative Example 3 3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylper
oxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3,
In Example 1, the same amount of methylfluoroalkylvinyl- 65 1,3-di(t-butylperoxyisopropyl)-benzene, 2,5-dimethyl-2,5-
based silicone rubber, a copolymerization proportion of di(benzoylperoxy)hexane, t-butylperoxybenzoate, and n-bu
whose Y.Y.Y-trifluoropropylmethylsiloxane copolymerization tyl-4,4-di(t-butylperoxy) Valerate.
 US 8,217,132 B2
7 8
2. A silicone rubber composition according to claim 1, 4. A high-pressure gas seal material Vulcanization-molded
wherein the silicone rubber is used whose methylfluoroalkyl- from a silicone rubber composition according to claim 1.
siloxane copolymerization unit is a Y.Y.Y-trifluoropropylm- 5. A high-pressure gas seal material according to claim 4.
ethylsiloxane copolymerization unit. for use as a high pressure hydrogen gas seal material.
3. A silicone rubber composition according to claim 1, 5
wherein 2-8 parts by weight of the hexamethyldisilazane is
used on the basis of 100 parts by weight of silica. k . . . .