US005.

716441A
United States Patent 19 11) Patent Number: 5,716,441
Nguyen et al. 45 Date of Patent: Feb. 10, 1998
54 STARCH-BASED, WATER RESISTANT OTHER PUBLICATIONS
ADHESVES
O.B. Wurzburg, “Modified Starches: Properties and Uses".
75) Inventors: Nina Nguyen, Somerset; Daniel B. e
Solarek. Belle Mead; Joseph 1986, no month avail. Chapter 9, 131-147.
Wieczorek, Jr., Flemington; Charles R.L. Whistler et al. “Starch: Chemistry and Technology",
W. Cline, Stockton; Jeffrey Atkinson, Second Edition, 1984, no month avail. pp. 341-349.
Neshanic Station, all of N.J.
R.L. Whistler et al., “Starch: Chemistry and Technology".
73) Assignee: National Starch and Chemical Second Edition, 1984, no month avail. pp. 599-610.
Investment Holding Corporation,
Wilmington, Del.
Primary Examiner-David Brunsman
(21) Appl. No.: 722,786 Attorney, Agent, or Firm-Eugene Zagarella, Jr.
22 Filed: Sep. 27, 1996 57 ABSTRACT
(51] Int. Cl. ......................... C09J 103/06 An aqueous water resistant, viscosity stable adhesive com
52 U.S. C. .................................................... 106/207.1 position for use in paper bonding applications comprising a
(58) Field of Search one wow so eason was so 106/207.1 hydrophobically modified fluidity corn starch having a water
fluidity of about 60 to 80 and a solids content of about 8 to
(56) References Cited 40%. The starch having the formula
U.S. PATENT DOCUMENTS COOY
2,661.349
sww.s 2/1953 Caldwell et al. ... ... 260/224 Starch-O-C-R-R
3.655,644 4/1972. Durand ......... . . 106/207.1 tacho--R
3,844,807 10/1974 Bramel ..... ... 106/213 O
4231803 11/1980 Bovier et al. ... ... 106/207.1
4,780,339 10/1988 Lacourse et al. ... 427/389.7
4,838,944 6/1989 Kruger ...................................... 127/71 wherein R is a dimethylene or trimethylene group, R is a
5,153,161 10/1992 Kerschner et al. ..................... 502/167 hydrocarbon group having 5-12 carbon atoms and Y is H.
FOREIGN PATENT DOCUMENTS alkali metal, alkaline earth metal or ammonium.
54-132634 10/1979 Japan ................................. CO9J 3/06
1 469 178 3/1977 United Kingdom .............. CO8L 3/02 24 Claims, No Drawings
 5,716.441
1 2
STARCH-BASED, WATER RESISTANT which is prepared by reacting the base corn starch with an
ADHESVES organic acid anhydride reagent material having the follow
ing structural formula:
BACKGROUND OF THE INVENTION
This invention relates to starch-based adhesives which are 5
water resistant without containing urea-formaldehyde or
other chemical crosslinkers and which further have desired
viscosity stability characteristics.
Starches have been used for some time in various adhe O
sive applications especially for paper products such as bags,
tubes and tissue towels. This is illustrated in "Starch: Chem
istry and Technology", second edition, edited by R. L. where R represents a dimethylene or trimethylene group and
Whistler et al., 1984, Chapter XX, pp. 599-609, where the R" is a substituent hydrocarbon group having 5 to 12. and
use of starch and dextrins in prepared adhesives including 15 preferably 8, carbon atoms. The hydrocarbon or hydropho
bag adhesives, laminating, tube winding and case and carton bic substituent group R' may be alkyl, aryl, alkenyl, aralkyl
sealing is shown. or aralkenyl with alkyl and alkenyl being preferred. Particu
While many starch products have been successfully used larly preferred for R is an octenyl group. Starch derivatives
in different adhesive formulations, when applications of this type are known and have been prepared using a
require water resistance, modification to the formulation is 20 standard esterification reaction where the reagent and starch
usually needed because a starch bond is normally not water suspended in water are mixed under alkaline conditions as
resistant. Consequently, in order to provide starch based disclosed in U.S. Pat. No. 2.661,349 issued on Dec. 1, 1953
adhesive formulations which provide water resistance, addi to C. Caldwell and O. Wurzburg. The starch derivatives and
tives such as urea-formaldehyde, resorcinol-formaldehyde method of preparation are further described in "Starch:
and other thermosetting resin and crosslinking agents are 25 Chemistry and Technology", Second Edition, edited by R. L.
typically used as further indicated in the Whistler et al. Whistler
Properties
et al., 1984, pp. 341-343 and "Modified Starches:
and Uses", edited by O. Wurzburg, 1986. Chapter
article noted above, at page 601. The use of a urea 9, pp. 131-147.
formaldehyde reaction product to provide water resistance in The base starch material used in preparing the hydropho
an alkali digested starch adhesive formulation is described in bically modified starch is corn starch which is converted to
British Patent No. 1469.178 and Japanese Patent No. 132,
634/79 discloses an epichlorohydrin-crosslinked hydroxy aabout water fluidity (WF) of from about 60 to 80. preferably
66 to 78 and more preferably from about 68 to 75. The
ethyl starch-based paper bag adhesive. U.S. Pat. No. 3,844, measurement for water fluidity as described herein is made
807 discloses water resistant starch-based paper bag using a Thomas Rotational Shear Type Viscometer
adhesives comprising a pre-blend mix of acid hydrolyzed (manufactured by Arthur H. Thomas Co., Philadelphia, Pa.)
starch, hydroxyethylated starch, a specific starch modifier 35 in accordance with standard procedures such as disclosed in
polyoxyethylene laminate and urea formaldehyde resin. Zwiercan et al., U.S. Pat. No. 4499,116 issued Feb. 12.
Despite the acknowledged use and availability of starch 1985, which patent is incorporated by reference herein. The
based, water resistant adhesive products as described above, derivatized corn starch may be converted or degraded to the
the ability to provide such a product without added form selected water fluidity using either oxidative hydrolysis or
aldehyde or other chemical crosslinking agents has been and acid hydrolysis. However, in order to get the most suitable
still is a desired goal, particularly one that also provides viscosity stability it is desirable and preferred to use an
suitable viscosity stability. oxidation hydrolysis procedure employing hydrogen perox
SUMMARY OF THE INVENTION ide and a catalytic amount of manganese ions, such as
potassium permanganate, in an alkaline slurry reaction.
It has now been found that a starch-based water resistant 45 The process of oxidation hydrolysis with hydrogen per
adhesive composition free of formaldehyde and other oxide may be carried out using a starch aqueous slurry
crosslinking additives is provided by the use of a selected ordinarily at 20 to 50% solids and raising the pH to about
hydrophobically modified, fluidity corn starch. 11.0 to 12.5 with sodium hydroxide. Temperatures ranging
More particularly, this invention is directed to a water from about 0° to 55° C. can be used to react the starch but
resistant, viscosity stable adhesive composition comprising 50 a range of about 22° to 45° C. is most practical and preferred
a hydrophobically modified fluidity corn starch having the in the process with the higher temperatures requiring less
formula: time for completion of the reaction. In order to achieve
improved reaction rates when using slurry temperatures
COOY (1) below room temperature (e.g., 0° to 20° C.), it is preferable
that the pH level be maintained at the upper portion of the
designated useful pH range (pH 11.8 to 12.5). In order to
O avoid gelatinization of the starch, the temperature should not
where ST is a fluidity corn starch having a water fluidity be allowed to go much about 50° C.
(WF) of from about 60 to 80; R is a dimethylene or Potassium permanganate catalyst is used in the hydrogen
trimethylene group, R is a hydrocarbon group having 5 to peroxide hydrolysis described herein, however, other man
12, and preferably 8, carbon atoms; and Y is H, alkali metal, ganese salts such as manganous chloride, manganic acetate,
alkaline earth metal or ammonium. manganous acetate and manganous nitrate as disclosed in
U.S. Pat. No. 4,838,944 issued Jun. 13, 1989 to L. Kruger
DETALED DESCRIPTION OF THE may also be used. Additionally, mangenese complexes such
INVENTION 65 as manganese (NNN")-trimethyl 1,4,7-triazocyclononane)
The water resistant adhesive composition of this invention hexafluorophosphate as disclosed in U.S. Pat. No. 5,153.161
comprises a hydrophobically modified fluidity corn starch issued Oct. 6, 1992 to J. Kerschner et al. may also be used.
 5,716441
3 4
Sufficient manganese metal salt or complex are added to of the starch and this can be from about 55° to 200° C. or
the slurry with stirring to provide a concentration of about higher depending on the conditions and type of cooking
0.05 to 150 ppm (parts per million) and preferably about 0.1 being utilized. Preferred cooking is at about 190° to 195°C.
to 90 ppm of manganese metalions based on the amount of As stated previously, while the use of different starches
5
starch solids. If desired the catalyst can be added to the and modified starches in adhesive formulations are known,
slurry prior to pH adjustment. the ability to provide a water resistant starch adhesive has
Hydrogen peroxide is then introduced into the slurry with generally required the addition of resins or crosslinking
the full amount added at once or if desired, divided into agents such as urea-formaldehyde to provide this function.
several portions (5 or 6 or more with larger amounts of 10 The selected hydrophobic fluidity corn starch of this inven
peroxide) and added at about one hour intervals or added tion has been found to provide a water-resistant adhesive
continuously as when metered in with a pump. The amount without requiring the use of a resin or crosslinking additive
of hydrogen peroxide employed is from about 0.0075 to and further has resulted in a formulation which gives good
15%, preferably about 0.01 to 2.0% anhydrous, and more viscosity stability. This combination of properties make this
preferably about 0.5 to 1.5% based on starch solids. The 15 starch-based adhesive useful in a number of paper bonding
reagent is ordinarily introduced by the addition of sufficient applications including laminating adhesives, e.g., tissued
30 to 35% aqueous hydrogen peroxide as is commonly towel; tube winding; case and carton and particularly as bag
supplied in commerce. adhesives, e.g., side seam, bottom paste and cross paste.
While the oxidation hydrolysis process of this invention 20 The viscosity of the adhesive compositions of this inven
has been described employing peroxide together with a tion used in paper bonding applications can vary depending
manganese catalyst, it will be understood that other com on the particular application but generally will vary between
pounds which yield hydrogen peroxide on contact with an initial viscosity of about 50 to 110,000 cFs Brookfield at
water can be substituted for the required hydrogen peroxide. 80° F (26.6° C), preferably between about 100 to 6000 cFs
Such hydrogen peroxide equivalents include alkali metal 25 and more preferably between 750 to 3000 cps. Viscosity
and alkaline earth metal peroxides such as sodium and stability describes the ability of an adhesive to maintain a
potassium peroxide, alkali metal perborates, mono workable consistency for an extended period of time, e.g.,
persulfates (e.g., Oxone, a registered trademark product of 24 hours (1 day) or 6/7 days in a given application. While
E. I. DuPont), perphosphates, superoxides, percarbonates 30 this characteristic may vary depending on the particular
and peracids such as peracetic acid. In addition, alkyl application and conditions, for paper bonding applications
hydroperoxides, such as t-butyl hydroperoxide, have been and especially in bag adhesive applications, desired viscos
found to be effective in the degradation process as an ity stability will be a percent viscosity change of less than
alternate oxidant. Other active oxygen specimens may also 150% in 24 hours and preferably less than 100%. Over a
be used. 35 longer period of 6 to 7 days, viscosity may increase to a
The hydrogen peroxide used in the process of this inven higher degree and still be acceptable but generally a percent
tion can be added to the starch slurry as a single shot or increase of less than 200% and preferably less than 150%
slowly over time as a number of portions, allowing time for over this period is a desired viscosity stability characteristic.
its reaction with starch. After the addition of two or more The starch-based adhesive composition of this invention
such portions, the degree of starch conversion or degrada has property characteristics which make it useful in different
tion can be determined and additional hydrogen peroxide paper bonding applications including the use as a bag
added as needed or the reaction can be terminated. In this adhesive or in laminating. These different applications may
slow addition procedure, the peroxide increments are involve the need for adhesive compositions with different
reacted as they are added and better control of the degra 45 properties. In the use as a bag adhesive, and especially in
dation end-point can be achieved. A potassium iodide spot side seaming, the adhesive composition of this invention
test can be used to confirm the presence or absence of will desirably have an initial Brookfield viscosity of about
hydrogen peroxide in the test slurry. 500 to 6000 cps, preferably about 750 to 3000 cps and a
The process of oxidation hydrolysis using hydrogen per starch solids content of about 15 to 40%, preferably about 18
oxide is further described in U.S. Pat. No. 4,838,944 noted 50 to 30%. Bag adhesives used in special applications such as
above, which patent is incorporated herein by reference bottom pastes may need higher initial viscosities of about
along with U.S. Pat. No. 5,153.161 which discloses man 100,000 cps (Brookfield) as found in the higher end of the
ganese complexes and which is also noted above. previously noted viscosity range. On the other hand, lami
The amount of hydrophobic modification of the corn 55 nating adhesives as used in tissue/towel applications will
starch can vary from about 0.5 to 6% by weight of bound prefer lower initial viscosities of about 50 to 1000 and more
ester substituent group based on the weight of starch, preferably about 100 to 500 cps (Brookfield) and starch
preferably from about 1.9 to 3.2% and more preferably from solids of about 8 to 20%, preferably about 10 to 15%. In
about 2.1 to 2.8%.
laminating adhesives, longer term viscosity stability is
The modified starch of this invention is prepared for use required, e.g., 60 to 90 days with typical viscosity changes
as an adhesive by cooking and dispersing the starch in water of 10 to 50%,
at a solids of about 8 to 40%, preferably 18 to 30%. The The adhesive composition of this invention will generally
starch may be cooked using any of the known techniques comprise an aqueous formulation of the modified fluidity
including atmospheric cooking and jet cooking or steam 65 corn starch and water. While it does not require the use of
injection cooking. Typical cooking conditions can range crosslinking or resin additives to provide water resistance
from a temperature of at least the gelatinization temperature other additives commonly known and used in adhesives may
 5,716.441
S 6
be used providing they do not affect the water resistance and tinued at 40° to 43° C. until the pH stabilized after 1 to 2
stability properties of the final product. Such additives may hours. The reacted slurry was removed from the temperature
include, for example, tackifiers, defoamers, plasticizers, bath, filtered and dried.
preservatives, bleaches, etc.
The following examples will further illustrate the embodi The modified fluidity corn starch prepared as described
ments of this invention. In these examples all parts are given above had a WF of 75 and a bound octenylsuccinic anhy
by weight and all temperatures in degrees Celsius unless dride content of 2.55%. This starch product was formed into
otherwise noted. The viscosity's were determined using a an adhesive composition by cooking in an aqueous solution
Brookfield viscometer at 80° F (26.6° C) unless otherwise of 22% solids at 195° F for 15 minutes. The prepared
noted. Reference to viscosity as used throughout the speci adhesive was evaluated for water resistance when used as a
fication and examples is to this Brookfield viscosity. paper bag adhesive in the following manner:
EXAMPLE Water Resistance Test
A fluidity corn starch was prepared as follows. The corn
starch base (100 parts) was slurried in water (125 parts) and 1. Paste used immediately at 80° F.
heated to 40° to 43° C. in a controlled temperature bath. A 2. Put 6 mil coating of paste on bag substrate
3% aqueous solution of sodium hydroxide (0.75 parts) was
slowly added to the mixture followed by the addition of 3. Mate with another substrate
0.0075 parts of a potassium permanganate as a 2% aqueous 4. Compress bond with roller (twice)
solution. The alkalinity of the mixture was adjusted to a pH 5. Place bonds between two glass plates
of 11.7 to 11.8 (50 mL of reaction slurry should require 35
to 45 mLs of 0.1N HCl to neutralize to a phenolphthalein 6. Place weight (25 lb.) on top of glass plates for 24 hours
endpoint) and 2.5 parts of 30% aqueous hydrogen peroxide 7. Age bonds for one week
added slowly. The pH of the mixture was maintained at 11.7 8. Water soak at room temperature
to 11.8 and the reaction continued for 2 to 2.5 hours until it
was nearly complete as indicated by a potassium iodide 9. Pull bonds at 1, 4, 8 and 24 hours; evaluate fiber tear
colorometric spottest run on a sample of the slurry mixture. (FT).
The pH of the mixture was then adjusted to 6.0 with a dilute The adhesive product was evaluated and had the follow
solution of hydrochloric acid. A sample of the prepared ing properties:

Initial Wisc.
Wisc. Change
Starch % at 80° F. at 6 36 Fiber Tear (FT)
Material WF Solids cPs days 1 hr. 4 hrs. 8 hrs. 24 hrs.
OSA modified 75 22 1900 62/167% 00% 100% 100% 100%
corn starch deep deep deep fiber
fiber fiber fiber tear
tea tear tear

converted starch was analyzed to determine its water fluidity EXAMPLE 2

(WF) using a Stormer viscometer and found to have a WF 45 Additional samples of modified fluidity corn starch were
of 75.
The converted corn starch was then modified by the prepared and formulated into adhesive compositions as in
addition of octenylsuccinic anhydride (OSA). The converted Example 1. These samples had varying amounts of modi
starch slurry was adjusted to a pH of 7.5 with 3% aqueous fying group (OSA) and also were converted or degraded
NaOH and octenylsuccinic anhydride (3 parts) was added in using either hydrogen peroxide (HO) or acid conversion.
/3 increments every thirty minutes. The reaction was con The results are shown in the following table.

%
Wiscosity Water Resistance
Change Fiber Tear
Sample Starch Type % Wiscosity 8 24
No. Material WF Conversion Solids cPs day 3 days 6-7 days 1 hr. 4 hrs. hrs. hrs.
A 2% OSA 71 HO 21 6900 88 O2 140 100 00 100 100
Corn
B 2%. OSA 71 Acid 21 13000 84 107 320 10O 100 100 100
Coin
C 3%, OSA 71 HO 21 5700 57 57 95 100 100 100 100
Corn
D 3%. OSA 71 Acid 21 3300 12 200 250 100 100 100 100
Corn
 5,716.441
7 8
-continued

Wiscosity Water Resistance

Change % Fiber Tear
Sample Starch Type 9. Wiscosity 8 24
No. Material WF Conversion Solids cPs day 3 days 6-7 days 1 hr. 4 hrs. hrs. hrs.
E 4 OSA 71 HO, 2 4500 24 15 36 OO sh 100 sh 100 O
Cola
F 49, OSA 7 Acid 2 18000 O O 4 100 100 OO 25
Corn

It is noted that while the acid converted starches of Samples EXAMPLE 5

B, D and F did provide comparable water resistance to the 15
OSA modified starch samples of different base starches,
hydrogen peroxide samples, viscosity stability was generally namely tapioca, wheat and potato were prepared as in
not as good. Examples 1 and 2. The modified tapioca and wheat starch
EXAMPLE 3 samples gave both poor water resistance and poor viscosity
20 while the modified potato starch gave fair water resistance
Additional test samples were run using pilot and plant test and very poor viscosity properties.
batches on modified fluidity corn starches prepared and EXAMPLE 6
formulated in a manner similar to Example 1. These samples
identified below had varying starch or solids content and A comparison of laminating adhesives for tissue-towel
gave viscosity stability results as shown in the table. application was made using a 3% OSA modified corn starch

9.
Initial Wiscosity
Starch Type Wiscosity Stability
Material WF Conversion Solids cPs 1 day 3 days 7 days
Pilot Batch

3. OSA Col. 75 HO 8 65 30 37 51
39, OSA Corn 75 H2O2 20 980 36 48 48
3. OSA Col. 75 HO 22 94 39 39 40
Plant Test Batch

3. OSA Corn 72 HO 8 850 88 68 96

32. OSAC 72 HO 20 1350 57 80 OO
3. OSA Cor 72 HO 22 1980 y1 88 OO

All pilot batch samples gave water resistance of 100% as in Example 1, a 6% solids partially hydrolyzed polyvinyl
fiber tear up to hours and all plant test samples gave 100% alcohol and a 13% solids waxy starch in different test
deep fiber tear up to 24 hours. 45 samples. All three samples were tested for one week vis
cosity stability, dry adhesion and water resistance. For the
EXAMPLE 4 adhesion and water resistance testing, bonds were prepared
Additional modified corn fluidity starches were prepared and cured for 72 hours before testing. Dry adhesion was
as in Examples 1 and 2 using varying amounts (2.5, 4 and evaluated on the basis of hand feel and bond strength. The
6%) of dodecenylsuccinic anhydride as the modifying products were rated versus one another (from 1 to 3) for
bond strength and hand feel. A rating of 1 is strongest bond
groups. These samples had a water fluidity (WF) of 75 and or best hand feel and a rating of 3 is weakest bond or stiffest
provided excellent water resistance properties of deep 100% lamination. Water resistance was tested by placing a lami
fiber tear up to 24 hours. However, viscosity stability at 3 55 nation in a beaker filled with water and then recording the
days was not good (200 to 400% change) in comparison to length of time for complete delamination of the two plies.
the OSA modified and HO converted starch samples. The results are shown in the table below.

Sample Material
Partially
OSAModified Hydrolyzed Waxy
Property Corn Polyvinyl Alcohol Stach
Initial viscosity cs 95 85 60
Solids? 3.8 6.6 3.4
 5.716441
9 10
-continued
Sample Material
Partially
OSAModified Hydrolyzed Waxy
Property Corn Polyvinyl Alcohol Starch
24 hr. viscosity cps 130 95 65
72 hr. viscosity cFs 128 94 62
1 week viscosity cPs 50 100 70
A viscosity % +36.7 +17.6 +16.7
Adhesion Destructive bond - 1 Good adhesion - 3 Stronger bond - 2
Stiffer lamination - 3 Good hand feel- 1 Good hand feel - 1
Water Resistance 3.74 0.5 10
minutes 3.33 0.33 O.75

15

It can be observed that the OSA modified corn greatly 10. The paper bag adhesive composition of claim 9
improves the water resistance over the standard polyvinyl wherein the corn starch is converted to said water fluidity
alcohol for towel laminations and the bond strength of a dry using oxidative hydrolysis employing hydrogen peroxide
bond is vastly improved over both the other currently used 20
and a catalytic amount of manganese ions.
products. 11. The composition of claim 10 wherein the starch has
What is claimed is: about 0.5 to 6% of bound ester substituent group.
1. An aqueous water resistant, viscosity stable adhesive 12. The composition of claim 11 wherein the solids is
composition free of formaldehyde and other crosslinking about 18 to 30% and the starch has a WF of from about 66
additives and comprising a hydrophobically modified fluid to 78.
25 13. The composition of claim 12 having an initial Brook
ity corn starch having the formula:
field viscosity of about 750 to 3000 cFs at 80° F.
COOY 14. The composition of claim 13 wherein the starch has
ST-0-C-R-R
about 1.9 to 3.2% of bound ester substituent group.
30
15. The composition of claim 1 wherein the corn starch is
O converted to said water fluidity using oxidative hydrolysis
employing hydrogen peroxide and a catalytic amount of
where ST is a fluidity corn starch having a water fluidity manganese ions.
(WF) of from about 60 to 80; R is a dimethylene or 16. The composition of claim 15 wherein the manganese
trimethylene group; R is a hydrocarbon group having 5 to 35
catalyst is potassium permanganate.
12 carbon atoms and Y is H, alkali metal, alkaline earth 17. The composition of claim 15 wherein R is a hydro
metal or ammonium; and wherein the composition has a carbon group having 8 carbon atoms.
solids content of 8 to 40%. 18. The composition of claim 17 wherein R is a dimeth
2. The composition of claim 1 wherein R is a hydrocar ylene group.
bon group having 8 carbon atoms. 19. The composition of claim 15 wherein the solids
3. The composition of claim2 wherein R is a dimethylene content is about 18 to 30%.
group. 20. The composition of claim 19 wherein the starch has a
4. The composition of claim 3 wherein the solids content WF of from about 66 to 78.
is 18 to 30%. 21. The composition of claim 20 wherein R is a hydro
5. The composition of claim 4 wherein the starch has a 45
carbon group of 8 carbon atoms and R is a dimethylene
WF of from about 66 to 78. group.
6. The composition of claim 3 wherein the starch has 22. The composition of claim 15 wherein the starch has
about 0.5 to 6% of bound ester substituent group. about 0.5 to 6% of bound ester substituent group.
7. The composition of claim 6 having an initial Brookfield 23. The composition of claim 22 having an initial Brook
viscosity of about 50 to 110,000 cps at 80° F. field viscosity of about 50 to 110,000 cps at 80° C.
8. The composition of claim 7 wherein the solids is about 24. The composition of claim 23 wherein R' is a hydro
18 to 30% and the starch has a WF of from about 66 to 78. cartbon group having 8 carbon atoms. R is a dimethylene
9. A paper bag adhesive composition comprising the group, the composition has a solids content of about 18 to
30% and the starch has a WF of from about 66 to 78.
composition of claim 3, having an initial Brookfield viscos
ity of about 500 to 6000 cps at 80° F. 55 sk sk s: k k

65