United States Patent (19) 11) 4,085,074

W00
45 Apr. 18, 1978
54 PRE-MIXED CATALYZED WINYLACETATE 56) References Cited
POLYMERADHESIVE COMPOSTION
U.S. PATENT DOCUMENTS
(75) Inventor: Ming Cho Woo, Willingboro, N.J. 3,213,051 10/1965 Pink ..........................., 260/29.6 WA
3,563,851 2/1971 Amour et al. .............. 260/29.6 WA
3,644,257 2/1972 Nickerson et al. ......... 260/29.6 WA
(73) Assignee: National Casein of New Jersey, Primary Examiner-Edward M. Woodberry
Riverton, N.J. Attorney, Agent, or Firm-Max R. Millman
57 ABSTRACT
(21) Appl. No.: 671,269 A pre-mixed adhesive composition comprised of a vinyl
acetate polymer emulsion including a cross-linking cata
22 Filed: Mar. 29, 1976 lyst and a cross-linking inhibitor providing a good
cured water resistant Type II bond and extended shelf
(51) Int. Cl’............................................... CO8 1/28 life so that the adhesive composition will not gel over an
extended period of time and will therefore be usable for
(52) U.S. C. ........................ 260/17 R 260/29.6 WA; direct gluing application to semi-porous and porous
- 428/514 substrates.
(58) Field of Search ...................... 26/17 R, 29.6 WA;
428/514 19 Claims, No Drawings
 4,085,074
1 2
PRE-MIXED CATALYZED VINYLACETATE carried on for about 3 to 6 hours and the resultant aque
ous resin emulsion has a solids content of about 40-60%.
POLYMER ADHESIVE COMPOSITION At present, this resin emulsion is used as a two-part
adhesive for admixture with an acidic metal cross-link
This invention relates to cross-linkable vinyl acetate 5
ing catalyst solution such as AlCl, Al(NO), CrCl and
polymer emulsions containing a curing or cross-linking Cr(NO3)3 at the site where application of the adhesive in
agent for use as an adhesive for porous and semi-porous appropriate pressing equipment is to be carried out. The
materials. resin emulsion perse can be stored at room temperature
Heretofore, gluing operations using cross-linkable for at least 3 months, but once the same is admixed with
vinyl acetate polymer emulsions required the mixing of 10 the cross-linking catalyst the mix has a considerably
the emulsion with a catalyst, i.e. a curing or cross-link reduced shelf or pot life. Over a range of 1.0 to 12.0
ing agent prior to application to the substrates to be
glued in presssing equipment. See, for example, the parts weight
by weight of the catalyst solution per 100 parts by
of the resin emulsion, where the acidic salt con
Armour et al patent No. 3,563,851. Because the cross centration
linking of the resin occurs over a relatively short period 15 equivalentsofperthe100gms
catalyst solution is about 0.21 gram
catalyst solution, the shelf life
of time after addition of the catalyst, the mix gels over varies from about 14 days to about 45 days. This mix
that relatively short period of time and therefore cannot yields a Type II water resistant bond as defined in Fed
then be employed as a workable adhesive.
The primary object of this invention is to provide an eral Specification MMM-A-188b, Nov. 8, 1960 entitled
adhesive emulsion comprising a polymerized cross-link 20 "Adhesive; Urea-Resin-Type (Liquid and Powder)",
able vinyl acetate resin, a cross-linking catalyst and a which is herein incorporated by reference.
In accordance with the instant invention, the resin
cross-linking inhibitor, which adhesive provides a cured
water resistant Type II bond and possesses increased emulsion includes about 0.0032 to 0.025 gram equiva
shelf life and can therefore be used over a relatively catalyst and grams
lents per 100 of emulsion of an acidic metal salt
a cross-linking inhibitor in sufficient
long period of time for direct application ot porous and 25
semi-porous substrates for gluing in appropriate press amount and concentration to at least increase, and pref.
ing equipment, erably double, the shelf life of the resin emulsion plus
Another object of the invention is to provide an adhe catalyst alone and provide a bond whose shear strength
sive composition comprising a cross-linkable vinyl ace is at least 50 psi when subjected to a preconditioning for
tate polymer resin emulsion, an acidic inorganic metal 30 one day and one-half hour boil test as set forth in par.
salt cross-linking catalyst and a basic organic cross-link 4.1 and condition 16 respectively of ASTM D-1151-72,
ing inhibitor, which adhesive composition provides a which is herein incorporated by reference.
Type II water resistant bond and possesses a shelf life The acidic metal salt cross-linking agent is preferably
considerably extended over the shelf life of a mixture of - added to the resin emulsion in the form of a solution
the resin emulsion and catalyst alone. 35 containing about 0.21 gram equivalents of the catalyst
Another object of the invention is to provide an adhe per 100 grams of the catalyst solution. Said catalyst
sive composition of the character described which pos solution is added to the resin emulsion in an amount of
sesses a shelf life increased over that of the composition about 1.5 to 12.0 parts by weight of the catalyst solution
without the inhibitor and a shear strength of at least 50 to 100 parts by weight of the resin emulsion. Thus, there
psi using a one-half hour boil test following the proce 40 is present in the resin emulsion about 0.0032 to 0.025
dure set forth in ASTM D-1151-72. gram equivalents of the catalyst per 100 grams of resin
The foregoing objects are obtained by providing an emulsion. The cross-linking inhibitor is present in the
aqueous resin emulsion containing vinyl acetate poly resin emulsion in an effective amount up to a maximum
merized with alkyl esters of acrylic acid or methacrylic mole ratio of inhibitor to catalyst of about 0.7 to 1.7.
acid, such as methyl acrylate, ethyl acrylate, butyl acry 45 The preferred adhesive composition includes a resin
late, methyl methacrylate and ethyl methacrylate and emulsion (hereinafter RE in the Tables), comprising a
N-alkylol derivatives of amides of alpha, beta monomer mixture of about 90-92% vinyl acetate, about
unsaturated carboxylic acids, such as N-methylol acryl 4-6% ethyl acrylate and about 2-5% N-methylol acryl
amide, a protective hydrocolloid emulsifier such as amide, by weight polymerized with the use of a redox
polyvinyl alcohol or cellulosic dispersing agents, e.g. 50 or free radical type catalyst system in an aqueous me
hydroxyethylcellulose, carboxymethylcellulose, etc., a dium containing about 5% polyvinyl alcohol, in the
cross-linking catalyst in the form of an acidic metal salt manner described hereinbefore, the solids content of the
such as aluminum chloride, aluminum nitrate, chromic resultant emulsion being about 50% by weight. The
chloride and chromic nitrate, and a cross-linking inhibi resin emulsion (RE) is white, has a pH of 4.5 to 5.5, a
tor in the form of an amine such as ammonia, the alkyl 55 viscosity of 3000-5000 cps (25° C) and a specific gravity
and alkanol amines, e.g. mono, di and triethylamine and of about 1.09. To this resin emulsion is added an aque
mono, di and triethanolamine. ous solution of aluminum chloride in an amount of
The resin emulsion is made by polymerization tech about 1.5 to 12.0 parts by weight of the aluminum chlo
niques known in the art using free radical or redox ride solution to 100 parts by weight of the resin emul
catalysts. A monomer mixture of 80-97% by weight of 60 sion, said aluminum chloride solution containing about
vinyl acetate, remainder in varying amounts of an alkyl 0.21 gram equivalents AlCl3/100 gms solution, thus
ester of acrylic acid and an N-alkylol derivative of an providing 0.0032 to 0.025 gram equivalents of AlClper
amide of an alpha, beta-unsaturated carboxylic acid is 100 grams of resin emulsion, and triethanolamine
refluxed at about 60°-90° C with agitation in an aqueous (TEOA) in a mole ratio of TEOA/AlClup to about 0.7
medium containing in addition to the monomer mixture 65 to 1.7 as a maximum. To obtain an adhesive composition
3-6% of a hydrocolloid by weight of the monomer which will possess a shelf life which is increased over
mixture, the free radical or redox polymerization cata that of the resin emulsion plus catalyst alone and also
lysts, a defoamer and an emulsifier. The reaction is possess a cured water resistance bond of at least 50 psi
 4,085,074
3 4.
in a one-half hour boil test, the minimum TEOA/AlCl4 instant invention, control compositions and compara
mole ratio is about 0.1 to 0.2. tive results as to shelf life and shear strength.
Table I
(Controls)
Example No. 1 2 3 4. 5 6
RE (Resin Emulsion), g 00 100 100 100 100 100
AlCl', Aqueous solution, g 1.0 2.0 5 8 10 12
Initial pH 3.35 3.10 2.85 2.75 2.45 2.40
Initial Viscosity, 3250 1835 1075 850 1365 825
cps (25' C)
Shelf or Pot Life, days 25 27 27 44 15 14
O/N Cured
Dry, psi - % W.F. 878-80 765-100 572-100 492-100
hr. Boil, psi - % W.F. 194-0 2560 266-1 39-85 --
48 hr. Soak, psi - % W.F. 330-7 472-36 46-100 374-100 ---
2. Week Cured
Dry, psi - % W.F. 821-56 m 493-100 450-100
2 Cycle Boil, psi - % W.F. De. ru 266-4 277-90
48 Hr. Soak, psi - % W.F. 358-0 477-100 346-100
Key: OMN = Overnight; Del. = delaminated
W.F. as Wood failure
"=" Baume, approx. 28 wt.% AICl (about 0.21 gm equivs. AlCl/100 gms soln.)

Table II
Example No. 7 8 9 10 11 12 13 14
RE (Resin Emulsion), g 100 100 100 100 100 100 100 100
Triethanolamine (TEOA) 0.5 1.5 1.85 2 5.5 3.67 5 7.4
85 wt.%, g
AlCls', aqueous solution,...g 2 4. 5 8 10 O 12 12
Mole Ratio (TEOA/AlCl) 0.68 1.0 1.0 0.68 1.5 1.0 1.1 1.67
Initial pH 3.7 3.7 3.65 3.45 3.8 3.4 3.5 3.70
Initial Viscosity, 1175 1050 1050 550 900 800 600 550
cps (25' C)
Shelf or Pot Life, days 186 180 111 207 171- 178- 190- 30
O/N Cured
Dry, psi - % W.F. 658-100 660-100 668-100 581-100 620-100 539-100 582-100 520-100
hr. Boil, psi-% W.F. 466-33 316-0 299-0 307-0 2540 234-0 276-0 48-0
48 hr, Soak, psi - % W.F. 534-35 452-25 38S-2 486-14 326-0 339-22 400-14 348-0
2 Week Cured
Dry, psi - % W.F. 645-100 604-100 681-100 535-100 636-100 S48-100 574-100 528-100
2 Cycle Boil, psi - % W.F. 384-1 311-0 288-0 214-0 194-0 : 198-0 256-0 Del.
48 Hr. Soak, psi - % W.F. 530-75 440-1 407-2 480-25 336-0 378-15 431-32 310-0
Same solution as in Table; Del is delaminated

Table III
Compositions of Instant Invention -- Controls
Example No. 15 6 17 8 19 20 21 22 23
RE (Resin Emulsion), g 100 100 100 100 100 100 100 100 100
AlCl', aqueous solution, g 4. 4. 4 O - - - - -
fielkonine 85 wt.%, g -- -- 1.48 0.86 - 1.94
Triethylamine 100wt.%, g - - ana - O - -
N-Methyl Ethanolamine m 0.42 OO --- - u- - --
100wt.%, g
NHOH 30wt.% as NHg - 0.58 re- - -- - -
Cr(NO), aqueous solution, g - --- 4. 4. O
AICNO), aqueous solution, g wo - W -- 2.3 2.3 ---
CrClaqueous solution, g W ---- --- - - --- - 4.4 5.3
Mole Ratio (amine/catalyst) 1.18 0.67 1.22 u 1.0 1.0 u 1.0
Initial pH 3.70 3.50 3.65 2.80 4.10 3.10 3,80 3.40 4.70
Initial Viscosity, cps (25' C) 350 975 1000 1600 1625 1400 1450 1275 900
Shelf or Pot Life, days 221 131 26S 21 56 45 63-- 24 61+
O/N Cured
Dry, psi - % W.F. 604-100. 560-100 709-100 717-60 738-75 727-100 778-80 6S-90 690-100
hr. Boil, psi-% W.F. 312-03 323-1 274-0 522-30 171-0 443-2 112-0 558-52 60-0
48 hr. Soak, psi - % W.F. 482-49 509- 486-23 S96-32 415-2 S06-50 416-0 S64-75 442-0
2 Week Cured
Dry, psi - % W.F. 534-100 587-100 648-88 890-100 731-100 812-100 876-82. 732-100 794-90
2 Cycle Boil, psi - % W.F. 281-2 251-0 290-0 216-0 Del. 162-0 48-0 276-0 48-0
48 Hr. Soak, psi - % W.F. 469-100 498-59 526-25 628-62 374-0 558-49 4.25-0 586-50 459-2
"about 0.21 gm equivs. catalyst/100gm solution
Del. = delaminated

The adhesive composition may also include, instead 60 The procedures used in testing the control and instant
of the terpolymerized resin emulsion described herein adhesive compositions of Tables I, II and III were as
before, a resin emulsion containing about 90-98% by follows. The test samples were prepared in accordance
weight vinyl acetate copolymerized with about 2-10% with ASTMD-906-64 (Reapproved 1970), herein incor
by weight of an N-alkylol derivative of an amide of an porated by reference, and applied to the birch test pan
alpha, beta-unsaturated carboxylic acid, preferably N 65 els at a glue spread rate of 40 lb./1000 sq. ft. single glue
methylol acrylamide. line, assembly time of 1 minute, a press temperature of
The following are illustrative but non-limitative ex 121 C, a press time of three minutes and a pressure of
amples in table form of the adhesive compositions of the 150 psi.
 4,085,074
5 6
The one-half hour boil test was carried out in accor and an N-alkylol derivative of an amide of an alpha,
dance with ASTM D-1151-72 using a preconditioning beta-unsaturated carboxylic acid in an aqueous medium
under par. 4.1 of one day and condition 16, i.e. inner containing about 3-6% by weight of a hydrocolloid
sion in boiling water for one-half hour and determining selected from the class consisting of polyvinyl alcohol,
the average strength after exposure in accordance with hydroxyethylcellulose and carboxymethylcellulose, by
par. 5.2.1. weight of the monomer mixture, (b) an acidic metal salt
The 2-cycle boil test was carried out in accordance cross-linking catalyst selected from the class consisting
with Commercial Standard CS35-61, Hardwood Ply of aluminum chloride, aluminum nitrate, chromic chlo
wood, published by U.S. Dept. of Commerce, Sup. of ride and chromic nitrate in an amount of about 0.0032 to
Docs., Washington 25, D.C., which is herein incorpo 10 0.025 gram equivalents per 100 grams of the resin emul
rated by reference, par. 5.4.2 thereof. sion, and (c) a cross-linking inhibitor selected from the
The 48 hour soak test is carried out in accordance class consisting of ammonia, alkyl amines and alkylol
with the procedure of ASTM D-1151-72, condition 6, amines wherein the mole ratio of the cross-linking inhib
wherein the specimen is immersed in water at a temper itor to catalyst ranges from a minimum of about 0.1 to
ature of 23 C for 48 hours and then subjected to the 15
0.2 to a maximum of about 0.7 to 1.7.
shear strength test. 2. The adhesive composition of claim 1 in which the
The shelf or pot life end point is taken as the time at polymerized vinyl acetate is made from a monomer
which the adhesive composition gels to the point that it mixture of about 90-98% vinyl acetate and about
will no longer flow from the container. The sample is 2-10% of an N-alkylol derivative of an amide of an
not agitated during the total test period and the con 20 alpha, beta-unsaturated carboxylic acid, by weight.
tainer is tightly capped so that no skin is formed. 3. The adhesive composition of claim 1 wherein the
It is to be noted that the pH of the RE resin emulsion
is about 4.5 to 5.5 without the addition of the AlCl N-alkylol derivative of an amide of an alpha, beta
solution thereto. When about 1.5 to 12.0 parts by weight unsaturated carboxylic acid is N-methylol acrylamide.
of the AlClssolution (containing about 0.21 gram equiv 25 4. The adhesive composition of claim 1 wherein the
alents AlCl/100gms) is added to 100 parts by weight of mole ratio of the inhibitor to the catalyst is sufficient to
the resin emulsion to thereby provide about 0.0032 to at least increase the shelf life of the resin emulsion plus
0.025 gram equivalents AlCl/100gms emulsion, the pH catalyst alone, the adhesive composition when applied
is lowered to about between 3.10 and 3.35 to 2.40. How to substrates providing a cured water resistant bond of
ever, the pH is then raised by the addition of the basic at least 50 psi when subjected to a one-half hour boil
triethanolamine in a mole ratio of TEOA/AICls of 0.68 test.
to 1.67 to about 3.4 to about 3.8. The triethanolamine 5. The adhesive composition of claim 1 wherein the
acts as a cross-linking inhibitor. It is postulated, al alkyl ester of acrylic acid is ethyl acrylate and the N
though the mechanism of action is not known to appli alkylol derivative of an amide of an alpha, beta
cant, that this inhibition may occur because the trietha 35 unsaturated carboxylic acid is N-methylol acrylamide.
nolamine raises the pH of the adhesive composition to 6. The adhesive composition of claim 5 wherein the
thus slow the catalytic action of the AlCls but not to the catalyst is aluminum chloride in an amount of about
lower pH value of 4.5 for the resin emulsion without the 0.0032 to 0.025 gram equivalents of AlClper 100 grams
catalyst, which would apparently destroy its adhesive of resin emulsion.
property. Another postulation is that triethanolamine 7. The adhesive composition of claim 6 wherein the
being a chelating agent ties up the Al- ++ and pre cross-linking inhibitor is triethanolamine.
vents the AlCl4 from catalyzing the cross-linking of the 8. The adhesive composition of claim 7 wherein the
resin polymer; then, curing the adhesive under pressure hydrocolloid is polyvinyl alcohol.
and elevated temperatures, the chelation is broken re 9. A pre-mixed catalyzed adhesive composition com
leasing the catalyst to initiate the cross-linking required 45 prised of (a) an aqueous cross-linkable vinyl acetate
to provide the adhesion. emulsion of a terpolymer made by polymerizing a mon- .
The instant adhesive composition is directly applica omer mixture of about 90-92% vinyl acetate, about
ble to semi-porous and porous substrates, such as hard 4-6% ethyl acrylate and about 2-5% N-methylol acryl
woods, softwoods, hardboard, particle board, high amide, in an aqueous medium containing about 3-6% of
pressure laminates and similar materials in appropriate SO
polyvinyl alcohol by weight of the monomer mixture,
pressing equipment in open assembly time up to about (b) an acidic catalyst of about 0.0032 to 0.025 gram
five minutes and closed assembly time up to about equivalents of aluminum chloride per 100 grams of the
twenty minutes. The adhesive is primarily applicable to resin emulsion and (c) a cross-linking inhibitor of trieth
hot press (pressures of about 25-200 psi) or high fre
quency cure although it will produce an effective Type 55 anolamine,
to 1.7 of
in a mole ratio of about 0.1-0.2 to about 0.7
triethanolamine to aluminum chloride.
II water resistant bond when pressed at room tempera 10. A structure comprising two substrates bonded
ture (25° C) for about 40 minutes. The press time will together by the adhesive composition of claim 1 in a
vary depending on the type of press, method of cure, cured condition.
temperature, spread rate, assembly time and type of
substrates being bonded. 60 11. A structure comprising two substrates bonded
What is claimed is: together by the adhesive composition of claim 2 in a
1. A pre-mixed catalyzed adhesive composition com cured condition.
prised of (a) an aqueous cross-linkable vinyl acetate 12. A structure comprising two substrates bonded
resin emulsion including polymerized vinyl acetate, in together by the adhesive composition of claim 4 in a
which the polymerized vinyl acetate is made from a 65 cured condition.
monomer mixture of 80-97% vinyl acetate and 3-20% 13. A structure comprising two substrates bonded
of a mixture of an alkyl ester of an acid selected from together by the adhesive composition of claim 5 in a
the class consisting of acrylic acid and methacrylic acid cured condition.
 4,085,074
7
14. A structure comprising two substrates bonded 17. The adhesive composition of claim 1 wherein the
together by the adhesive composition of claim 6 in a N-alkylol derivative of an amide of an alpha, beta
cured condition. unsaturated carboxylic acid is N-methylol acrylamide.
15. A structure comprising two substrates bonded 18. The adhesive composition of claim 1 wherein the
together by the adhesive composition of claim 7 in a catalyst is aluminum chloride and the inhibitor is trieth
cured condition. anolamine.
16. A structure comprising two substrates bonded 19. The adhesive composition of claim 1 wherein the
together by the adhesive composition of claim 9 in a hydrocolloid is polyvinyl alcohol.
k . . . . . . .
cured condition.
10

15

20

25

30

35

45

50

55

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 UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 4,085,074 Dated April 18, 1978
Inventor(s) Mind Cho Woo
It is certified that error appears in the above-identified patent
and that said Letters Patent are hereby corrected as shown below:

Col. l, line 25, change "ot" to ---to---.

RUTH C. MASON DONALD W. BANNER