CA1331495C - Adhesive for low temperature applications - Google Patents
Adhesive for low temperature applicationsInfo
- Publication number
- CA1331495C CA1331495C CA000606983A CA606983A CA1331495C CA 1331495 C CA1331495 C CA 1331495C CA 000606983 A CA000606983 A CA 000606983A CA 606983 A CA606983 A CA 606983A CA 1331495 C CA1331495 C CA 1331495C
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- adhesive
- core
- methyl methacrylate
- shell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
Abstract
ADHESIVE FOR LOW TEMPERATURE APPLICATIONS
Abstract of the Disclosure Adhesive compositions are made from methacrylate ester monomers, elastomeric polymers having a Tg below -25°C and which are soluble in the monomers, core-shell polymers which swell in the monomers but do not dissolve therein, and free radical producing catalysts. These adhesive compositions when used in bonded assemblies exhibit a combination of high adhesive bond impact strength and high bulk tensile elongation.
Abstract of the Disclosure Adhesive compositions are made from methacrylate ester monomers, elastomeric polymers having a Tg below -25°C and which are soluble in the monomers, core-shell polymers which swell in the monomers but do not dissolve therein, and free radical producing catalysts. These adhesive compositions when used in bonded assemblies exhibit a combination of high adhesive bond impact strength and high bulk tensile elongation.
Description
13314~5 ~
AD~ESIVE FOR LOW TEMPERATURE APPLICATIOMS
Backqround of the Invention The field of art to which this invention pertains is structural acrylic adhesives.
5Structural acrylic adhesives are rubber-toughened adhesive systems that cure rapidly at room temperature to give e~cellent adhesive properties. Such adhesives are characterized by high peel strength, shear strength and chemical resistance. They are also tolerant of a variety of substrate surface contaminants, such as oil.
Fast curing adhesives are described in U.S. Patent No.
3,832,274. These adheslves are made from elastomers having Tg of less than 15 F, acrylic monomers and a redox catalyst. .
Structural adhesives which contain chlorosulfonated polyethylene or sulfonyl chloride and chlorinated polymers are disclosed in such patents as U.S. 3,890,407, 3,962,372 and 4,287,106.
U.S. Patents Nos. 4,126,504, 4r348r503 and 4,451,615 ~: disclose various combinations of elastomers, acrylic monomers, catalysts and other additives. .
Adhesives based on diene polymers, such as polybutadienes, polyisoprenes, butadiene-styrene copolymers and ABS graft polymers, plus villyl monomers, adhesion promoters and the like are described in ~.S. Patent No. 4r287~106.
AD~ESIVE FOR LOW TEMPERATURE APPLICATIOMS
Backqround of the Invention The field of art to which this invention pertains is structural acrylic adhesives.
5Structural acrylic adhesives are rubber-toughened adhesive systems that cure rapidly at room temperature to give e~cellent adhesive properties. Such adhesives are characterized by high peel strength, shear strength and chemical resistance. They are also tolerant of a variety of substrate surface contaminants, such as oil.
Fast curing adhesives are described in U.S. Patent No.
3,832,274. These adheslves are made from elastomers having Tg of less than 15 F, acrylic monomers and a redox catalyst. .
Structural adhesives which contain chlorosulfonated polyethylene or sulfonyl chloride and chlorinated polymers are disclosed in such patents as U.S. 3,890,407, 3,962,372 and 4,287,106.
U.S. Patents Nos. 4,126,504, 4r348r503 and 4,451,615 ~: disclose various combinations of elastomers, acrylic monomers, catalysts and other additives. .
Adhesives based on diene polymers, such as polybutadienes, polyisoprenes, butadiene-styrene copolymers and ABS graft polymers, plus villyl monomers, adhesion promoters and the like are described in ~.S. Patent No. 4r287~106.
2~Methacrylate based adhesives which contain chlorinated or ::
1 33 1 ~95 .
chlorosulfonated polyethylene polymers and graft copolymers of the core-shell type are disclosed in U.S. Patent No. 4,536,546.
With the use of more and more plastics in structures, e.g. automobiles, there is a continuing and even increasing need for adhesives which can be used on plastics as well as metals to form bonds which will hold up under a wide variety of adverse conditions.
There is a particular need for structural adhesives which not only have high adhesive bond impact strength but also have high bulk tensile elongation when measured at low temperatures. ~ :
Summary of Invention :~
This invention is directed to structural adhesive~ ~
compositions. In one aspect, this invention pertains to~;
structural adhesives which have high adhesive bond impact .
:
strength. In another aspect, this invention relates to .:
structural adhesives which have high bulk tensile elongation -when measured at temperatures of -10F (-23C) or lower. In still another aspect, this invention relates to structural -~
~ .
adhesives, the bulk tensile elongations of which are largely . ::: .:
reversible even at low temperatures.
The adhesive compositions of this invention are generally ~ ~ .
comprised of a) about 55 to about 75 weight percent of a methacrylate ester monomer such as methyl methacrylate, b) 0 to about 15 weight percent methacrylic acid, c) about 5 to about 20 weight percent of an elastomeric polymer such as polychloroprene, nitrile rubber, or a block copolymer or isoprene and styrene which is soluble in methyl methacrylate and which has a Tg below about -25C and d) about 10 to about 30 ;;, :.
weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein the weight percents are based on the total weight of (a), (b), (c) and (d).
,:
` `-" 13314q5 The adhesive compositions of this inventio~, when used in bonded assemblies, exhibit a combination of high adhesive bond impact strength (at least 15- ft-lb/s~.in.) and high bulk tensile elongation (~reater than 10 percent~ when measured at -10F
(-23C) or below.
Descri~tion of the Invention The monomers useful in this invention are methacrylate ester monomers wherein the alcohol portion of the ester group contains one to eight car~on atoms. Examples of such ester monomers are methyl methacrylate, ethyl methacrylate, 2-ethyhexyl methacrylate, cyclohexyl methacryla~e and mixtures thereof. The preferred ester monomer is methyl methacrylate.
Additional monomers which can be used in combination with the methacr~late monomers are acrylate esters wherein the alcohol portion of the ester contains 1 to 8 carbon atoms, examples of which are methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethyhexyl acrylate. Other useful monomers are acrylonitrile, methacrylonitrile, styrene, vinyl toluene, and the like.
The useful monomer composition contains at least about 50 weight percent methacrylate monomer and, preferably, at least about 50 weight percent methyl methacrylate monomer.
. . .
Additional monomers which are used in combination with the methacrylate ester monomers are free radical polymerizable `
e~hylenically unsaturated mono or polycarboxylic acids. Acrylic -acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid are examples o~ such acids. The preferred acid is , 1331~9~
methacrylic acid.
The elastomers useful in this in~ention have a second order glass transition temperature (Tg) of less than -2S and are soluble in the monomers described hereinabove. Useful elastomers are synthetic high polymers which exhibit plastic flow. The preferred elastomers are those which are supplied commercially as adhesive or cement grades.
A pre~erred class of elastomers for use in this invention are polychloroprene and copolymers of butadiene or isoprene with styrene, acrylonitrile, acrylate estexs, methacrylate esters, and the like. Additional useful elastomers are copolymers of ethylene and acrylate es~ers, homopolymers of epichlorohydrin and , ~ copolymers of epichlorohydrin and ethylene.
: ., .: ., : :
Specific examples of useful polymers using their letter ~15 designation according to ASTM D1418, their trade or common name ~ y and chemical description are: CR-Neoprene-polychloroprene;
. . , ~,, :. .
NBR-Nitrile rubber-butadiene acrylonitrile copolymer containing ``~ ~
.- - .
; about 25 to about 45 weight percent acrylonitrile; COX - Hyca~
1072-butadiene-acrylonitrile copolymer modified with carboxylic ~20 groups; SBR-GR-S-styrene-butadiene copolymer containing about 10 to about 30 weight percent styrene; ABR - Acrylic rubber acrylàte butadiene copolymer; and CO, ECO-~ydrin*100 and 200-homopolymer or a copolymer of epichlorohydrin and ethylene oxide. Additional useful elastomers are copolymers o~ e~hylene and acrylate esters, such as methyl acry:Late and ethyl acrylate, ~herein the copolymer contains a~ least 30 weight percent acrylate ester which * Trade Marks elastomers are sold commercially by duPont under the Vamac trademark.
Elastomers useful in this invention are described in detail in the "Handbook of Plastics and Elastomers" pages 1-106-119, (1975) McGraw-Hill, Inc., which may be referred to ~or further detail.
Particularly useful elastomers are polychloroprene and block copolymers of styrene and butadiene or isoprene, such block copolymers being sold under the trademark Kraton by Shell Oil Company. Block copolymers of styrene and diene monomers are described in detail in U.S. Paten~s No. 4,041,103 and 4,242,470 which may be referred to for further details.
Other elastomeric polymers having a Tg below -25C and .. . .
solubility in the methyl methacrylate monomer can be employed since, other than the low Tg and solubility characteristics, there are no other limitations on the identity o~ the elastomers except for the specific requirements of the particular adhesive being formulated, such as suitable molecular weight, viscosity characteristics and compatibility with the other ingredients of the adhesive.
Use~ul elastomers are those which are soluble in the monomers used in the adhesives of this invention. These elastomers can form solutions of from about 10 to about 35 weight percent elastomer in methyl methacrylate. As used herein the term "solution " is intended to cover not only true solu~ions but colloidal dispersion which exhibit normal or substantially newtonian rhe~logy characteristics.
,: ~
,~ ~
The core-shell graft copolymers useful in this invention have a "rubbery" core, a "hard" shell, and swell in the monomer compositions but do not dissolve therein. The "core" or backbone polymer of the graft copolymers has a glass transition temperature substantially below ~nbient temperatures. The "shell" polymer which is grafted onto the backbone polymer has a ;
glass transition temperature substantially above ambient ~ ~ ~
temperatures. Ambient temperature is defined as the temperature ~;
range in which the adhesive is used. -Examples of useful core-shell graft copolymers are those where "hard" monomers, such as styrene, acrylonitrile or methvl methacrylate, are grafted onto a rubbery core made from polymers or "soft" or "elastomeric;' monomers, such as butadiene or ethyl acrylate. ~ ;~
::
U.S~ Patent No. 3,985,703, which may be referred to for further details, describes useful core-shell polymers, the cores o~
which are made prefexably from butyl acrylate but can be based on ethyl, isobutyl, 2-ethylhexyl, or other alkyl acrylates or mixtures thereo~. The core polymer, optionally, can contain up to 20 percent of o~her copolymerizable monomers, such as styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene and the like. The core polymer optionally, can contain up to 5 percent ~i,, .
of a crosslinking monomer having two or more nonconjugated double bonds of approximately eoual reactivity, such as ethylene glycol ;~
~25 diacrylate, butylene glycol dimethacrylate and the like. It also optionally can contain up to 5 percent of a graft-linking monomer .., .- . i.
1 331 4q5 having two or more nonconjugated do~le bonds of unequal reactivity, such as diallyl maleate and allyl methacrylate.
The shell stage is preferably polymeriæed ~rom methyl methacrylate and optionally other lower alkyl methacxylates, such as ethyl, butyl, or mixtures thereof. Up to about 40 percent by weigh~ of the shell monomers can be styrene, vinyl acetate, vinyl chloride/ and the like.
Additionally useful core-shell graft copolymers are described in U.S. Patents No. 3,984,497, No. 4,096,202, and No.
4,034,013, which may be referred to for further details.
Still other useful core shell polymers are the "MBS"
polymers such as those described in UOS. Patent No. 4,304,709 wnich may be referred to for further detail. The MBS polymers are made by polymerizing methyl methacrylate in the presence of polybutadiene or a polybutadiene copolymer rubber.
Other patents which describe various useful core-shell graft copolymers are U.S. Patents No. 3,944,631, No. 4,306,040 and No.
4,495,3~4, each of which may be referred to for further details. -The core-shell gra~t polymers used in this invention swell in size in the adhesive formulation but do not dissolve. The adhesives, so formulated, exhibi~ improved spreading and 1Ow properties which are highly desirable in many adhesive ;
applications. For example, when an adhesive is applied to an article by means of a syringe-type application, many adhesives "string-out" between the point where the applicator was applied and the next position of the applicator. With the present ,.'; : ~
.... , ,, ... . . .. . .. . .. ,.. ,.. , . ., ,., ~., .. ~. ,. ... ,.. ,.~. ,,.. ,. .,,,;.. ... .
~ ' ' ' ~ ' I ' , ~ , ! ' , ' ', ._.
~ 1 33 1 495 invention, a small drop of adhesive can be applied to the article to be bonded with no adhesive string forming~
Additional components of the composition of this invention are polymeriæation catalysts with or without other components which enhance the reactivity of the calalysts. The catalysts are free radical generators which trigger the polymerization of acrylate and methacrylate compounds. Such catalysts are peroxides, hydroperoxides, peresters, peracids, radiant energy, e.g., ultraviolet light, and heat. Examples of these catalysts are benzoyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, tertiary butyl peroxide acetate, tertiary butyl perbenzoate, ditertiary butyl azodiisobutyronitrile and the li~e. These free radical producing catalysts are used in amounts of about 0.01 to about 10 weight percent based on the weight of the adhesive composition.
Pre~erably, the catalysts will be used in the amount of about 0.05 to about 3 weight percent.
Other components which enhance the reactivity of the catalysts are initiators or activators and promoters. Initiators and activators, which terms are used interchangeably, include tertiary amines and aldehyde-amine reaction products. Useful tertiary amines include N,N-dimethylaniline, N,N-dimethyl-toluidine, N,N-diethylaniline, N,N-diethyltoluidine and the like.
Aldehyde-amine reaction products include such compositions as butyraldehyde-aniline and butyraldehyde-butylamine compositions.
A promoter is an organic salt of a transition metal, such as .~ -. . .
~,- . . .
,'; :;;',i . ~:;
-8- ; ~
: ';'' ' .`'~' 1 331 49~
cobalt, nickel, manganese or iron naphthenate, copper octoate, copper acetylacetonate, iron hexoate, or iron propionate.
The initiators or activators, iiE used, are added in the amount of up to about 15 weight percent based on the weight of the adhesive. Preferred amounts are 0~01 to about 5 percent.
Promoters are used in amounts up to about 0.5 weight percent, preferably about 1 part per million to about 0.5 weight percent.
The compositions o~ this invention are usually prepared in two parts wherein 1 part contains the free radical catalysts and the other part contains the initiator or activator and the promoter if it is used. Just prior to use, the two parts are mixed together and the mixtur~ is applied to at least one of the surfaces to be bonded. Alternatively, the part containing the catalyst can be applied to one surface and the part containing the activator can be applied to the other surface. When pressed together, the two parts mix together and polymerization with resultant adhesive bonding takes place.
The adhesive compositions of this invention will contain about 55 to about 75 weight percent methacrylate ester monomer, 0 to about 15 weight percent acid monomer, about 5 to about 20 weight percent elastomer and about 10 ~o about 30 weight percent core-shell graft copolymer, said weight percents being based on the total weight of the components. Preferably, the compositions contains about 60 to about 70 weight percent methacrylate ester monomer, about 2 to about 10 weight percent acid monomer, about 8 to about 15 weight percent elastomer and about lS to about 20 we~ght percent core--shell graft copolymer.
1 33 1 4q5 The adhesive compositions of this invention have high adhesive bond impact strength (>15ft-lb/sq~in) and hign bulk tensile elongation (>10 percent) when measured at -10F (-23C) or below. The bulX tensilè elongation of these compositions is largely reversible even at low test temperatures. This reversible high elongation contributes to the superior performance of these adhesives in structures which undergo impacts at low temperatures.
The compositions of this invention are par~icularly useful for bonding thermoplastic automobile bumpers which must pass simulated crash impact tests at -10 to -20F (-23 to -29C).
In these tests, which measure energy management capability, .. .. ~; . .
bumpers are mounted horizontally and are impacted at various positions and angles with a pendulum or hydraulic ram at a rate that simulates a 2.5 or a 5 mile per hour crash. In this test, the bumper and the adhesive bondline experience both high impact -forces and a deflection of as much as 3 or 4 inches at the `
center. After the test, the bùmper springs back to its original shape. The high impact strength and high elongation, especially ~ --reversible elongation at low temperatures, of the compositions of this invention are clearly advantageous in this bumper -application.
The combination of relatively high modulus up to temperatures of 180F (82C) and high impact strength and ~;
elongation at temperatures of -10F (-23C) or below is very ad~antag~ous for bumpers and other structural applications which -10- ; "
' ' ' . :. ` ' 1 331 4qS
require high stiffness and structural integrity together with resistPnce to impact and other high stresses.
In the following examples, the elastomers were dissolved in the monomers by mixing until a uniform solution was obtained and no visible rubber particles were present. The other components, e.g., the core-shell polymers were then added to the elastomer solution and were stirred until a coarse paste was formed.
Further mixing with a high shear dispersion apparatus was continued until a smooth paste was obtained.
Adhesive strength tests were performed by mixing the formulations with a peroxide catalyst paste, or by combining two ~; ~ adhesive polymer-in-monomer solutions, one of which contained a peroxide, the other a catalyst activator.
The adhesives were tested as follows:
La~ Shear Strenqth (ASTM D-1002) The adhesive shear strength of bonds formed between substrates, e.g., a polycarbonate/polyester thermoplastic resin (Xenoy*, obtained from General Electric Company), was measured by ;
applying sufficient adhesive to one end of a 25 mm x 76 mm x 6.3 mm coupon of the substrate to completely fill a 25 mm x 12.5 mm x ! ,~ .25 mm bond gap. A 0.25 mm wire shim or washer was used to control bond thickness. A second coupon was placed over the coupon coated with adhesive to provide the proper lap shear configuratlon in a mold designed to properly align the specimen.
After a cure time o~ 24 to 48 hours at room temperature, the bonds were tested at a separation rate of 1.27 mm per minute.
* Trade Mark ~.
Im~act Strenqth (ASTM_D-950~
The impact strength of the adhesives was tested using the procedure of ASTM D-950 except that steel bars or rods having diameters of 12.7 mm and lengths of 76.2 mm and 9.5 mm, respectively, were used instead of t:he test specimens having dimensions specified in the ASTM testing method. Surfaces to be bonded together were first solvent cleaned and then grit blasted.
After being bonded, the specimens were conditioned for two days at room temperature prior to testing.
Bulk Adhesive Stress - Strain (ASTM B-638) Sufficient adhesive components were mixed to form a sheet of cured adhesive approximately 2.5 mm in thic~ness from which tensile test "dumbbells" were cut using a metal die as specified in the ASTM testing method. Unless otherwise specified, the stress-strain tests were performed at the indicated temperatures using a separation rate of 5 mm per minute.
Cold Im~act Test on Plastic Substrates This test was devised to simulate the impact and deflection forces that bonded structural assemblies, such as bumpers, experience under test conditions. This test was useful in evaluating the effect of "squeeze-out" at bond edges on the impact performance of the overall bonded assemblies. If the cured adhesive is not sufficiently elastic to relax under impact and elongation conditions, a crack can initiate in the adhesive bead and ~ropagate through the bonded assembly, leading to failures.
'' , , -12~
' ., ' In conducting the tests, a lS.2 cm long 5 gram bead of mixed adhesive was applied lengthwise on the centerline of a 15.2 cm x 2.5 cm plastic coupon. A 2.5 cm length of 1.3 mm diameter stainless steel wire was placed approxi~ately 6 mm from each end parallel to the plastic and perpendicular to the bead of adhesive. A 15.2 cm x 1.3 cm plastic strip was pressed down onto the adhesive until it made contact with the wire. The bonded assembly was allowed to cure at room temperature for at least 24 hours.
Before testing, the assembly was placed in a -10F (-23c) freezer for at leas~ 15 hours. The cold sample was tested by placing it in a modified National Forge Model TM S2004 Izod-Charpy impact tester fitted with a 10 ft/lb hammer. A
fixture was used to hold the sample at each end with the 2.5 cm plastic strip facing the impact hammer and the hammer was allowed to impact the plastic. The area of the hammer which contacts the -plastic is approximately 1 cm2. At the lowest point in the swing ; where the assembly is impacted, the hammer is travelling at 11 feet per second. If, after the hammer impacts ~he cold plastic, the hammer re~ounds and the test specimen remains intact, the result is recorded as a pass. If the plastic breaks at the point . .
of impact, the result is recorded as a failure. Occasionally, the hammer impacts the plastic and rebounds~ but the end of the plastic in the fixture cracks. This is recorded as an "end crack". It is considered a gualified pass, since the action of the fixturing assembly against the plastic imposes extraordinary - , .' ~ ' ~' : :- : .::
- : ::
. . ~, . ..
stresses on the bonded asse~bly at these fulcrum points.
The components used in the examples are identified as follows:
-,':-MMA - Methyl methacrylate monomer containin~ 22-28ppm of hydroguinone inhibitor MAA - Methacrylic acid cont:aining 250 ppm of :,.
hydroquinone inihibit:or ~ :
BMA - - Butyl methacrylate ~
2-EHMA - 2-Ethylhexyl methacrylate ~ .
Neo~rene - Polychloroprene homopolymer having a Brookfield solution viscosity (S weight percent in toluene) of about 20 to 3~ mPa as measured on Model LVT
visometer with UL adaptor Nitrile - Carboxy modified butadiene-acrylonitrile ~lastomer Rubber with medium acrylonitrile content, specific O
gravity of 0.98 and Mooney viscosity ML-4, 212 F ~. .
of 30-45 :~ :
Hypalo~ - Chlorosulfo~ated polyethylene containing 43 percent chlorine and l.l percent sulfur - duPont :-Paraloid* - Core-shell polymer of methacrylate-butadiene - -~
KM 753 styrene with high butadiene content - Rohm & Haas . Paraloid* - All acrylic core-shell polymer - Rohm & Haas . ~.
:~ ~M 330 ~ ~
: Geloy* - Core-shell polymer of acrylate rubber core and ~ -1020 styrene~acrylonitrile shell 25 Hydrin* - Liquid epichlorohydrin hgmopolymer with5a 10 x 1 BrookfOeld viscosity (27 C) of 2.5 x 10 cps, a Tg . ~:
of -25 C and a number average molecular weight of 4,000.
DMT - N,N-dimethyl-p-tolidine `
ZMTI - Zinc 2-mercaptotoluimidazole ~ .
VAMAC* ~ ethylene-methyl acrylate copolymer gum-duPont KRATO~ - st:yrene-isoprene branched copolymer-D 1320x Shell Oil Co.
"~ ,. ..
* Trade Marks .. ~ .
TYRIN* - Chlorinated polyethylene containing 42% chlorine, Dow Che.~.ical Co.
DPESC - Diphenyl ether disulfonyl chloride BH~ - 2,6-Di-tert butyl p-cresol CHP - Cumene hydroperoxide r 80 weight percent in cumene ~PO Paste - A paste o~ 55 percent: benzoyl peroxide in benzyl butyl phthalate plast:icizer VANAX*808 - Butyraldehyde-aniline condensation product - R..
Vanderbilt Co.
The Peroxide Paste used in the examples was prepared as follows: Hydrin lOxl, 25 parts by weight, and trioctyl trimellitate plasticizer, 25 parts by weight, were placed in a plastic container and were heated to 110F (43C). KM 753, 10 parts was gradualIy added as the mixture was sheared with a laboratory Hochmeyer high shear mixture. After all the KM 753 ~; had been added, shearing was continued for 5 minutes. The ~; mixture was then ~laced in a 110F (43C) oven for one hour and was again sheared until a smooth paste was obtained. After cooling, the BPO paste, 40 parts, was added and the mixture was again sheared until a uniform smooth paste was obtained.
The following tables list components used to formulate adhesive compositions and show test results o~ cured adhesives.
In preparing the adhesives, the Neoprene, nitrile rubber ~and Hypalon elastomer were dissolved in MMA to give solutions of 20, ~ 25 25 and 40 weight percent, respe~tively. All other ingredients `~ were combined by clirect addition and were mixed as described ~-.,, . ,~, hereinbefore.
* Trade Marks : ~ --.,~, ~::.
~ 15 ;~
- 1 33 1 4q5 ~;., The examples which have A and B parts are two part adhesives which are combined in a ~:1 weight ratio just prior to use. In the other examples (the 1 part adhesivesl~ the Peroxide Paste was added prior to use, the mix ratio being 1:10 paste to adhesive.
Table I illustrates greatly lmproved cold elongation of the compositions of this invention, Ex 1 and 2, compared to a prior art example, Ex 3.
TABLE I
Exam~le 1 _ 2 3 A B
Composition - --5 Parts.by wt MM~ 62.85 60.25 54.40 74.65 MAA 5.0 5.0 9.7 Neoprene 11.4 Nitrile rubber 14.0 ::
1~ Hypalon 30 23.3 Paraloid KM 753 20.0 20.0 12.05 :
Paraloid KM 330 8.2 . :
Geloy 1020 9.6 DMT 0 75 0 75 -~
~:15:CHP 0 3 ~ :
Vanax 808 Peroxide Paste 10 10 ~-;
~ ~ stress/strOin .
:20 at ~ O F
: (-24 + .5 C) Tensile s~rength :;
::~ at break, psi 5300 4800 6000 Elongation at break 25% Average 23 30 % Maximum 26 44 12 Tg, C of elastomer -39 -20 & -30 10C `. ;
: , ~
,,~ . .' '~' :','', ;' ' ~ `,.':. :
-17~
- - . .,..:
.~ ." ~, 1 331 ~95 Table II illustrates the improvement in impact resistance at low temperatures of plastic assemblies bonded with the compositions of this invention, Ex 4 and 5, compared with a prior art composition, EX 6. The steel imp~ct tes~ resu'ts show that Ex 4, 5 and 6 have similar impact strengths when measured by conventional methods.
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TABLE II
ExamPle _ _ 4_ 5 6 A B A
Composi~ion 5 ~ts bY wt . - ~ .. . .
MMA 62.5 61.0S 72.0554. ~0 74.65 MAA 5.0 9.6 9.7 Neoprene 11.35 11.05 11.25 ~ ;
Hypalon 30 23.3 Paraloid KM 753 19.9 14.45 14.75 12.05 Paralsid KM 330 8.2 Geloy 1020 9.6 DMT 0.75 1.95 CHP
~15 BHT .25 ZMTI 0.5 Vanax 808 7.55 ;
Peroxide Paste 10 ~PO Paste 3.85 Lap Shear Stgth, psi 1555 1595 1460 ;
on Xenoy 1102 Cold Tmpact Test Pass 6 4 on xenoY 1102 Fail 0 1 S
-12 ~ 2~F Crac~ 0 1 0 S~eel Impact Stgth. l9. S 23.1 22.0 .... .. ~: ~.
.. . ~ ~ . . ~, : ;: ~ , . .~ :.
. ~ ~... ...; .
- ~: :.
-; ~,:, :. . :
- - ... , .. ,,,, ~
~ :: .
~- 1331~95 Table III lists additional examples of adhesive compositions which provide adhesives with high elongation and resistance to low temperature impact failures when used to bond plastic.
Examples 7 and B are made using elastomers having Tg's of less than -25C, Example 9 uses an elastomer having a Tg higher than : ' "
.
' ~'' , -20- ~ ~
r~
1 331 4q5 TABLE I I I
Exam~le _ _ 7 8 9 _ A B A B AB
Composition BMA 35 - 5 73 - 5 35 - 5 73 - 5 35 5 73 - 5 ;~ ; ~
~AA 10 10 10 ,. ~,' 10 ~AM~C G 11.5 11.5 ,~
KRATON 11.5 11. 1 5 TYRIN 11.5 1 .
Paraloid KM 753 15 15 15 15 15 15 DMT 2 2 2 ~;
Elongation % at -11 + 1F 17 20 5 24 + .5 C) teeltlm~aC~t T20F ( -29C ) 24 - 4 21.0 8.9 Cold impact test 12x+no2~Fllo2 ~ 83 100 17 -24 + .5~C~
~ ~2 %gP 8c of Elastomer -27.8 -56 +10 : ., , ~
.' ,:: ., '' .
:~ ~
, .~ ,:',',,, .' -21- - ~ ~
'` ;'''`'`''.',~
13314q5 The examples listed in Table IV show additional adhesive tested at low temperatures. The Example 10 adhesive contains a core-shell polymer but no low Tg elastomer. Example 11 has a core-shell polymer and an elastomer having a Tg above - 25C.
Example 12 has a low Tg elastomer but no core-shell polymer.
Example 13 contains a low Tg elastomex and no core-shell polymer.
This adhesive exhibits decreased bonding strength on Xenoy plastic as shown in Table V. Example 14 contains both a low Tg elastomer and a core-shell polymer.
1 331 ~q5 :, .,.: .
", TABLE I~
. .
~x~le 10111.213 14 A B
Composition ;
5Dart by wei~ht , .
MM~62.8562.8~6~.27 62.85 62.60 66.74 ~AA 5.05.0 5.05.0 9.68 Neoprene 24.98 11.15 11.15 Nitrile rubber 31.4 10Hypalon 30 11.4 Paraloid R~ 753 31.4 20.0 14.56~ 14.56 DMT 0.75 0.75 0 75 0 75 0.3 -B~T 0.25 ~15 Vanax 808 , 7-55 DPESC 1.46 Peroxide Paste10 10 10 10 Stress/Strain ;~
a~ 1 ~-24 + .5 C
Tensile Stgth at break, psi6031 6980 3029 5025 4975 Elongation at break % AVG <5% <5% 6% 52% 11 ~AX <5~ <8~ 6~ 70~ 16% ~ ;
~25 Tg ~C o~ ela~tomer +10 -34.3 -20 & -30 -34.3 i ~
, ~ .~ :..., .-,., ,;, . ,.;, ,:, ,.
' .' ...., - :.~ .
'"'.~'., .~ '., , :;:','~'':.
,`",'~,',, '',,' ~ i ' ~'. .''' " `'' 1 33 1 ~
The examples listed in Table V illustrate the decrease in adhesion to Xenoy plastic with increasing levels of nitrile rubber. Example 15 which contains the highest ~mount of nitrile rubber and no core shell pol~mer h,as the lowest Lap Shear Strength on Xenoy plastic. Examples 16 and 17, which contain elastomer and core-shell polymer within the limits of the invention, have good tensile strength elongation at break and adhesion to Xenoy plastic. Example 18 which contains less elastomer than claimed in the inven~ion has good tensile strength lo and adhesion but poor elongation at break.
.:
, ~`
-13314C)5 TABLE V
Example _ 15 16 17 _ 18 Composition :
parts by weight MMA 70.9 60.3 ~8 63.4 :~
Nitrile rubber 23.6 14.1 6.5 1.3 Paraloid KM 753 20.1 30 29.8 ~:
DMT .5 .5 .5 .5 10 Stress/StrOin ; ::`
at -11 + 1 F
(-23 + .5 C) :
Tensile Strength :
at break, psi 4590 5040 6400 ~ -.
15 Elongation at . .
:break % AVG 18 15 4 ;~
% MAX 25 15 5 Lap Shear Strength, psi 965 1480 1615 1663 , r' ~ ' .
"` :.",.: ': " ';``
,,: '" ', ~
..... '' ~ :. ' "''~'~"' ,' ', ' ' ~` ~" '.
'''~''''''''"''' '''''' ~!' :~ ' ,, ' ~,.
'~
The principles, preferred embodiments ancl modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
1 33 1 ~95 .
chlorosulfonated polyethylene polymers and graft copolymers of the core-shell type are disclosed in U.S. Patent No. 4,536,546.
With the use of more and more plastics in structures, e.g. automobiles, there is a continuing and even increasing need for adhesives which can be used on plastics as well as metals to form bonds which will hold up under a wide variety of adverse conditions.
There is a particular need for structural adhesives which not only have high adhesive bond impact strength but also have high bulk tensile elongation when measured at low temperatures. ~ :
Summary of Invention :~
This invention is directed to structural adhesive~ ~
compositions. In one aspect, this invention pertains to~;
structural adhesives which have high adhesive bond impact .
:
strength. In another aspect, this invention relates to .:
structural adhesives which have high bulk tensile elongation -when measured at temperatures of -10F (-23C) or lower. In still another aspect, this invention relates to structural -~
~ .
adhesives, the bulk tensile elongations of which are largely . ::: .:
reversible even at low temperatures.
The adhesive compositions of this invention are generally ~ ~ .
comprised of a) about 55 to about 75 weight percent of a methacrylate ester monomer such as methyl methacrylate, b) 0 to about 15 weight percent methacrylic acid, c) about 5 to about 20 weight percent of an elastomeric polymer such as polychloroprene, nitrile rubber, or a block copolymer or isoprene and styrene which is soluble in methyl methacrylate and which has a Tg below about -25C and d) about 10 to about 30 ;;, :.
weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein the weight percents are based on the total weight of (a), (b), (c) and (d).
,:
` `-" 13314q5 The adhesive compositions of this inventio~, when used in bonded assemblies, exhibit a combination of high adhesive bond impact strength (at least 15- ft-lb/s~.in.) and high bulk tensile elongation (~reater than 10 percent~ when measured at -10F
(-23C) or below.
Descri~tion of the Invention The monomers useful in this invention are methacrylate ester monomers wherein the alcohol portion of the ester group contains one to eight car~on atoms. Examples of such ester monomers are methyl methacrylate, ethyl methacrylate, 2-ethyhexyl methacrylate, cyclohexyl methacryla~e and mixtures thereof. The preferred ester monomer is methyl methacrylate.
Additional monomers which can be used in combination with the methacr~late monomers are acrylate esters wherein the alcohol portion of the ester contains 1 to 8 carbon atoms, examples of which are methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethyhexyl acrylate. Other useful monomers are acrylonitrile, methacrylonitrile, styrene, vinyl toluene, and the like.
The useful monomer composition contains at least about 50 weight percent methacrylate monomer and, preferably, at least about 50 weight percent methyl methacrylate monomer.
. . .
Additional monomers which are used in combination with the methacrylate ester monomers are free radical polymerizable `
e~hylenically unsaturated mono or polycarboxylic acids. Acrylic -acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid are examples o~ such acids. The preferred acid is , 1331~9~
methacrylic acid.
The elastomers useful in this in~ention have a second order glass transition temperature (Tg) of less than -2S and are soluble in the monomers described hereinabove. Useful elastomers are synthetic high polymers which exhibit plastic flow. The preferred elastomers are those which are supplied commercially as adhesive or cement grades.
A pre~erred class of elastomers for use in this invention are polychloroprene and copolymers of butadiene or isoprene with styrene, acrylonitrile, acrylate estexs, methacrylate esters, and the like. Additional useful elastomers are copolymers of ethylene and acrylate es~ers, homopolymers of epichlorohydrin and , ~ copolymers of epichlorohydrin and ethylene.
: ., .: ., : :
Specific examples of useful polymers using their letter ~15 designation according to ASTM D1418, their trade or common name ~ y and chemical description are: CR-Neoprene-polychloroprene;
. . , ~,, :. .
NBR-Nitrile rubber-butadiene acrylonitrile copolymer containing ``~ ~
.- - .
; about 25 to about 45 weight percent acrylonitrile; COX - Hyca~
1072-butadiene-acrylonitrile copolymer modified with carboxylic ~20 groups; SBR-GR-S-styrene-butadiene copolymer containing about 10 to about 30 weight percent styrene; ABR - Acrylic rubber acrylàte butadiene copolymer; and CO, ECO-~ydrin*100 and 200-homopolymer or a copolymer of epichlorohydrin and ethylene oxide. Additional useful elastomers are copolymers o~ e~hylene and acrylate esters, such as methyl acry:Late and ethyl acrylate, ~herein the copolymer contains a~ least 30 weight percent acrylate ester which * Trade Marks elastomers are sold commercially by duPont under the Vamac trademark.
Elastomers useful in this invention are described in detail in the "Handbook of Plastics and Elastomers" pages 1-106-119, (1975) McGraw-Hill, Inc., which may be referred to ~or further detail.
Particularly useful elastomers are polychloroprene and block copolymers of styrene and butadiene or isoprene, such block copolymers being sold under the trademark Kraton by Shell Oil Company. Block copolymers of styrene and diene monomers are described in detail in U.S. Paten~s No. 4,041,103 and 4,242,470 which may be referred to for further details.
Other elastomeric polymers having a Tg below -25C and .. . .
solubility in the methyl methacrylate monomer can be employed since, other than the low Tg and solubility characteristics, there are no other limitations on the identity o~ the elastomers except for the specific requirements of the particular adhesive being formulated, such as suitable molecular weight, viscosity characteristics and compatibility with the other ingredients of the adhesive.
Use~ul elastomers are those which are soluble in the monomers used in the adhesives of this invention. These elastomers can form solutions of from about 10 to about 35 weight percent elastomer in methyl methacrylate. As used herein the term "solution " is intended to cover not only true solu~ions but colloidal dispersion which exhibit normal or substantially newtonian rhe~logy characteristics.
,: ~
,~ ~
The core-shell graft copolymers useful in this invention have a "rubbery" core, a "hard" shell, and swell in the monomer compositions but do not dissolve therein. The "core" or backbone polymer of the graft copolymers has a glass transition temperature substantially below ~nbient temperatures. The "shell" polymer which is grafted onto the backbone polymer has a ;
glass transition temperature substantially above ambient ~ ~ ~
temperatures. Ambient temperature is defined as the temperature ~;
range in which the adhesive is used. -Examples of useful core-shell graft copolymers are those where "hard" monomers, such as styrene, acrylonitrile or methvl methacrylate, are grafted onto a rubbery core made from polymers or "soft" or "elastomeric;' monomers, such as butadiene or ethyl acrylate. ~ ;~
::
U.S~ Patent No. 3,985,703, which may be referred to for further details, describes useful core-shell polymers, the cores o~
which are made prefexably from butyl acrylate but can be based on ethyl, isobutyl, 2-ethylhexyl, or other alkyl acrylates or mixtures thereo~. The core polymer, optionally, can contain up to 20 percent of o~her copolymerizable monomers, such as styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene and the like. The core polymer optionally, can contain up to 5 percent ~i,, .
of a crosslinking monomer having two or more nonconjugated double bonds of approximately eoual reactivity, such as ethylene glycol ;~
~25 diacrylate, butylene glycol dimethacrylate and the like. It also optionally can contain up to 5 percent of a graft-linking monomer .., .- . i.
1 331 4q5 having two or more nonconjugated do~le bonds of unequal reactivity, such as diallyl maleate and allyl methacrylate.
The shell stage is preferably polymeriæed ~rom methyl methacrylate and optionally other lower alkyl methacxylates, such as ethyl, butyl, or mixtures thereof. Up to about 40 percent by weigh~ of the shell monomers can be styrene, vinyl acetate, vinyl chloride/ and the like.
Additionally useful core-shell graft copolymers are described in U.S. Patents No. 3,984,497, No. 4,096,202, and No.
4,034,013, which may be referred to for further details.
Still other useful core shell polymers are the "MBS"
polymers such as those described in UOS. Patent No. 4,304,709 wnich may be referred to for further detail. The MBS polymers are made by polymerizing methyl methacrylate in the presence of polybutadiene or a polybutadiene copolymer rubber.
Other patents which describe various useful core-shell graft copolymers are U.S. Patents No. 3,944,631, No. 4,306,040 and No.
4,495,3~4, each of which may be referred to for further details. -The core-shell gra~t polymers used in this invention swell in size in the adhesive formulation but do not dissolve. The adhesives, so formulated, exhibi~ improved spreading and 1Ow properties which are highly desirable in many adhesive ;
applications. For example, when an adhesive is applied to an article by means of a syringe-type application, many adhesives "string-out" between the point where the applicator was applied and the next position of the applicator. With the present ,.'; : ~
.... , ,, ... . . .. . .. . .. ,.. ,.. , . ., ,., ~., .. ~. ,. ... ,.. ,.~. ,,.. ,. .,,,;.. ... .
~ ' ' ' ~ ' I ' , ~ , ! ' , ' ', ._.
~ 1 33 1 495 invention, a small drop of adhesive can be applied to the article to be bonded with no adhesive string forming~
Additional components of the composition of this invention are polymeriæation catalysts with or without other components which enhance the reactivity of the calalysts. The catalysts are free radical generators which trigger the polymerization of acrylate and methacrylate compounds. Such catalysts are peroxides, hydroperoxides, peresters, peracids, radiant energy, e.g., ultraviolet light, and heat. Examples of these catalysts are benzoyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, tertiary butyl peroxide acetate, tertiary butyl perbenzoate, ditertiary butyl azodiisobutyronitrile and the li~e. These free radical producing catalysts are used in amounts of about 0.01 to about 10 weight percent based on the weight of the adhesive composition.
Pre~erably, the catalysts will be used in the amount of about 0.05 to about 3 weight percent.
Other components which enhance the reactivity of the catalysts are initiators or activators and promoters. Initiators and activators, which terms are used interchangeably, include tertiary amines and aldehyde-amine reaction products. Useful tertiary amines include N,N-dimethylaniline, N,N-dimethyl-toluidine, N,N-diethylaniline, N,N-diethyltoluidine and the like.
Aldehyde-amine reaction products include such compositions as butyraldehyde-aniline and butyraldehyde-butylamine compositions.
A promoter is an organic salt of a transition metal, such as .~ -. . .
~,- . . .
,'; :;;',i . ~:;
-8- ; ~
: ';'' ' .`'~' 1 331 49~
cobalt, nickel, manganese or iron naphthenate, copper octoate, copper acetylacetonate, iron hexoate, or iron propionate.
The initiators or activators, iiE used, are added in the amount of up to about 15 weight percent based on the weight of the adhesive. Preferred amounts are 0~01 to about 5 percent.
Promoters are used in amounts up to about 0.5 weight percent, preferably about 1 part per million to about 0.5 weight percent.
The compositions o~ this invention are usually prepared in two parts wherein 1 part contains the free radical catalysts and the other part contains the initiator or activator and the promoter if it is used. Just prior to use, the two parts are mixed together and the mixtur~ is applied to at least one of the surfaces to be bonded. Alternatively, the part containing the catalyst can be applied to one surface and the part containing the activator can be applied to the other surface. When pressed together, the two parts mix together and polymerization with resultant adhesive bonding takes place.
The adhesive compositions of this invention will contain about 55 to about 75 weight percent methacrylate ester monomer, 0 to about 15 weight percent acid monomer, about 5 to about 20 weight percent elastomer and about 10 ~o about 30 weight percent core-shell graft copolymer, said weight percents being based on the total weight of the components. Preferably, the compositions contains about 60 to about 70 weight percent methacrylate ester monomer, about 2 to about 10 weight percent acid monomer, about 8 to about 15 weight percent elastomer and about lS to about 20 we~ght percent core--shell graft copolymer.
1 33 1 4q5 The adhesive compositions of this invention have high adhesive bond impact strength (>15ft-lb/sq~in) and hign bulk tensile elongation (>10 percent) when measured at -10F (-23C) or below. The bulX tensilè elongation of these compositions is largely reversible even at low test temperatures. This reversible high elongation contributes to the superior performance of these adhesives in structures which undergo impacts at low temperatures.
The compositions of this invention are par~icularly useful for bonding thermoplastic automobile bumpers which must pass simulated crash impact tests at -10 to -20F (-23 to -29C).
In these tests, which measure energy management capability, .. .. ~; . .
bumpers are mounted horizontally and are impacted at various positions and angles with a pendulum or hydraulic ram at a rate that simulates a 2.5 or a 5 mile per hour crash. In this test, the bumper and the adhesive bondline experience both high impact -forces and a deflection of as much as 3 or 4 inches at the `
center. After the test, the bùmper springs back to its original shape. The high impact strength and high elongation, especially ~ --reversible elongation at low temperatures, of the compositions of this invention are clearly advantageous in this bumper -application.
The combination of relatively high modulus up to temperatures of 180F (82C) and high impact strength and ~;
elongation at temperatures of -10F (-23C) or below is very ad~antag~ous for bumpers and other structural applications which -10- ; "
' ' ' . :. ` ' 1 331 4qS
require high stiffness and structural integrity together with resistPnce to impact and other high stresses.
In the following examples, the elastomers were dissolved in the monomers by mixing until a uniform solution was obtained and no visible rubber particles were present. The other components, e.g., the core-shell polymers were then added to the elastomer solution and were stirred until a coarse paste was formed.
Further mixing with a high shear dispersion apparatus was continued until a smooth paste was obtained.
Adhesive strength tests were performed by mixing the formulations with a peroxide catalyst paste, or by combining two ~; ~ adhesive polymer-in-monomer solutions, one of which contained a peroxide, the other a catalyst activator.
The adhesives were tested as follows:
La~ Shear Strenqth (ASTM D-1002) The adhesive shear strength of bonds formed between substrates, e.g., a polycarbonate/polyester thermoplastic resin (Xenoy*, obtained from General Electric Company), was measured by ;
applying sufficient adhesive to one end of a 25 mm x 76 mm x 6.3 mm coupon of the substrate to completely fill a 25 mm x 12.5 mm x ! ,~ .25 mm bond gap. A 0.25 mm wire shim or washer was used to control bond thickness. A second coupon was placed over the coupon coated with adhesive to provide the proper lap shear configuratlon in a mold designed to properly align the specimen.
After a cure time o~ 24 to 48 hours at room temperature, the bonds were tested at a separation rate of 1.27 mm per minute.
* Trade Mark ~.
Im~act Strenqth (ASTM_D-950~
The impact strength of the adhesives was tested using the procedure of ASTM D-950 except that steel bars or rods having diameters of 12.7 mm and lengths of 76.2 mm and 9.5 mm, respectively, were used instead of t:he test specimens having dimensions specified in the ASTM testing method. Surfaces to be bonded together were first solvent cleaned and then grit blasted.
After being bonded, the specimens were conditioned for two days at room temperature prior to testing.
Bulk Adhesive Stress - Strain (ASTM B-638) Sufficient adhesive components were mixed to form a sheet of cured adhesive approximately 2.5 mm in thic~ness from which tensile test "dumbbells" were cut using a metal die as specified in the ASTM testing method. Unless otherwise specified, the stress-strain tests were performed at the indicated temperatures using a separation rate of 5 mm per minute.
Cold Im~act Test on Plastic Substrates This test was devised to simulate the impact and deflection forces that bonded structural assemblies, such as bumpers, experience under test conditions. This test was useful in evaluating the effect of "squeeze-out" at bond edges on the impact performance of the overall bonded assemblies. If the cured adhesive is not sufficiently elastic to relax under impact and elongation conditions, a crack can initiate in the adhesive bead and ~ropagate through the bonded assembly, leading to failures.
'' , , -12~
' ., ' In conducting the tests, a lS.2 cm long 5 gram bead of mixed adhesive was applied lengthwise on the centerline of a 15.2 cm x 2.5 cm plastic coupon. A 2.5 cm length of 1.3 mm diameter stainless steel wire was placed approxi~ately 6 mm from each end parallel to the plastic and perpendicular to the bead of adhesive. A 15.2 cm x 1.3 cm plastic strip was pressed down onto the adhesive until it made contact with the wire. The bonded assembly was allowed to cure at room temperature for at least 24 hours.
Before testing, the assembly was placed in a -10F (-23c) freezer for at leas~ 15 hours. The cold sample was tested by placing it in a modified National Forge Model TM S2004 Izod-Charpy impact tester fitted with a 10 ft/lb hammer. A
fixture was used to hold the sample at each end with the 2.5 cm plastic strip facing the impact hammer and the hammer was allowed to impact the plastic. The area of the hammer which contacts the -plastic is approximately 1 cm2. At the lowest point in the swing ; where the assembly is impacted, the hammer is travelling at 11 feet per second. If, after the hammer impacts ~he cold plastic, the hammer re~ounds and the test specimen remains intact, the result is recorded as a pass. If the plastic breaks at the point . .
of impact, the result is recorded as a failure. Occasionally, the hammer impacts the plastic and rebounds~ but the end of the plastic in the fixture cracks. This is recorded as an "end crack". It is considered a gualified pass, since the action of the fixturing assembly against the plastic imposes extraordinary - , .' ~ ' ~' : :- : .::
- : ::
. . ~, . ..
stresses on the bonded asse~bly at these fulcrum points.
The components used in the examples are identified as follows:
-,':-MMA - Methyl methacrylate monomer containin~ 22-28ppm of hydroguinone inhibitor MAA - Methacrylic acid cont:aining 250 ppm of :,.
hydroquinone inihibit:or ~ :
BMA - - Butyl methacrylate ~
2-EHMA - 2-Ethylhexyl methacrylate ~ .
Neo~rene - Polychloroprene homopolymer having a Brookfield solution viscosity (S weight percent in toluene) of about 20 to 3~ mPa as measured on Model LVT
visometer with UL adaptor Nitrile - Carboxy modified butadiene-acrylonitrile ~lastomer Rubber with medium acrylonitrile content, specific O
gravity of 0.98 and Mooney viscosity ML-4, 212 F ~. .
of 30-45 :~ :
Hypalo~ - Chlorosulfo~ated polyethylene containing 43 percent chlorine and l.l percent sulfur - duPont :-Paraloid* - Core-shell polymer of methacrylate-butadiene - -~
KM 753 styrene with high butadiene content - Rohm & Haas . Paraloid* - All acrylic core-shell polymer - Rohm & Haas . ~.
:~ ~M 330 ~ ~
: Geloy* - Core-shell polymer of acrylate rubber core and ~ -1020 styrene~acrylonitrile shell 25 Hydrin* - Liquid epichlorohydrin hgmopolymer with5a 10 x 1 BrookfOeld viscosity (27 C) of 2.5 x 10 cps, a Tg . ~:
of -25 C and a number average molecular weight of 4,000.
DMT - N,N-dimethyl-p-tolidine `
ZMTI - Zinc 2-mercaptotoluimidazole ~ .
VAMAC* ~ ethylene-methyl acrylate copolymer gum-duPont KRATO~ - st:yrene-isoprene branched copolymer-D 1320x Shell Oil Co.
"~ ,. ..
* Trade Marks .. ~ .
TYRIN* - Chlorinated polyethylene containing 42% chlorine, Dow Che.~.ical Co.
DPESC - Diphenyl ether disulfonyl chloride BH~ - 2,6-Di-tert butyl p-cresol CHP - Cumene hydroperoxide r 80 weight percent in cumene ~PO Paste - A paste o~ 55 percent: benzoyl peroxide in benzyl butyl phthalate plast:icizer VANAX*808 - Butyraldehyde-aniline condensation product - R..
Vanderbilt Co.
The Peroxide Paste used in the examples was prepared as follows: Hydrin lOxl, 25 parts by weight, and trioctyl trimellitate plasticizer, 25 parts by weight, were placed in a plastic container and were heated to 110F (43C). KM 753, 10 parts was gradualIy added as the mixture was sheared with a laboratory Hochmeyer high shear mixture. After all the KM 753 ~; had been added, shearing was continued for 5 minutes. The ~; mixture was then ~laced in a 110F (43C) oven for one hour and was again sheared until a smooth paste was obtained. After cooling, the BPO paste, 40 parts, was added and the mixture was again sheared until a uniform smooth paste was obtained.
The following tables list components used to formulate adhesive compositions and show test results o~ cured adhesives.
In preparing the adhesives, the Neoprene, nitrile rubber ~and Hypalon elastomer were dissolved in MMA to give solutions of 20, ~ 25 25 and 40 weight percent, respe~tively. All other ingredients `~ were combined by clirect addition and were mixed as described ~-.,, . ,~, hereinbefore.
* Trade Marks : ~ --.,~, ~::.
~ 15 ;~
- 1 33 1 4q5 ~;., The examples which have A and B parts are two part adhesives which are combined in a ~:1 weight ratio just prior to use. In the other examples (the 1 part adhesivesl~ the Peroxide Paste was added prior to use, the mix ratio being 1:10 paste to adhesive.
Table I illustrates greatly lmproved cold elongation of the compositions of this invention, Ex 1 and 2, compared to a prior art example, Ex 3.
TABLE I
Exam~le 1 _ 2 3 A B
Composition - --5 Parts.by wt MM~ 62.85 60.25 54.40 74.65 MAA 5.0 5.0 9.7 Neoprene 11.4 Nitrile rubber 14.0 ::
1~ Hypalon 30 23.3 Paraloid KM 753 20.0 20.0 12.05 :
Paraloid KM 330 8.2 . :
Geloy 1020 9.6 DMT 0 75 0 75 -~
~:15:CHP 0 3 ~ :
Vanax 808 Peroxide Paste 10 10 ~-;
~ ~ stress/strOin .
:20 at ~ O F
: (-24 + .5 C) Tensile s~rength :;
::~ at break, psi 5300 4800 6000 Elongation at break 25% Average 23 30 % Maximum 26 44 12 Tg, C of elastomer -39 -20 & -30 10C `. ;
: , ~
,,~ . .' '~' :','', ;' ' ~ `,.':. :
-17~
- - . .,..:
.~ ." ~, 1 331 ~95 Table II illustrates the improvement in impact resistance at low temperatures of plastic assemblies bonded with the compositions of this invention, Ex 4 and 5, compared with a prior art composition, EX 6. The steel imp~ct tes~ resu'ts show that Ex 4, 5 and 6 have similar impact strengths when measured by conventional methods.
~.,':.,',, ,.`.~ ~ . ` ~' :, -, -18- ;~
TABLE II
ExamPle _ _ 4_ 5 6 A B A
Composi~ion 5 ~ts bY wt . - ~ .. . .
MMA 62.5 61.0S 72.0554. ~0 74.65 MAA 5.0 9.6 9.7 Neoprene 11.35 11.05 11.25 ~ ;
Hypalon 30 23.3 Paraloid KM 753 19.9 14.45 14.75 12.05 Paralsid KM 330 8.2 Geloy 1020 9.6 DMT 0.75 1.95 CHP
~15 BHT .25 ZMTI 0.5 Vanax 808 7.55 ;
Peroxide Paste 10 ~PO Paste 3.85 Lap Shear Stgth, psi 1555 1595 1460 ;
on Xenoy 1102 Cold Tmpact Test Pass 6 4 on xenoY 1102 Fail 0 1 S
-12 ~ 2~F Crac~ 0 1 0 S~eel Impact Stgth. l9. S 23.1 22.0 .... .. ~: ~.
.. . ~ ~ . . ~, : ;: ~ , . .~ :.
. ~ ~... ...; .
- ~: :.
-; ~,:, :. . :
- - ... , .. ,,,, ~
~ :: .
~- 1331~95 Table III lists additional examples of adhesive compositions which provide adhesives with high elongation and resistance to low temperature impact failures when used to bond plastic.
Examples 7 and B are made using elastomers having Tg's of less than -25C, Example 9 uses an elastomer having a Tg higher than : ' "
.
' ~'' , -20- ~ ~
r~
1 331 4q5 TABLE I I I
Exam~le _ _ 7 8 9 _ A B A B AB
Composition BMA 35 - 5 73 - 5 35 - 5 73 - 5 35 5 73 - 5 ;~ ; ~
~AA 10 10 10 ,. ~,' 10 ~AM~C G 11.5 11.5 ,~
KRATON 11.5 11. 1 5 TYRIN 11.5 1 .
Paraloid KM 753 15 15 15 15 15 15 DMT 2 2 2 ~;
Elongation % at -11 + 1F 17 20 5 24 + .5 C) teeltlm~aC~t T20F ( -29C ) 24 - 4 21.0 8.9 Cold impact test 12x+no2~Fllo2 ~ 83 100 17 -24 + .5~C~
~ ~2 %gP 8c of Elastomer -27.8 -56 +10 : ., , ~
.' ,:: ., '' .
:~ ~
, .~ ,:',',,, .' -21- - ~ ~
'` ;'''`'`''.',~
13314q5 The examples listed in Table IV show additional adhesive tested at low temperatures. The Example 10 adhesive contains a core-shell polymer but no low Tg elastomer. Example 11 has a core-shell polymer and an elastomer having a Tg above - 25C.
Example 12 has a low Tg elastomer but no core-shell polymer.
Example 13 contains a low Tg elastomex and no core-shell polymer.
This adhesive exhibits decreased bonding strength on Xenoy plastic as shown in Table V. Example 14 contains both a low Tg elastomer and a core-shell polymer.
1 331 ~q5 :, .,.: .
", TABLE I~
. .
~x~le 10111.213 14 A B
Composition ;
5Dart by wei~ht , .
MM~62.8562.8~6~.27 62.85 62.60 66.74 ~AA 5.05.0 5.05.0 9.68 Neoprene 24.98 11.15 11.15 Nitrile rubber 31.4 10Hypalon 30 11.4 Paraloid R~ 753 31.4 20.0 14.56~ 14.56 DMT 0.75 0.75 0 75 0 75 0.3 -B~T 0.25 ~15 Vanax 808 , 7-55 DPESC 1.46 Peroxide Paste10 10 10 10 Stress/Strain ;~
a~ 1 ~-24 + .5 C
Tensile Stgth at break, psi6031 6980 3029 5025 4975 Elongation at break % AVG <5% <5% 6% 52% 11 ~AX <5~ <8~ 6~ 70~ 16% ~ ;
~25 Tg ~C o~ ela~tomer +10 -34.3 -20 & -30 -34.3 i ~
, ~ .~ :..., .-,., ,;, . ,.;, ,:, ,.
' .' ...., - :.~ .
'"'.~'., .~ '., , :;:','~'':.
,`",'~,',, '',,' ~ i ' ~'. .''' " `'' 1 33 1 ~
The examples listed in Table V illustrate the decrease in adhesion to Xenoy plastic with increasing levels of nitrile rubber. Example 15 which contains the highest ~mount of nitrile rubber and no core shell pol~mer h,as the lowest Lap Shear Strength on Xenoy plastic. Examples 16 and 17, which contain elastomer and core-shell polymer within the limits of the invention, have good tensile strength elongation at break and adhesion to Xenoy plastic. Example 18 which contains less elastomer than claimed in the inven~ion has good tensile strength lo and adhesion but poor elongation at break.
.:
, ~`
-13314C)5 TABLE V
Example _ 15 16 17 _ 18 Composition :
parts by weight MMA 70.9 60.3 ~8 63.4 :~
Nitrile rubber 23.6 14.1 6.5 1.3 Paraloid KM 753 20.1 30 29.8 ~:
DMT .5 .5 .5 .5 10 Stress/StrOin ; ::`
at -11 + 1 F
(-23 + .5 C) :
Tensile Strength :
at break, psi 4590 5040 6400 ~ -.
15 Elongation at . .
:break % AVG 18 15 4 ;~
% MAX 25 15 5 Lap Shear Strength, psi 965 1480 1615 1663 , r' ~ ' .
"` :.",.: ': " ';``
,,: '" ', ~
..... '' ~ :. ' "''~'~"' ,' ', ' ' ~` ~" '.
'''~''''''''"''' '''''' ~!' :~ ' ,, ' ~,.
'~
The principles, preferred embodiments ancl modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
Claims (6)
1. An adhesive composition comprising:
a) about 55 to about 75 weight percent methyl methacrylate;
b) 0 to about 15 weight percent methacrylic acid;
c) about 5 to about 20 weight percent polychloroprene which is soluble in methyl methacrylate and which has a Tg below about -25°C; and d) about 10 to about 30 weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein said weight percents are based on the total weight of (a), (b), (c) and (d).
a) about 55 to about 75 weight percent methyl methacrylate;
b) 0 to about 15 weight percent methacrylic acid;
c) about 5 to about 20 weight percent polychloroprene which is soluble in methyl methacrylate and which has a Tg below about -25°C; and d) about 10 to about 30 weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein said weight percents are based on the total weight of (a), (b), (c) and (d).
2. The adhesive composition of claim 1 wherein the methyl methacrylate is present in the amount of about 60 to about 70 weight percent, the methacrylic acid is present in the amount of about 2 to about 10 weight percent, the polychloroprene is present in the amount of about 8 to about 15 weight percent and the core-shell graft copolymer is present in the amount of about 15 to about 20 weight percent.
3. An adhesive composition comprising:
a) about 55 to about 75 weight percent methyl methacrylate;
b) 0 to about 15 weight percent methacrylic acid;
c) about 5 to about 20 weight percent nitrile rubber which is soluble in methyl methacrylate and which has a Tg below about -25°C; and d) about 10 to about 30 weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein said weight percents are based on the total weight of (a), (b), (c) and (d).
a) about 55 to about 75 weight percent methyl methacrylate;
b) 0 to about 15 weight percent methacrylic acid;
c) about 5 to about 20 weight percent nitrile rubber which is soluble in methyl methacrylate and which has a Tg below about -25°C; and d) about 10 to about 30 weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein said weight percents are based on the total weight of (a), (b), (c) and (d).
4. The adhesive composition of claim 3 wherein the methyl methacrylate is present in the amount of about 60 to about 70 weight percent, the methacrylic acid is present in the amount of about 2 to about 10 weight percent, the nitrile rubber is present in the amount of about 8 to about 15 weight percent and the core-shell graft copolymer is present in the amount of about 15 to about 20 weight percent.
5. An adhesive composition comprising:
a) about 55 to about 75 weight percent methyl methacrylate;
b) 0 to about 15 weight percent methacrylic acid;
c) about 5 to about 20 weight percent of a block copolymer of butadiene or isoprene and styrene which is soluble in methyl methacrylate and which has a Tg below about -25°C; and d) about 10 to about 30 weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein said weight percents are based on the total weight of (a), (b), (c) and (d).
a) about 55 to about 75 weight percent methyl methacrylate;
b) 0 to about 15 weight percent methacrylic acid;
c) about 5 to about 20 weight percent of a block copolymer of butadiene or isoprene and styrene which is soluble in methyl methacrylate and which has a Tg below about -25°C; and d) about 10 to about 30 weight percent of a core-shell graft copolymer which has a butadiene-styrene core and a methyl methacrylate shell and which swells in the monomer but does not dissolve therein, wherein said weight percents are based on the total weight of (a), (b), (c) and (d).
6. The adhesive composition of claim 5 wherein the methyl methacrylate is present in the amount of about 60 to about 70 weight percent, the methacrylic acid is present in the amount of about 2 to about 10 weight percent, the block copolymer is present in the amount of about 8 to about 15 weight percent and the core-shell graft copolymer is present in the amount of about 15 to about 20 weight percent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/238,302 US4942201A (en) | 1988-08-29 | 1988-08-29 | Adhesive for low temperature applications |
| US238,302 | 1988-08-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1331495C true CA1331495C (en) | 1994-08-16 |
Family
ID=22897314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000606983A Expired - Lifetime CA1331495C (en) | 1988-08-29 | 1989-07-28 | Adhesive for low temperature applications |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US4942201A (en) |
| EP (1) | EP0357304B1 (en) |
| JP (1) | JP2745425B2 (en) |
| KR (2) | KR930004702B1 (en) |
| AU (1) | AU3904589A (en) |
| CA (1) | CA1331495C (en) |
| DE (1) | DE68913867T2 (en) |
| ES (1) | ES2062016T3 (en) |
| IE (1) | IE80687B1 (en) |
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-
1988
- 1988-08-29 US US07/238,302 patent/US4942201A/en not_active Expired - Lifetime
-
1989
- 1989-07-27 AU AU39045/89A patent/AU3904589A/en not_active Abandoned
- 1989-07-28 CA CA000606983A patent/CA1331495C/en not_active Expired - Lifetime
- 1989-08-18 ES ES89308392T patent/ES2062016T3/en not_active Expired - Lifetime
- 1989-08-18 DE DE68913867T patent/DE68913867T2/en not_active Expired - Lifetime
- 1989-08-18 EP EP89308392A patent/EP0357304B1/en not_active Expired - Lifetime
- 1989-08-24 JP JP1216190A patent/JP2745425B2/en not_active Expired - Lifetime
- 1989-08-28 IE IE275689A patent/IE80687B1/en not_active IP Right Cessation
- 1989-08-29 KR KR1019890012236A patent/KR930004702B1/en not_active IP Right Cessation
-
1990
- 1990-07-05 US US07/547,969 patent/US5206288A/en not_active Expired - Lifetime
-
1991
- 1991-07-03 KR KR1019910011237A patent/KR920002729A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU3904589A (en) | 1990-03-01 |
| US4942201A (en) | 1990-07-17 |
| IE80687B1 (en) | 1998-12-02 |
| ES2062016T3 (en) | 1994-12-16 |
| KR920002729A (en) | 1992-02-28 |
| JPH02167377A (en) | 1990-06-27 |
| KR930004702B1 (en) | 1993-06-03 |
| EP0357304A3 (en) | 1991-04-03 |
| DE68913867T2 (en) | 1994-06-30 |
| EP0357304B1 (en) | 1994-03-16 |
| JP2745425B2 (en) | 1998-04-28 |
| EP0357304A2 (en) | 1990-03-07 |
| US5206288A (en) | 1993-04-27 |
| IE892756L (en) | 1990-02-28 |
| KR900003323A (en) | 1990-03-26 |
| DE68913867D1 (en) | 1994-04-21 |
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