Adhesive for low temperature applications

Abstract: 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: Field of the Invention This invention relates to structural acrylic adhesives. Background of the Invention Structural acrylic adhesives are rubber-toughened adhesive systems that cure rapidly at room temperature to give excellent adhesive properties. Such adhesives are characterised 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 US-A-3832274. These adhesives are made from elastomers having Tg of less than 15°F (-9°C) acrylic monomers and a redox catalyst. Structural adhesives which contain chlorosulfonated polyethylene or sulfonyl chloride and chlorinated polymers are disclosed in US-A-3890407, US-A-3962372 and US-A-4287106. US-A-4126504 and US-A-4348503 disclose various combinations of elastomers, acrylic monomers, catalysts and other additives. In particular, US-A-4451615 (=EP-A-0040079) discloses a structurally-toughened adhesive composition comprising a methacrylate ester monomer in a concentration of e.g. 80 wt%, an elastomeric copolymer consisting of isoprene and styrene and a radical-producing catalyst. The components of the copolymer have glass transition temperatures of -100°C (styrene block) and -72°C (isoprene block). Adhesives based on diene polymers, such as polybutadienes, polyisoprenes, butadiene-styrene copolymers and ABS graft polymers, plus vinyl monomers and adhesion promoters, are described in US-A-4287106. Methacrylate-based adhesives which contain chlorinated or chlorosulfonated polyethylene polymers, a catalyst and, as impact-modifiers, graft copolymers of the core-shell type are disclosed in US-A-4536546 (=EP-A-0142923). 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 the Invention An adhesive composition of this invention comprises: a) 50 to 75% methacrylate ester monomer; b) 0 to 15% of an ethylenically-unsaturated polymerisable mono or poly-carboxylic acid; c) 5 to 20% of an elastomeric polymer having a Tg below -25°C; and d) 10 to 30% of a core-shell graft polymer which swells in the monomer but does not dissolve therein; wherein the percentages are by weight based on the total weight of a), b), c) and d). The adhesive compositions of this invention, when used in bonded assemblies, exhibit a combination of high adhesive bond impact strength, e.g. at least 0.03 J/mm² (15 ft-lb/in²) and high bulk tensile elongation (greater than 10%) when measured at -10°F (-23°C) or below. Description of the Invention The monomers useful in this invention are methacrylate ester monomers wherein the alcohol portion of the ester group contains 1 to 8 carbon atoms. Examples of such ester monomers are methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and mixtures thereof. The preferred ester monomer is methyl methacrylate. Additional monomers which can be used in combination with the methacrylate 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-ethylhexyl acrylate. Other useful monomers are acrylonitrile, methacrylonitrile, styrene and vinyltoluene. The composition contains at least 50%, and preferably 55 to 75%, by weight methacrylate monomer. The composition most preferably comprises 60 to 70% methyl methacrylate monomer, 2 to 10% acid monomer, 8 to 15% elastomer, and 15 to 20% core-shell graft copolymer. The acid used in the present invention is preferably free-radical polymerisable. Acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid are examples of such acids. The preferred acid is methacrylic acid. The elastomers useful in this invention have a second order glass transition temperature (Tg) of less than -25° 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 preferred class of elastomers for use in this invention are polychloroprene and copolymers of butadiene or isoprene with styrene, acrylonitrile, acrylate esters, methacrylate esters, and the like. Additional useful elastomers are copolymers of ethylene and acrylate esters, homopolymers of epichlorohydrin and copolymers of epichlorohydrin and ethylene. Specific examples of useful polymers using their letter designation according to ASTM D1418, their trade or common name and chemical description are: CR-Neoprene-polychloroprene; NBR-Nitrile rubber-butadiene acrylonitrile copolymer containing about 25 to about 45 weight percent acrylonitrile; COX - Hycar 1072-butadiene-acrylonitrile copolymer modified with carboxylic groups; SBR-GR-S-styrene-butadiene copolymer containing about 10 to about 30 weight percent styrene; ABR - Acrylic rubber acrylate butadiene copolymer; and CO, ECO-Hydrin 100 and 200-homopolymer or a copolymer of epichlorohydrin and ethylene oxide. Additional useful elastomers are copolymers of ethylene and acrylate esters, such as methyl acrylate and ethyl acrylate, wherein the copolymer contains at least 30 weight percent acrylate ester which 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 is hereby incorporated by reference. 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. Patents No. 4,041,103 and 4,242,470 which are hereby incorporated by reference. Other elastomeric polymers having a Tg below -25°C 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 of 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. Useful 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 tern "solution " is intended to cover not only true solutions but colloidal dispersion which exhibit normal or substantially newtonian rheology 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 ambient 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 methyl methacrylate, are grafted onto a rubbery core made from polymers of "soft" or "elastomeric" monomers, such as butadiene or ethyl acrylate. U.S. Patent No. 3,985,703, which is hereby incorporated by reference, describes useful core-shell polymers, the cores of which are made preferably from butyl acrylate but can be based on ethyl, isobutyl, 2-ethylhexyl, or other alkyl acrylates or mixtures thereof. The core polymer, optionally, can contain up to 20 percent of other copolymerizable monomers, such as styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene and the like. The core polymer, optionally, can contain up to 5 percent of a crosslinking monomer having two or more nonconjugated double bonds of approximately equal reactivity, such as ethylene glycol diacrylate, butylene glycol dimethacrylate and the like. It also optionally can contain up to 5 percent of a graft-linking monomer having two or more nonconjugated double bonds of unequal reactivity, such as diallyl maleate and allyl methacrylate. The shell stage is preferably polymerized from methyl methacrylate and optionally other lower alkyl methacrylates, such as ethyl, butyl, or mixtures thereof. Up to about 40 percent by weight 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 are hereby incorporated by reference. Still other useful core shell polymers are the "MBS" polymers such as those described in U.S. Patent No. 4,304,709 which is hereby incorporated by reference. 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. 4,495,324, each of which is hereby incorporated by reference. The core-shell graft polymers used in this invention swell in size in the adhesive formulation but do not dissolve. The adhesives, so formulated, exhibit improved spreading and flow 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 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 polymerization catalysts with or without other components which enhance the reactivity of the catalysts. 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 like. 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. Preferably, 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-dimethyltoluidine, 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 cobalt, nickel, manganese or iron naphthenate, copper octoate, copper acetylacetonate, iron hexoate, or iron propionate. The initiators or activators, if 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 of 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 mixture 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 have high adhesive bond impact strength ( 0.03 J/mm²) and high bulk tensile elongation (>10 percent) when measured at -10°F (-23°C) or below. The bulk tensile 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 particularly useful for bonding thermoplastic automobile bumpers which must pass simulated crash impact tests at -10° to -20°F (-23° to -29°C). 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 1.1 or 2.2 m/s crash. In this test, the bumper and the adhesive bondline experience both high impact forces and a deflection of as much as 75 or 100 mm at the center. After the test, the bumper 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 180°F (82°C) and high impact strength and elongation at temperatures of -10°F (-23°C) or below is very advantageous for bumpers and other structural applications which requires high stiffness and structural integrity together with resistance 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: Lap Shear Strength (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 0.25 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 configuration in a mold designed to properly align the specimen. After a cure time of 24 to 48 hours at room temperature, the bonds were tested at a separation rate of 1.27 mm per minute. Impact Strength (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 the 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 forth a sheet of cured adhesive approximately 2.5 mm in thickness 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 Impact 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 propagate through the bonded assembly, leading to failures. In conducting the tests, a 15.2 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 approximately 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 -10°F (-23°C) freezer for at least 15 hours. The cold sample was tested by placing it in a modified National Forge Model TM 52004 Izod-Charpy impact tester fitted with a 0.67 m/kg (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 0.305 m/s (11 feet per second). If, after the hammer impacts the cold plastic, the hammer rebounds 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 qualified pass, since the action of the fixturing assembly against the plastic imposes extraordinary stresses on the bonded assembly at these fulcrum points. The components used in the examples are identified as follows: MMA - Methyl methacrylate monomer containing 22-28ppm of hydroquinone inhibitor MAA - Methacrylic acid containing 250 ppm of hydroquinone inihibitor BMA - Butyl methacrylate 2-EHMA - 2-Ethylhexyl methacrylate Neoprene - Polychloroprene homopolymer having a Brookfield solution viscosity (5 weight percent in toluene) of about 20 to 35 mPa as measured on Model LVT visometer with UL adaptor Nitrile Rubber - Carboxy modified butadiene-acrylonitrile elastomer with medium acrylonitrile content, specific gravity of 0.98 and Mooney viscosity ML-4, 100°C, of 30-45 Hypalon 30 - Chlorosulfonated polyethylene containing 43 percent chlorine and 1.1 percent sulfur - duPont Paraloid KM 753 - Core-shell polymer of methacrylate-butadiene-styrene with high butadiene content - Rohm & Haas Paraloid KM 330 - All acrylic core-shell polymer - Rohm & Haas Geloy 1020 - Core-shell polymer of acrylate rubber core and styrene-acrylonitrile shell Hydrin 10 x 1 - Liquid epichlorohydrin homopolymer with a Brookfield viscosity (27°C) of 2.5 x 10⁵ 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 KRATON D 1320x - styrene-isoprene branched copolymer-Shell Oil Co. TYRIN - Chlorinated polyethylene containing 42% chlorine, Dow Chemical Co. DPESC - Diphenyl ether disulfonyl chloride BHT - 2,6-Di-tert-butyl-p-cresol CHP - Cumene hydroperoxide, 80 weight percent in cumene BPO Paste - A paste of 55 percent benzoyl peroxide in benzyl butyl phthalate plasticizer VANAX 808 - Butyraldehyde-aniline condensation product - R.. Vanderbilt Co. The Peroxide Paste used in the examples was prepared as follows: Hydrin 10x1, 25 parts by weight, and trioctyl trimellitate plasticizer, 25 parts by weight, were placed in a plastic container and were heated to 110°F (43°C). KM 753, 10 parts was gradually 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 placed in a 110°F (43°C) 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 of cured adhesives. In preparing the adhesives, the Neoprene, nitrile rubber and Hypalon elastomer were dissolved in MMA to give solutions of 20, 25 and 40 weight percent, respectively. All other ingredients were combined by direct addition and were mixed as described hereinbefore. The examples which have A and B parts are two part adhesives which are combined in a 1:1 weight ratio just prior to use. In the other examples (the 1 part adhesives), the Peroxide Paste was added prior to use, the mix ratio being 1:10 paste to adhesive. Table I illustrates greatly improved cold elongation of the compositions of this invention, Ex 1 and 2, compared to a prior art example, Ex 3. 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 impact test results show that Ex 4, 5 and 6 have similar impact strengths when measured by conventional methods. Example 4 5 6 A B A B Composition parts by wt MMA 62.5 61.05 72.05 54.40 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 Paraloid KM 330 8.2 Geloy 1020 9.6 DMT 0.75 1.95 CHP .3 BHT .25 ZMTI 0.5 Vanax 808 7.55 Peroxide Paste 10 BPO Paste 3.85 Lap Shear Stgth, kPa on Xenoy 1102 10700 11000 10100 Cold Impact Test on Xenoy 1102 -12 ± 2°F (-24.5 ± 1°C) Pass 6 4 1 Fail 0 1 5 Crack 0 1 0 Steel Impact Stgth. 19.5 23.1 22.0 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 8 are made using elastomers having Tg's of less than -25°C, Example 9 uses an elastomer having a Tg higher than -25°C. Example 7 8 9 A B A B A B Composition parts by weight MMA 35.5 73.5 35.5 73.5 35.5 73.5 BMA 14 14 14 2-EHMA 14 14 14 MAA 10 10 10 VAMAC G 11.5 11.5 KRATON 11.5 11.5 TYRIN 11.5 11.5 Paraloid KM 753 15 15 15 15 15 15 DMT 2 2 2 BPO PASTE 4 4 4 Elongation % at -11 ± 1°F (-24 ± .5°C) 17 20 5 Steel impact Test J/mm² at -20°F (-29°C) 0.05 0.04 0.02 Cold impact test on Xenoy 1102, -12 ± 2°F (-24 ± .5°C) % passed 83 100 17 Tg, °C of Elastomer -27.8 -56 +10 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 - 25°C. Example 12 has a low Tg elastomer but no core-shell polymer. Example 13 contains a low Tg elastomer 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. 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 amount of nitrile rubber and no core shell polymer has 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 invention has good tensile strength and adhesion but poor elongation at break.

Claims: An adhesive composition comprising: a) 50 to 75% methacrylate ester monomer; b) 0 to 15% of an ethylenically-unsaturated polymerisable mono or poly-carboxylic acid; c) 5 to 20% of an elastomeric polymer having a Tg below -25°C; and d) 10 to 30% of a core-shell graft polymer which swells in the monomer but does not dissolve therein; wherein the percentages are by weight based on the total weight of a), b), c) and d). A composition according to claim 1, which comprises 55 to 75% by weight of the ester monomer. A composition according to claim 1, which comprises 60 to 70% by weight of the ester monomer, 8 to 15% by weight of the acid, and 15 to 20% by weight of the graft copolymer. A composition according to any preceding claim, wherein the ester monomer is methyl methacrylate. A composition according to any preceding claim, wherein the acid is free radical-polymerisable. A composition according to any preceding claim, wherein the acid is methacrylic acid. A composition according to claim 5 or claim 6, which additionally comprises a free radical-producing catalyst. A composition according to any preceding claim, wherein the ester monomer is methyl methacrylate, the acid is methacrylic acid, the elastomeric polymer is polychloroprene, and the graft copolymer has a butadiene-styrene core and a methyl methacrylate shell. A composition according to any of claims 1 to 7, wherein the elastomeric polymer is nitrile rubber. A composition according to any preceding claim, wherein the elastomeric polymer is soluble in the monomer, in an amount of 10 to 35% by weight, based on the weight of the solution. A composition according to any preceding claim, wherein the Tg of the core of the graft copolymer is substantially below ambient temperatures and the Tg of the shell is substantially above ambient temperatures. Use of a composition according to any preceding claim, to bond an assembly. Use according to claim 12, wherein the cured adhesive has an adhesive bond strength of at least 0.03 J/mm² (15 ft-lb/in²) and a bulk tensile elongation greater than 10% at -23°C or below.

Inventors: BRIGGS PAUL C, GOSIEWSKI DONALD E, BRIGGS, PAUL C., GOSIEWSKI, DONALD E.
Applicants: ILLINOIS TOOL WORKS, ILLINOIS TOOL WORKS INC.
Application year: 1989
Main classification: C09J4
IPC codes: C09J4, C09J111, C09J151