AU2005262499B2

AU2005262499B2 - Adhesive composition, method for bonding to a metal surface and rubber to metal adhesive

Info

Publication number: AU2005262499B2
Application number: AU2005262499A
Authority: AU
Inventors: Christian C. Green; Jack N. Tallmadge
Original assignee: Lord Corp
Current assignee: Lord Corp
Priority date: 2004-06-16
Filing date: 2005-06-16
Publication date: 2007-09-13
Anticipated expiration: 2025-06-16
Also published as: AU2005262499C1; AU2005262499A1

Description

ADHESIVE COMPOSITION, METHOD FOR BONDING TO A METAL SURFACE AND RUBBER TO METAL ADHESIVE FIELD OF THE INVENTION [002] The invention relates to formulated adhesives applied to bond rubber to s metal, in which bonding takes place under heat and pressure during the vulcanization process.

BACKGROUND OF THE INVENTION [003] Bonding of vulcanizable rubber to rigid substrates, especially metal is conventionally obtained by two-coat approaches using a primer and covercoat or a i0 one-coat, primerless system. In order to provide durable bonds under stress and environmental attack, adhesive compositions must exhibit a high degree of retention of rubber on the substrate after bond destruction. In order to achieve such performance, in the application of adhesive, careful control of dry film thickness must be maintained, and the adhesive must wet the substrate surface and provide adequate sweep resistance ability of the uncured, dry adhesive coating to completely cover the bonding area against the force of injected rubber in the mold cavity. RTM adhesives should also have good storage stability in the wet adhesive [004] In the literature relating to adhesives for bonding rubber to metal (RTM), the essential components include one or more halogenated film formers, crosslinkers, acid acceptors and other additives such as organosilanes, dispersing agents, adhesion promoting resins such as phenol formaldehyde, and fillers such as carbon black, silica, talc and calcium carbonate.

WO 2006/007438 PCT/US2005/021520 [005] Adhesive compositions widely used commercially for bonding rubber to metal have been developed from the pioneering patents of Coleman et al, U.S.

Pat. No. 3,258,388, and employ nitroso aromatic compounds. The conventional adhesives include compositions also typically contain thermosetting condensation polymers; polymers and copolymers of polar ethylenically unsaturated materials, halogenated rubbers, and/or polyisocyanates. The Coleman et al adhesive compositions provide good to excellent primary adhesion values with a wide variety of elastomers; however, such compositions do not by themselves provide desired levels of environmental resistance as measured by exposure to boiling water, salt spray or high humidity conditions. To obtain at least reasonable levels of environmental resistance, it has been necessary to employ primers such as phenolic-containing compositions; or incorporate additives such as silanes, silane-isocyanate adducts, phenolic materials, and the like, into the adhesive compositions.

[006] Primerless one-coat adhesive compositions exhibiting excellent environmental resistance are described in U.S. Pat. No. 4,119,587. This patent describes an adhesive composition comprised of the three essential constituents: (a) halogenated polyolefinic, aromatic nitroso compound, and lead salts.

[007] Conventional RTM adhesives are dispersions of finely ground active ingredients in particulate form, including crosslinkers, film formers, metal oxides, carbon black and the like typically, and must be diluted from the as-received total solids wt.% content (TSC) 40% down to 15 20% in order to provide adequate sprayability and at the same time control the dry film thickness of the adhesive coating on the metal substrate. Often even at reduced solids these dispersions spray poorly, as evidenced by spattering, and poor wet film coverage over the intended bonding area. It is critical to maintain the DFT in a preselected range of from about 0.3 to 2 mils in a one-coat or two-coat application, and within a variability 0.1 0.3 mils for each coating on the metal surface. Without dilution the RTM adhesive dispersions often exhibit poor sprayability, and DFT control.

[008] Another problem in the use of fine particulate dispersions as RTM adhesives relates to incidences of increasing viscosity after shelf aging. Over time, WO 2006/007438 PCT/US2005/021520 the viscosity of a conventional K I M adhesive can double or triple as measured by Brookfield viscometers. In order to reduce the adhesive at the time of use to a form which is sprayable, the adhesive must be diluted. This introduces variability to a process which must keep critical control of dry film thickness. Dilution using solvents introduces unwanted environmental hazards from the presence of VOC's. It would be commercially important to reduce the VOC content of RTM adhesives containing fine dispersions of active particulates while at the same time to improve the sprayability and hence DFT control.

[009] Inert fillers are typically used in RTM adhesives. For some formulations of active ingredients exhibit poor sweep resistance, which is the ability of the dry adhesive film to resist being swept out of the bonding area by the molded elastomer.

It is known that sweep resistance can be improved by the use of about 1-5 wt.% of fumed silica, characterized by a BET surface area, using nitrogen gas in the range of about 40 to about 600, and more usually in a range of about 50 to about 300 square meters per gram (m 2 These additives however interfere with sprayability.

Conventional RTM adhesives typically utilize inert fillers such as talc which has a surface area of from about 3 to about 14 m 2 clay which has a surface area of from about 7 to about 21 m 2 /g and/or calcium carbonate which has a surface area of from about 5 to 10.5 m 2 /g.

[010] None of the conventional inert fillers improves the problems of sprayability and viscosity stability in an RTM adhesive dispersion, and dilution is required, however the diluted adhesives still can exhibit poor spraying characteristics and difficulty in achieving control and uniformity of dry film thickness.

O In a first aspect the invention provides an adhesive composition having a pigment C grind of 0-2 mils (0 to 0.05 mm) measured by the Hegman® gauge, said adhesive is Ssprayable at a total solids concentration of 25 2 has a viscosity of from 50 to 500 cps (Brookfield LVT 2 30 rpm) and comprises a nitroso compound, film-forming halogenated polyolefin, acid acceptor and from 5% to 35 dry wt.% of inert, incompressible, spheroidal particles having a BET surface area of from 0.1 to 10 m2/g and a 50 h percentile particle diameter (D50) of 5 to 25 pm.

In a second aspect the invention provides a method for spray applying a rubber-to- IN metal adhesive according to the first aspect of the invention comprising spraying onto a 0o metal surface in an amount to provide a dry film thickness of from 0.0003 to 0.002 inch (0.007 to 0.0508 mm) 0.0001 to 0.0003 (0.0025 to 0.0076 mm) in one or two sprayed layers.

In a third aspect the invention provides a method of bonding an elastomer to a metal surface, said method comprised of: providing a metal surface, providing a rubber to metal adhesive including a nitroso compound, a film-forming halogenated polyolefin, an acid acceptor and from 5% to 35 dry wt.% of spheroidal particles having a BET surface area of from 0.1 to 10 m 2 /g and a 5 0 th percentile particle diameter (D50) of 5 to 25 gm, said rubber to metal adhesive having a viscosity of from 50 to 500 cps (Brookfield LVT 2 rpm), and spraying said provided rubber to metal adhesive onto said metal surface.

In a fourth aspect the invention provides a rubber to metal adhesive comprised of a nitroso compound, a film-forming halogenated polyolefin, an acid acceptor and a plurality of microspheres, said adhesive having a weight percent concentration of at least one percent of said microspheres, wherein said adhesive has a viscosity less than 500 cps (Brookfield LVT 2 30 rpm).

In a fifth aspect the invention provides a method of making an elastomer to metal adhesive, said method comprising: providing an elastomer to metal adhesive fluid composition, said fluid composition comprising a nitroso compound, a film-forming halogenated polyolefin, and an acid acceptor, providing a plurality of microspheres, adding said plurality of microspheres to said elastomer to metal adhesive fluid to provide an elastomer to metal adhesive having a viscosity less than 500 cps (Brookfield LVT 2 30 rpm).

In a sixth aspect the invention provides an elastomer to metal adhesive prepared according to the method of the fifth aspect of the invention.

AH21(911549_1) AAK WO 2006/007438 PCT/US2005/021520 [015] It is to be understood that both the foregoing general description and the following detailed description are exemplary of the invention, and are intended to provide an overview or framework for understanding the nature and character of the invention as it is claimed. The claims of the invention, together with the description, serve to explain the principals and operation of the invention.

Detailed Description of Preferred Embodiments [016] Additional features and advantages of the invention will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the invention as described herein, including the detailed description which follows and the claims.

[017] Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are disclosed.

[018] The essential components of the RTM adhesive dispersions according to the invention comprise a nitroso compound or precursor, one or more halogenated polymers, an acid acceptor, and a specified type and amount of inert, incompressible, spheroidal particles (ISP). The adhesive can be prepared in a concentration, however the general practice is to prepare a concentrate at a solids level of from 30 50 wt.%, and select a TSC range at the time of application taking into account the desired DFT.

Best results are obtained at a TSC range of 25 3 wt.% solids.

[019] Optional, but preferably included ingredients for the RTM adhesive dispersions are zero to 10% carbon black; zero to 10% of non-spheroidal fillers as replacement for a corresponding amount of ISP; zero to 35%, preferably 5 15 wt.% of a co-curative capable of forming covalent crossbonding/ crosslinking bonds with the adhesive and elastomer bonded thereto. Percentages indicated hereinbelow are on a dry weight basis [020] It is essential in the practice of the invention to employ one or more halogen-containing film-forming polymers, including post-halogenated natural rubber and/or synthetic addition-polymerized, halogenated elastomer. The halogens WO 2006/007438 PCT/US2005/021520 employed in the halogen atedelasfomers will usually be chlorine or bromine, although fluorine can also be used. A combination of halogen atoms can also be employed in which case the halogen-containing polymer elastomer will have more than one halogen substituted thereon. Exemplary synthetic film formers are the halogencontaining polyolefinic elastomers. Their preparation is well known in the art and many types are available commercially. Representative halogen-containing polyolefinic elastomers include, but are not limited to chlorinated natural rubber, chlorinated polychloroprene, chlorinated polybutadiene, chlorinated butadiene-styrene copolymers, chlorinated ethylene propylene copolymers, chlorinated ethylene/propylene/non-conjugated diene terpolymers, chlorinated polyethylene, chlorosulfonated polyethylene, copolymers of c-chloroacrylonitrile and 2,3-dichloro- 1,3-butadiene (DCD), brominated poly(2,3-dichloro-1,3-butadiene), copolymers of ahaloacrylonitriles and 2,3-dichloro-1,3-butadiene, chlorinated poly(vinyl chloride), vinyl chloride-vinylidene chloride-acrylate or acrylic acid terpolymers, and the like, including mixtures of such halogen-containing elastomers.

[021] An exemplary mixture of film formers is chlorosulfonated polyethylene and chlorinated natural rubber. Thus, substantially any of the known halogencontaining derivatives of natural and synthetic elastomers are preferably employed in the practice of this invention, including mixtures of halogenated and non-halogenated elastomers. Chlorosulfonated polyethylene elastomers alone or in combination with chlorinated natural rubber are the most preferred mixed halogen-containing film formers. Chlorosulfonated polyethylene is commercially available from E. I. Du Pont de Nemours Co. under the HYPALON mark.

[022] Chlorinated polyolefin can be used as a primary film former, and should contain at least 40 wt. percent chlorine and a molecular weight greater than about 500. Such chlorine contents can be obtained by a process involving the dispersion and chlorination of high surface area polyolefinic particles in an aqueous medium taught in U.S. Patent No. 5,534,991.

WO 2006/007438 PCT/US2005/021520 [023] Chl6oriated ratural rubber (CNR) is a preferred film former and several grades are commercially available from Bayer Aktiengesellschaft, under the PERGUT® mark.

[024] Chlorosulfonated polyethylene (CSM) is a preferred film former and typically has a molecular weight in the range of about 30,000-150,000, preferably about 60,000-120,000. The chlorine content of suitable chlorosulfonated polyethylenes is in the range of about 20-50 wt. preferably about 25 to 45 wt.%.

percent. The sulfur content is typically in the range of about 0.01 to 2, preferably about 1.0 to 1.5 percent.

[025] The most preferred embodiments contain chlorinated natural rubber and chlorosulfonated polyethylene in a total amount ranging from about 30 to 40 dry wt.%, and preferably in 50:50 mixtures of 13-17 wt. each on a dry weight basis of the adhesive.

[026] A latex of the halogenated polyolefin of the present invention can be prepared according to methods known in the art such as by dissolving the halogenated polyolefin in a solvent and adding a surfactant to the resulting solution.

Water can then be added to the solution under high shear to emulsify the polymer.

The solvent is then stripped to obtain a latex having a total solids content of from about 10 to 60, preferably 25 to 50, percent by weight. The latex can also be prepared by emulsion polymerization of chlorinated ethylenically unsaturated monomers.

[027] The utilization of chlorinated natural rubber either in solvent solution or as a latex is most preferred in forming the adhesive of the present invention inasmuch as generally other types of rubbers, halogenated and non-halogenated, and the like do not result in as good pre-bake properties. Accordingly, other types of rubbers are less preferred film formers. Aqueous dispersions of halogenated or preferably chlorinated natural rubbers are made by conventional techniques for producing aqueous dispersions. Examples of suitable processes and chlorinated natural rubbers which can be utilized are set forth in U.S. Patent Nos. 3,968,067; 4,070,825; 4,145,816; 4,243,566; and 6,103,786; the entire disclosure of each is hereby fully incorporated by reference.

WO 2006/007438 PCT/US2005/021520 Generally, the various prioessesiivolve dissolving the elastomer in an organic solvent, followed by forming a water-based dispersion thereof with the aid of a surfactant. Any remaining solvent can be removed as by steam stripping. The chlorinated natural rubber generally contains from about 60% to about 75% and desirably from about 65% to about 68% by weight of chlorine therein based upon the total weight of the natural rubber. The chlorinated natural rubber latex generally contains from about 25 to about 75 and desirably from about 40 to about 60 weight percent of solids.

[028] The incompressible spheroidal particulates contained in the RTM adhesives exhibit a compression strength of at least 200 a 50 t h percentile particle size ranging from 5 to 25 im, and a BET surface area of from 0.1 to 10 m 2 /g.

The incompressible spheroidal particulates are inert to the reactive adhesive components, and are nonmetallic materials of a crystalline nature and selected from natural and synthetic calcined aluminum oxide, aluminosilicate, silicon dioxide, and ceramics materials. "Aluminum oxide" as used herein may include any aluminum oxide including A1 2 0 3 products having up to 1% impurities not limited to native alumina, found as the mineral carborundum and refined by the Bayer process to remove impurities and produce a nominal 99.5% A1 2 0 3 product. The aluminum oxide may be any of the commercially available alumina products.

[029] The spheroidal ceramic spheres of which those naturally occurring or synthetically produced such that the compositions can include those containing about to about 99% by weight silicon dioxide. Other components include up to about aluminum oxide, sodium oxide from 0 to up to about 11%, potassium oxide up to about carbon up to about 3% and/or calcium oxide, ferric oxide, magnesium oxide, titanium oxide, sulfur trioxide in quantities from 0 to about 2%.

[030] The ceramic spheres preferably will be silica and alumina or alkali aluminosilicate ceramic. Such products can be obtained commercially including 3M® Zeeospheres® ceramic microspheres. Hollow ceramic spheres must have compression or crush strength of at least 200 p.s.i. and preferably have crush strength of 20,000 60,000 p.s.i.

WO 2006/007438 PCT/US2005/021520 [031] Other incompressible spheroidal particulates suitable herein are spheroidal silicon dioxide particles. These typically have a composition of from about to about 99% by weight silicon dioxide and 0 to about 30 aluminum oxide, as the key components, and contain sodium oxide from 0 to about 11%, potassium oxide from 0 to about carbon from 0 to about 3% and/or calcium oxide, ferric oxide, magnesium oxide, titanium oxide, sulfur trioxide in quantities from 0 to about The silicon dioxide material may be any of the commercially available products meeting the requirements set forth herein. One preferred silicon dioxide material has a composition of about 99% silicon dioxide. This material occurs naturally in globular balls and is process treated with high purity heat and sold commercially as Goresil®.

The particle size of the silicon dioxide suitably employed herein is a 5 0 th percentile diameter of 5 to 35 microns and preferably about 5 to 20 microns.

[032] The incompressible sheroidal spheres are effective in improving the processability of the adhesive, maintaining a higher solids sprayable adhesive while at the same time providing industrially acceptable bonding performance when utilized in an amount of from 5 to 35 preferably from 20 to 25 wt.% on dry wt. of adhesive.

[033] The adhesive according to the invention can be formulated using water as the liquid carrier, in which case the halogenated polymer must be provided as an aqueous dispersion or latice. Suitable latices include the emulsion polymer latexes.

Baled elastomers can be rendered as aqueous dispersions when converted from solvent solutions. The preferred aqueous-based film-formers are halogenated diene latices. A combination of a halogenated diene-type latex and an aqueous dispersion of a halogenated polyolefin is preferred. The preferred butadiene latices are disclosed in the following U.S. Patents: 6,268,422, 6,132,870, 5,496,884, 5,281,638, 5,717,031, 5,300,555, and 5,200,459, all incorporated herein by reference. The halogenated polyolefin of the latex can essentially be any natural or synthetic halogenated polyolefin elastomer. The halogens employed in the halogenated polyolefinic elastomer are typically chlorine or bromine, although fluorine can also be used. Mixtures of halogens can also be employed in which case the halogencontaining polyolefinic elastomer will have more than one type of halogen substituted thereon. The amount of halogen does not appear critical and can range from as low WO 2006/007438 PCT/US2005/021520 as about 3 weight percent to more than 70 weight percent, depending on the nature of the base elastomer or polymer.

[034] Representative halogenated polyolefins include chlorinated natural rubber, chlorine- and bromine-containing synthetic rubbers including polychloroprene, chlorinated polychloroprene, chlorinated polybutadiene, hexachloropentadiene, butadiene/halogenated cyclic conjugated diene adducts, chlorinated butadiene styrene copolymers, chlorinated ethylene propylene copolymers and ethylene/propylene/non-conjugated diene terpolymers, chlorinated polyethylene, chlorosulfonated polyethylene, brominated poly(2,3-dichloro-1,3-butadiene), copolymers of a-haloacrylonitriles and 2,3-dichloro-1,3-butadiene, chlorinated poly(vinyl chloride), and the like, including mixtures of two or more halogenated polyolefins. Thus substantially any of the known halogen-containing derivatives of natural and synthetic elastomers can be employed in the practice of this invention, including mixtures of such elastomers.

[035] Particularly preferred halogenated polyolefins utilized herein are 40-60 60-40 wt. ratio blend of chlorosulfonated polyethylene to chlorinated rubber, as well as a 60-70 40-30 wt. ratio blend of chlorosulfonated polyethylene to chlorinated rubber.

[036] Preferred for the aqueous RTM adhesives herein are brominated poly(2,3-dichloro-1,3-butadiene, and copolymers of a-haloacrylo-nitriles and 2,3dichloro-1,3-butadiene as disclosed in U.S. Pat. No. 5,496,884, incorporated herein by reference.

[037] An aqueous dispersion of halogenated polyolefin can be prepared according to methods known in the art such as by dissolving the halogenated polyolefin in a solvent and adding a surfactant to the resulting solution. Water is added to the solution under high shear mixing, or in a jacketed colloidal energy mill to invert the initial continuous phase from solvent to water resulting in a colloidally stable polymer dispersion. The solvent is stripped to obtain a latex having a total solids content of from about 10 to 50, preferably 25 to 45 wt. percent solids. Latices are also prepared by conventional emulsion polymerization of chlorinated ethylenically WO 2006/007438 PCT/US2005/021520 unsaturated monomhiers. Suiitable aqueous dispersions of halogenated polyolefins such as chlorosulfonated polyethylene are available from Lord Corporation.

[038] A supplemental polymeric film-forming component may be a latex, dispersion, emulsion of a non-halogenated polymeric material. Examples of such non-halogenated polymeric materials, which may be utilized in aqueous form, include epoxy resins, phenoxy resins, resorcinol resins, melamine resins, styrenebutadiene copolymer rubber, natural rubber, polyacrylates, polybutadienes and polyvinylacetates. It should be noted that in addition to acting as a supplemental filmformer, an epoxy resin may also act as an acid acceptor and used in conjunction with or as a replacement for particulate acid acceptors, e.g. zinc oxide.

[039] If employed, the supplemental polymeric film-forming component of the present invention is typically utilized in an amount ranging from about 0.1 to preferably from about 5 to 20 percent by dry weight (excluding solvent and water) of the total adhesive composition.

[040] An essential component of the adhesive compositions of the present invention is a nitroso compound or precursor such as quinone dioxime. The nitroso groups function by crosslinking. Included are nitroso compounds or precursors capable of being converted by oxidation to a nitroso compound at elevated temperatures, such as occurs on exposure to temperatures from about 140 to 200 °C.

A suitable precursor is found in the class of quinone compounds. Examples of quinone compound derivatives useful as nitroso compound precursors in the present invention include quinone dioxime, dibenzoquinone dioxime, 1,2,4,5tetrachlorobenzoquinone, 2-methyl-1,4-benzoquinone dioxime, 1,4-naphthoquinone dioxime, 1,2-naphthoquinone dioxime, and 2,6-naphthoquinone dioxime. The nitroso compound may be replaced by the corresponding oxime or the corresponding nitro compound with the appropriate oxidation/reduction agent. The nitroso compounds are preferred and are based on aromatic hydrocarbons, such as benzenes, naphthalenes, anthracenes, biphenyls, and the like, containing at least two nitroso groups attached directly to non-adjacent ring carbon atoms. More particularly, such WO 2006/007438 PCT/US2005/021520 nitroso compounds are described as aromatic compounds having from 1 to 3 aromatic nuclei, including fused aromatic nuclei, having from 2 to 6 nitroso groups attached directly to non-adjacent nuclear carbon atoms. The preferred nitroso compounds are the dinitroso aromatic compounds, especially the dinitrosobenzenes and dinitrosonaphthalenes, such as the meta- or para-dinitrosobenzenes and the meta- or para-dinitrosonaphthalenes. The nuclear hydrogen atoms of the aromatic nucleus can be replaced by alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl, arylamine, arylnitroso, amino, halogen, and like groups. The presence of such substituents on the aromatic nuclei has little effect on the activity of the nitroso compounds in the present invention.

As far as is presently known, there is no limitation as to the character of the substituent, and such substituents can be organic or inorganic in nature. Thus, where reference is made herein to nitroso compound, it will be understood to include both substituted and unsubstituted nitroso compounds, unless otherwise specified.

[041] The preferred poly-C-nitroso materials are the di-nitroso aromatic compounds as (R)m -Ar-(NO) 2 where Ar is phenylene or napthalene, especially the m- or p-dinitrosobenzenes (DNB) and dinitrosonaphthalenes. R in (R)m -Ar-(NO) 2 is a monovalent organic radical selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, alkaryl, arylamine and alkoxy radicals having from 1 to 20 carbon atoms, amino, or halogen, and is preferably an alkyl group having from 1 to 8 carbon atoms; and m is zero, 1, 2, 3, or 4. Preferably m is zero. DNB is incorporated into the adhesive composition by addition as a solvent dispersion. Exemplary nitroso compounds are m-dinitrosobenzene, p-dinitrosobenzene, m-dinitrosonaphthalene, pdinitrosonaphthalene, 2,5-dinitroso-p-cymeme, 2-methyl- ,4-dinitrosobenzene, 2- 1,4-dinitrosobenzene, 2-fluoro-1,4-dinitrosobenzene, 2-methoxy-1-3dinitroso-benzene, 5-chloro-1,3-dinitrosobenzene, 2-benzyl-1,4-dinitrosobenzene, 2cyclohexyl-1,4-dinitrosobenzene and combinations thereof. Particularly preferred nitroso compounds include p-dinitrosobenzene and m-dinitrosobenzene.

[042] Nitroso compounds are utilized in an amount ranging from about 15 to and preferably from 17 to 23 wt% on dry weight of the total adhesive composition.

WO 2006/007438 PCT/US2005/021520 [043] The optional co-curing agent contains at least two groups capable of forming covalent crossbonding and crosslinking between the other components of the RTM adhesive, bonded rubber, and/or primer, such as, by way of an addition polymerization or condensation polymerization. As employed herein, co-curing agents reactive by way of addition polymerization undergo a free-radical reaction, or they may undergo an anionic polymerization, a cationic polymerization, a ring-opening polymerization, or coordinative polymerization.

[044] The preferred crossbonding/ crosslinking reactive moiety participates in an addition polymerization. Preferred addition polymerizable moieties include, for example, optionally substituted alkenyl, oxyalkenyl, alkynyl, cycloalkenyl, bicycloalkenyl, styryl, (meth)acrylate, itaconate, maleimide, vinyl ester, epoxy, cyanate ester, nitrile, diallyl amide, benzocyclobutene, aromatic propargyl ether, aromatic acetylene, oxazoline, and the like. More preferred addition polymerizable moieties include alkenyl, oxyalkenyl, (meth)acrylate, maleimide, or cycloalkenyl. The most preferred adhesive compositions of the present invention further comprise a maleimide co-curing compound. The maleimide compound crosslinker can essentially be any compound containing at least two maleimide groups, as in bis-maleimide groups, as well as poly-bis maleimides. The maleimide groups may be attached to one another or may be joined to and separated by an intervening divalent radical such as alkylene, cyclo-alkylene, epoxydimethylene, phenylene (all 3 isomers), 2,6dimethylene-4-alkylphenol, or sulfonyl. An example of a maleimide compound wherein the maleimide groups are attached to a phenylene radical is m-phenylene bismaleimide and is available as HVA-2 from E. I. Du Pont de Nemours Co.

[045] The suitable poly(bismaleimides) are aromatic polymaleimides having from about 2 to 100 aromatic nuclei wherein no more than one maleimide group is directly attached to each adjacent aromatic ring are preferred.

Particularly preferred polymaleimide compounds have the formula: WO 2006/007438 PCT/US2005/021520 o N 0 0 N 0 0 N 0

CH-CH

2 (pm x wherein x is from about 1 to 100. An exemplary commercial poly(bismaleimide) is sold as BMI-M-20 and BMI-S designation by Mitsui Toatsu Fine Chemicals, Incorporated.

[046] The preferred co-curing agent maleimide compound is preferably utilized in the present invention in an amount ranging from about 5 to 15 preferably from about 5 to 10 wt.% on dry weight of the total adhesive composition.

[047] The adhesive compositions of the present invention may optionally contain a vulcanizing agent. The vulcanizing agent of the present invention can be any known vulcanizing agent which is capable of crosslinking elastomers at conventional temperatures. Preferred vulcanizing agents for use in the invention are selenium, sulphur, and tellurium, with selenium being most preferred. Optional vulcanizing agents can be employed in an amount ranging from about 1 to preferably from about 2 to 7, percent by dry weight of the total adhesive composition.

[048] An essential component of the adhesive compositions of the present invention is an acid acceptor. The acid acceptor is preferably a metal oxide, phosphate, phosphite, hydroxide and the like capable of scavenging free halogenous acids, oxides, phosphates, phosphites, and/or hydroxides. Example acid acceptors include oxides of zinc, cadmium, calcium, magnesium, lead, and zirconium; litharge; red lead; zirconium salts; and combinations thereof, and to a lesser extent calcium hydroxide, calcium carbonate and dibasic lead phosphite. Mixtures of more than one acid acceptor may be used in this invention, such as a preferred combination of dibasic lead phosphite (Dyphos) and zinc oxide. Specific examples of lead salts include dibasic lead phthalate, monohydrous tribasic lead maleate, tetrabasic lead fumarate, dibasic lead phosphite, and combinations thereof. Other examples of leadcontaining compounds include basic lead carbonate, lead oxide and lead dioxide.

14 WO 2006/007438 PCT/US2005/021520 Lead-containing acid acceptorTsare very effective, such as polybasic lead salts of phosphorous acid and saturated and unsaturated organic dicarboxylic acids and acid anhydrides, however lead-containing compounds are coming under increased concern for bioaccumulation. For environmental reasons, metal oxides are preferred over lead-containing compounds for purposes of the invention. A suitable replacement for lead-containing acid acceptors are metal phosphates, aluminum phosphate surface treated with a zinc compound, such as treatment with zinc hydroxide, and conversion to zinc oxide by filtering, washing with water, drying and heat-treating. The phosphates treated with Zn compounds can be used alone or in any mixtures with aluminum and/or zinc oxides. A more preferred acid scavenger is a mixture of from 25-35 wt.% zinc oxide, 25-35 wt.% zinc phosphate and 25-35 wt.% aluminum phosphate. A preferred lead substitute is a 1:1:1 mixture of zinc oxide, zinc phosphate and aluminum phosphate commercially available from Heubach Company as Heucophos®.

[049] Acid acceptor is preferably utilized in an amount ranging from about to 30 preferably 10 to 15 depending upon the selection of acceptor type and wt. and halogen content of the halogenated polyolefin.

[050] The solid components of the adhesive are contained in a volatile solvent or aqueous carrier. For solvent based embodiments, example suitable solvents are aromatic and halogenated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and the like; halogenated aliphatic hydrocarbons such as trichloroethylene, perchloroethylene, propylene dichloride and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and the like; ethers, naphthas, etc., including mixtures of such carriers. The amount of the carrier employed is that which provides a composition suitable for use as an adhesive. A conventional amount will ordinarily be such as to provide a total solids content ranging from about 5 to 80, preferably about 15 to about 40 percent by weight.

[051] The adhesive compositions of the present invention can optionally contain other well-known additives including plasticizers, pigment. Those embodiments utilizing organic solvents as the carrier are essentially absent WO 2006/007438 PCT/US2005/021520 surfactants. Other inert iparticlte- fillers having a BET surface area greater than m 2 e.g. talc, clay and CaCO 3 can be employed in quantities not exceeding 10 wt.% as a substitute of the corresponding amount of incompressible sheroidal particles.

Those embodiments containing water as the carrier typically contain a minor amount of dispersing agent, such as lignosulfonates, and/or wetting agents. In some instances it is preferable to include carbon or glass reinforcing filaments, and the like, in amounts employed by those skilled in the adhesive arts to obtain a desired color and consistency. Examples of optional ingredients include carbon black, silica such as fumed silica, and titanium dioxide.

[052] The adhesive compositions of the present invention may be prepared by any method known in the art, but are preferably prepared by combining and milling or shaking the ingredients and solvent or water vehicle in a ball-mill, sand-mill, ceramic bead-mill, steel bead-mill, high speed media-mill, or the like. The adhesive compositions may be applied to a surface to be bonded by spraying, dipping, brushing, wiping, roll-coating or the like, after which the adhesive composition is permitted to dry. The adhesive composition is typically applied in an amount sufficient to form a dry film thickness ranging from about 0.3 to 2.0 mils, preferably from about 0.3 to 0.8 mils. Adhesive dry film thickness above 2 mils total causes cohesive failure, while film thickness less than 0.1 mils can generate failure due to inadequate surface coverage. In the case of a two-coat adhesive composition, the adhesive is applied in a similar manner over the primer coat which has been permitted to completely dry.

[053] The one-coat adhesive embodiments of the invention are especially adapted to be utilized to bond elastomers to metal surfaces without the use of a primer. The composition may be applied any substrate surface, to the metal surface, by spraying, dipping, brushing, wiping or the like, after which the wet adhesive coating is permitted to dry. The adhesive composition is typically applied to metal surfaces and the coated metal surface and elastomeric substrate are then brought together under heat and pressure for substantial contact and bonding completed in the rubber vulcanizing procedure. In some cases, it may be desirable to preheat (35 -80 0 C) the metal surface prior to application of the adhesive composition to assist in drying of the adhesive composition. The coated surface of the metal and WO 2006/007438 PCT/US2005/021520 the elastomeric substrat are typically brought together under a pressure of from about 20.7 to 172.4 Mega Pascals (MPa), preferably from about 20 MPa to 50 MPa.

The resulting rubber-metal assembly is simultaneously heated to a temperature of from about 1400 C to about 2000 preferably from about 150°C to 1700 C. The assembly should remain under the applied pressure and temperature for a period of from about 3 minutes to 60 minutes, depending on the vulcanizable elastomer cure rate and thickness of the elastomer substrate. This process may be carried out by applying the rubber substrate as a semi-molten material to the metal surface as in, for example, an injection-molding process. The process may also be carried out by utilizing compression molding, transfer molding or autoclave curing techniques. After the process is complete, the bonded adhesive and elastomer are fully vulcanized and ready for use in a final application, such as engine mount, damper, or belting, to name a few typical uses.

[054] The adhesive compositions of the present invention may be prepared by any method known in the art, but are preferably prepared by combining and milling or shaking the ingredients and water in a ball-mill, sand-mill, ceramic bead-mill, steel bead-mill, high speed media-mill, or the like.

[055] The adhesive compositions may be applied to a surface to be bonded by spraying, dipping, brushing, wiping, roll-coating or the like, after which the adhesive composition is permitted to dry. The one-coat adhesives are suitably applied in an amount sufficient to form a dry film thickness ranging from about 0.3 to 2.0 mils (8 to jim), preferably from about 0.3 to 0.8 mils. In the case of a two-coat adhesive composition as described more fully hereinafter, the adhesive is applied in a similar manner over the primer coat which has been permitted to completely dry.

[056] The adhesive compositions of the present invention are capable of bonding any substrate or surface capable of receiving the adhesive composition. The adhesive is designed especially for bonding metal surfaces to a polymeric material, and especially elastomeric materials selected from natural rubber, olefinic synthetic rubber including polychloroprene, polybutadiene, neoprene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene 17 WO 2006/007438 PCT/US2005/021520 copolymer rubber, ethylene-irojdyene-diene terpolymer rubber, butyl rubber, brominated butyl rubber, alkylated chlorosulfonated polyethylene and the like. The material may also be a thermoplastic elastomer such as the thermoplastic elastomers sold under the tradenames SANTOPRENE and ALCRYN by Monsanto and DuPont, respectively. The material is most preferably an elastomeric material such as natural rubber (cis-polyisoprene). The surface to which the material is bonded can be any surface capable of receiving the adhesive such as a glass, plastic, or fabric surface, and is preferably a metal surface selected from any of the common structural metals such as iron, steel (including stainless steel), lead, aluminum, copper, brass, bronze, MONEL metal alloy (Huntington Alloy Products Div., International Nickel Co., Inc.), nickel, zinc, and the like. Prior to bonding, a metal surface is typically cleaned according to one or more methods known in the art such as degreasing, grit-blasting and zinc-phosphatizing.

[057] The RTM adhesive disclosed herein can be utilized to bond rubber to metal as a one-coat adhesive, or as a two-coat combination of the adhesive as a cover coat applied over a primer. The primer is applied directly to the metal surface and can be a conventional water-based or solvent-based primer. Suitable waterbased primers include phenolic resin-type primers such as CHEMLOK® 802, CHEMLOK@ 805, CHEMLOK® 8006, 8007 and CHEMLOK@ 8401 produced by Lord Corporation. Suitable solvent-based primers include phenolic resin-type primers such as CHEMLOK 205( or CHEMLOK 207@ produced by Lord Corporation. The invention as covercoat is applied directly to the primer which has been applied to the metal so as to ensure contact between the adhesive composition and the elastomeric substrate which is brought into contact with the coated metal surface.

[058] The adhesive compositions of the present invention are preferably prepared by combining and milling or shaking the solid ingredients and solvent or water carrier vehicle in a ball-mill, sand-mill, ceramic bead-mill, steel bead-mill, high speed media-mill, or the like. The adhesive compositions are applied to a surface to be bonded by spraying, dipping, and dip-spinning after which the adhesive composition is permitted to dry. The adhesive composition performs well when applied in an amount sufficient to form a dry film thickness ranging from about 0.3 to 2.0 mils.

18 WO 2006/007438 PCT/US2005/021520 Adhesive dry filii thiKnea-i9'bo0e 2 mils tends to cause a cohesive failure within the adhesive, while film thickness less than 0.3 mills can generate failure due to inadequate surface coverage. In the case of a two-coat adhesive composition, the adhesive is applied in a similar manner over the primer coat which has been permitted to completely dry.

[059] Adhesive may be coated on metal parts as-received, or in some cases, it is desirable to preheat the metal parts to a temperature in a range of from 35 to about 800C prior to application of the adhesive composition to assist in drying. The coated surface of the metal and the elastomeric substrate are typically brought together under a pressure of from about 20.7 to 172.4 Mega Pascals (MPa), preferably from about MPa to 50 MPa. The resulting rubber-metal assembly is simultaneously heated to a temperature within a range of from about 1350 C (275 IF) to about 171 C (375 0

F),

and preferably from about 150 0 C to 1700 C. The assembly should remain under the applied pressure and temperature for a period of from about 3 minutes to 60 minutes, depending on the vulcanizable elastomer cure rate and thickness of the elastomer substrate. This process may be carried out by applying the rubber substrate as a semi-molten material to the metal surface as in, for example, an injection-molding process. The bonding process may also be carried out by utilizing compression molding, transfer molding or autoclave curing techniques. After the process is complete, the bonded adhesive and elastomer are fully vulcanized and ready for use in a final application, such as engine mount, damper, or belting, to name a few typical uses.

[060] The adhesives according to the invention are able to form rubber-tearing bonds even after soaking at elevated temperatures prior to contact with the vulcanizable elastomer. This is referred to as pre-bake resistance as a capability of tolerating a prebake cycle of up to about 12 minutes at 340'F (171 0C) and still maintain the capability of providing a high percentage (80% 100% rubber tearing or retention on the metal surface after vulcanization of the rubber compound. That is, even though heated for up to 12 minutes at 340'F before contact with the rubber, after cure of the rubber, the adhesive does not fail but rather generally at least 80%, desirably at least 85% or WO 2006/007438 PCT/US2005/021520 and preferably at least 95% br100% of the bonded rubber tears during destructive testing.

EXAMPLES

[061] The following testing of examples are disclosed in order to further illustrate and fully disclose the invention and are not intended to limit in any manner the scope of the invention which is defined by the claims.

[062] Primary Adhesion (PA) bonded parts are pulled to destruction according to ASTM Test D429-Method B. Parts are tested in peel with a peel angle of degrees. The test is conducted at room temperature with a specified test speed of, for example 2 or 20 inches per minute. After the bonded part fails, the peak peel strength value (measured in pounds per lineal inch) and the percent rubber retention on the adhesive coated area of the part are measured.

[063] 72-Hour Salt Spray (SS) Bonded parts are buffed on the edges with a grinding wheel. The rubber is then tied back over the metal with stainless steel wire so as to stress the bonded area. This exposes the bond line to the environment. Failure is initiated by scoring the bond line with a razor blade. The parts are then strung on stainless steel wire and placed in a salt spray chamber. The environment inside the chamber is 100 OF, 100 percent relative humidity, and 5 percent dissolved salt in the spray, which is dispersed throughout the chamber. The parts remain in this environment for 72 hours. Upon removal, the rubber is peeled from the metal with pliers. The percent rubber retention on the parts is then measured.

[064] Hot Tear (HT) is performed after bonded parts have soaked for 15 min.

at 300 OF.

[065] 2-Hour Boiling Water (BW) Bonded parts are prepared the same way as they are for the salt spray test; however, in this test, the parts are placed in a beaker filled with boiling tap water. The parts remain in this environment for 2 hours.

WO 2006/007438 PCT/US2005/021520 Upon removal, the rubber is peeled from the metal with pliers. The percent rubber retention on the parts is then measured.

[066] 7-Day Room Temperature Water-Immersion [067] Bonded parts are prepared the same way as they are for the salt spray test. In this test, the parts are placed in a beaker filled with tap water which is at room temperature. The parts remain in this environment for 7 days. Upon removal, the rubber is peeled from the metal with pliers. The percent rubber retention on the part is then measured.

[068] The following examples are disclosed in order to further illustrate and fully disclose the invention and are not intended to limit in any manner the scope of the invention which is defined by the claims. Illustrated results of the above tests are set forth in tables below. In the data, reference is made to failure in the rubber body Failure is expressed in terms of percent, and a high percent of failure in the rubber is desirable since this indicates that the adhesive bond is stronger than the rubber itself.

[069] Adhesive Example 1 (See Example 70-R, series 70 below) Component Description Wt. Dry Weight Wet Weight Dinitrosobenzene (DNB) 20.6 5.37 15.34 Zinc oxide 1.03 2.68 2.68 m-phen bismaleimide 1.03 2.68 2.68 C NR 15.5 4.04 4.04 Carbon Black 1 0.26 0.26 CSM 16.4 4.27 4.27 Ceramic spheres 25.7 6.70 6.70 Xylene 0.00 64.03 26.00 100.0 WO 2006/007438 PCT/US2005/021520 [070] Adhesive Example 2 (See Example 70-Q in series 70 below) Component Description Wt. Dry Weight Wet Weight Dinitrosobenzene 20.0 5.20 14.86 Zinc oxide 10.0 2.60 2.60 Bismaleimide** 10.0 2.60 2.60 Chlorinated natural rubber 15.1 3.92 3.92 Carbon Black** 4.0 1.04 1.04 Chlorosulfonated PE (CSM) 15.9 4.14 4.14 Ceramic spheres** 25 6.50 6.50 Xylene 0.00 64.34 26.0 100.0 [071] Preparation procedure: these solids were pre-dried in an oven at 170OF (76 for 48 hrs.

Xylene was charged to a tank equipped with a Hockmeyer® mixer.

CNR rubber, carbon black, maleimide, zinc oxide and ceramic spheres were added and mixed for 30 minutes. Speed was adjusted upwards if needed.

a pre-agitated 35% solution of DNB in xylene was added with mixing for minutes.

Ingredients were pumped to a sandmill and recirculated back to the tank until a o to 2.0 mil grind is obtained using a Hegman® grind guage available from Precision Guage Tool Co. Dayton, Ohio. Carbon black and CNR are preferably pre-ground using a Kady@ mill for larger batches prior to processing through the sand mill.

The pump and sandmill were cleaned with xylene, and added to the tank.

CSM was added with mixing until dissolution.

[072] The following series 12 examples according to the invention were prepared at the same TSC level as a commercial control, at 28%. Viscosity was measured after shelf aging at room temperature.

WO 2006/007438 WO 206/07438PCT/US2005!021520 [073] Masterbatch Raw Miaterials TSC DNB 35 Pb phosphite 100 2nD 100 spheres 100 c. Black 100 Maleimide 100 Fumed silica 100 CNR 25 Xylene 0 TSC Di'y K/t Raw Materials TSC CSM 20 CNR 25 Xylene 0 TSC Dry Wt %A Total Dry WtA Masterbatch Commercial12 2 12] c.,ontrol I 12B 12C 12D 2 2 2 24.50 21.85 19.65 17.50 15.31 15.15 13.46 27.12 0.00 0.00 0.00 0.00 0.00 0.00 0.00 35.00 31.53 28.00 24.50 15.00 10.00 0.00 0.00 10.00 20.00 30.00 40.00 50.00 6.73 5.96 5.36 4.77 4.19 4.12 3.65 10.62 9.50 8.54 7.60 6.65 6.58 5.85 2.65 2.35 2.12 1.88 1.62 1.62 1.46 1.23 1.08 0.96 0.85 0.77 0.73 0.00 0.00 0.00 0.00 0.00 0.00 0.00 28.49% 28.11% 28.00%/ 28.00% 28.00% 28.00% 28.00% 73 76 78 81 83 83 Adhesive 12A 12B 12C 12D 12E i2F 12G 20.31 6.85 0.00 26.00% 27 100 18.15 16.34 14.52 12.69 12.5 11. 6.12 5-50 4.88 4.27 4.23 3.77 0.00 0.00 0.00 0.00 0.00 0.00 26.00% 26.00% 26.00% 26.00% 26.00% 26.00% 24 22 19 17 17 100 100 100 100 100 100 [074] Testing: Brookfield viscosity of shelf-aged samples 12A 12B 12C 12D 12E 12F 12G cPs (2 30rpm) Initial 318 249 160 124 75 64 +1 Week 353 223 132 95 -2 Weeks 419 202 125 81 +3 Weeks 472 191 120 81 +4 Weeks 620 219 146 89 Weeks 750 210 130 85 58 54 48 46 42 41 44 44 39 48 46 53 48 44 WO 2006/007438 PCT/US2005/021520 [0751 Series 12 Bonding performance rubber retained 1 r 1 r FX. O Avg PA. 4' R STD FX. 4' BW, 0' BW, 4' 1 SS, 0' SS, 4' PAO' CH 253X 100 100 83 88 92 92 100 100 94.4 6.6 PC16NL 100 100 30 38 90 98 100 100 82.0 29.9 12A 99 100 65 93 100 88 100 100 93.0 12.2 12B 100 100 67 93 100 92 100 100 94.0 11.4 12C 99 100 87 70 100 93 100 100 93.6 10.6 12D 100 100 97 70 93 92 100 100 94.0 10.2 12E 100 99 53 33 97 93 100 100 84.4 26.2 12F 100 97 48 40 93 82 100 100 82.5 24.6 12G 100 100 17 20 80 88 100 100 75.6 36.0 [076] Examples adhesive from series 51 Adhesive Formulations Raw Materials

DNB

ZnO spheres Carbon black Bismaleimide Fumed silica

CNR

Xylene Raw Materials

CSM

CNR

Xylene Masterbatch %TSC 51A I SIB I1C I 61D I 61E 61F 1 IG 35 20.00 20.00 20.00 20.00 20.00 20.00 20.00 100 10.00 10.00 10.00 10.00 10.00 10.00 10.00 100 30.00 30.00 30.00 30.00 25.00 25.00 25.00 100 4.62 4.00 4.00 4.00 4.00 4.00 4.00 100 10.00 7.50 7.50 7.50 10.00 10.00 10.00 100 1.85 0.00 0.00 0.00 0.00 0.00 0.00 25 0.92 1.00 1.00 1.00 1.00 1.00 1.00 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TSC 30% 30% 30% 30% 30% 30% Dry Wt 77 73 73 73 70 70 Adhesive %SC 51 51 51C I 51D I 51E 5F 61G 20 15.92 15.92 20.81 18.37 15.92 23.31 19.62 25 6.69 11.58 669 9.13 14.08 6.69 10.38 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TSC 26% 26% 26% 26% 26% 26% 26% Dry Wt 23 28 28 28 30 30 Total Dry Wt% 100.0 100.0 100.0 100.0 100.0 100.0 100.0 WO 2006/007438 WO 206/07438PCT/US2005!021520 [077] Testing Parameters Application: Spray@~ 1 500F Adhesives:, DFT@ 0.80- 1.0 Omits-I1 coat DFT 0. 65 0.85 mils 2 coat ElastomerstCures Elastomer used: 40-45 A durometer sulfur cured NR cured at 320 IF (160 C) for 16.5' Rubber was compression Molded' Curing time is the time to a 90% cure 10 min. (t:90 Commercial controls Chemlok 253X and PC1 6NL Testing Primer DFT 0.25 0.35 mils Commercial primer Chemlok 205 Salt Spray 5 day stressed Prebake: Primary Adhesion Boiling Water 2 hrs stressed Hot Tear after 15 min. soak 300'17 Phy sicalProperties_____ (Units) 51 A 51B 51C 51 D 51E 51F 51G Viscosity CPS 193 184 266 233 218 366 286 Density lb/gal 8.3 8,3 8.3 8 8.3 83 8.3 8.3 Solids (3B) %-68 0 C 25.3 25.17 23.54 25.38 25.14 24.97 -25.49 Grindl mils 0 0 0 0 0 0 0 WO 2006/007438 PCT/US2005/021520 [078] Series 51 Performance Summary Data: Elastomer: 40-45 A durometer sulfur cured NR cured at 320OF 12 min I Coat Testing (test type, prebake) rubber retention Test BW, 0' BW, 3' SS, 0' SS, 3' HT, 0' HT, 3' PA, 0' PA, 3' Avg %R STD System CH 253X PC16NL 51A 51B 51C 51D 51E 51F 51G 100 100 100 100 100 100 99.0 2.8 73 43 100 100 100 100 70.1 35.6 100 100 100 100 100 100 93.9 14.0 97 90 100 100 100 100 90.0 15.0 100 95 100 100 100 100 91.0 15.2 98 93 100 100 100 100 87.8 20.4 95 100 100 100 100 100 96.0 6.4 96 70 100 100 100 100 78.6 32.5 99 72 100 100 100 100 83.4 27.6 2 Coat Testing Test BW, 0' BW, 3' SS, 0' SS, 3' HT, 0' HT, 3' PA, 0' PA, 3' Avg %R STD System 205 CH 253X 73 2051PC16NL 100 205151A 84 205/51B 52 205/51C 100 205/51D 88 205151E 95 205/51F 87 205/51G 88 100 100 100 100 100 100 94.1 11.0 100 98 100 100 100 100 98.5 98 97 100 100 100 100 94.3 97 95 100 100 100 100 86.8 22.1 98 95 100 100 100 100 96.9 6.3 99 98 100 100 100 100 93.4 13.3 98 98 100 100 100 100 96.4 6.8 100 95 100 100 100 100 92.5 14.7 98 98 100 100 100 100 93.9 11.6 Combined Avg %R STD 205/CH 253X CH 253X 96.6 8.2 205/PC16NL PC16NL 84.3 28.5 205/51A 51A 94.1 11.6 205/51B 51B 88.4 18.4 205/51C 51C 93.9 11.6 205/51D 51D 90.6 16.9 205/51E 51E 96.2 6.4 205 /51F 51F 85.6 25.4 205/51G 51G 88.6 21.2 WO 2006/007438 PCT/US2005/021520 [079] Example adhesives from series Adhesive Formulations Raw Materials

DNB

ZnO ZnAI Phos spheres Bismaleimide Poly-bismaleimide Carbon black Fumed silica CNR1 CNR2 Xylene Raw Materials

CSM

CNR1 CNR2 Xylene Raw Materials

DNB

ZnO ZnAI Phos spheres Bismaleimide Poly-bismaleimide Carbon black 1 Carbon black 2 Fumed silica CNR1 CNR2 Xylene Raw Materials

CSM

CNR1 CNR2 Xylene TSC 70A 35 21.85 100 35.00 100 0.00 100 0.00 100 9.50 100 0.00 100 5.96 100 2.35 25 1.08 30 0.00 0 0.00 TSC 30% TSC 70A 20 18.15 25 6.12 30 0.00 0 0.00 TSC 26% Total Dry Wt% 100 TSC 70K 35 20.00 100 10.00 100 0.00 100 30.00 100 10.00 100 0.00 100 4.62 100 0.00 100 1.85 25 0.00 30 0.92 0 0.00 TSC 30% TSC 70K 20 15.92 25 0.00 30 6.69 0 0.00 TSC%: 26% Total Dry Wt% 100 70B 23.00 36.85 0.00 0.00 10.00 0.00 1.00 2.46 1.15 0.00 0.00 30% 70C 21.85 35.00 0.00 0.00 0.00 9.50 5.96 2.35 1.08 0.00 0.00 30% Masterbatch 70D 70E 70F 23.00 21.85 23.00 36.85 35.00 36.85 0.00 0.00 0.00 0.00 D.00 0.00 0.00 9.50 10.00 10.00 0.00 0.00 1.00 5.96 1.00 2.46 2.35 2.46 1.15 0.00 0.00 0.00 1.08 1.15 0.00 0.00 0.00 30% 30% 30% Adhesive 70D 70E 70F 19.12 18.15 19.12 6.42 0.00 0.00 0.00 6.12 6.42 0.00 0.00 0.00 26% 26% 26% 100 100 100 70B 70C 19.12 18.15 6.42 6.12 0.00 0.00 0.00 0.00 26% 26% 100 100 70L 20.75 10.38 0.00 31.12 10.38 0.00 1.00 0.00 1.92 0.00 0.96 0.00 30% 70L 16.52 0.00 6.96 0.00 26% 100 70M 20.00 10.00 0.00 25.00 10.00 0.00 4.00 0.00 0.00 1.00 0.00 0.00 30% 70M 15.92 14.08 0.00 0.00 26% 100 70N 20.65 10.31 0.00 25.77 10.31 0.00 1.00 0.00 0.00 1.04 0.00 0.00 30% 70N 16.42 14.50 0.00 0.00 26% 100 Masterbatch 700 70P 20.00 20.65 10.00 10.31 0.00 0.00 25.00 25.77 0.00 0.00 10.00 10.31 4.00 1.00 0.00 0.00 0.00 0.00 1.00 1.04 0.00 0.00 0.00 0.00 30% 30% Adhesive 700 70P 15.92 16.42 14.08 14.50 0.00 0.00 0.00 0.00 26% 26% 100 100 70G 70H 701 20.00 20.75 20.00 20.75 10.00 10.38 10.00 10.38 0.00 0.00 0.00 0.00 30.00 31.12 30.00 31.12 10.00 10.38 0.00 0.00 0.00 0.00 10.00 10.38 4.62 1.00 4.62 1.00 1.85 1.92 1.85 1.92 0.92 0.96 0.92 0.96 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 30% 30% 30% 70G 70H 701 15.92 16.52 15.92 16.52 6.69 6.96 6.69 6.96 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 26% 26% 26% 26% 100 100 100 100 70Q 70R 70S 20.00 20.65 28.14 30.16 10.00 10.31 0.00 0.00 0.00 0.00 19.31 20.69 25.00 25.77 0.00 0.00 10.00 10.31 11.00 11.81 0.00 0.00 0.00 0.00 4.00 1.00 0.00 0.00 0.00 0.00 7.58 1.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.00 1.04 1.00 1.07 0.00 0.00 0.00 0.00 30% 30% 30% 70Q 70R 70S 15.92 16.42 22.97 24.58 0.00 0.00 0.00 0.00 14.08 14.50 10.00 10.69 0.00 0.00 0.00 0.00 26% 26% 26% 26% 100 100 100 100 WO 2006/007438 PCT/US2005/021520 [080] Testing Parameters Application: Spray 150°F Adhesives: DFT 0.65 0.85 milse 2 coat Commercial Control CH 253X Commercial control PC-16NL Primer: DFT 0.25 0.35 mils Commercial primer Chemlok 205 ElastomerslCures 40-45 A durometer sulfur cured NR cured @320 °F (160 for 16' Compression Molded (t90 Primary Adhesion Boiling Water 2 hrs stressed Salt Spray 5 day stressed Prebake: 0 and 4 minute Substrate ZPS Coupon 3 ppt [081] Example series 70 Performance Summary Data: 2 Coat Testinc Tes BW, 0' BW,4' SS,0' SS,4' PA, 0' PA, 4' Avg %R STD System 205/CH253X 100 100 100 97 100 100 99.5 1.2 205/PC16NL 100 100 97 97 100 100 99.0 205/70A 100 100 97 100 100 100 99.5 1.2 205/70B 100 100 97 100 100 100 99.5 1.2 205/70C 100 100 100 100 100 100 100.0 0.0 205/70D 100 100 97 100 100 100 99.5 1.2 205/70E 100 100 97 100 100 100 99.5 1.2 205/70F 100 100 100 100 100 100 100.0 0.0 205/70G 100 100 95 95 100 100 98.3 2.6 205/70H 30 30 96 90 100 100 74.3 34.5 205/701 100 100 100 100 100 100 100.0 0.0 20570J 100 100 100 100 100 100 100.0 0.0 205/70K 100 100 95 92 100 100 97.8 205/70L 100 100 100 100 100 100 100.0 0.0 205/70M 100 100 98 98 100 100 99.3 205/70N 100 100 97 93 100 100 98.3 2.9 205/700 100 100 100 100 100 100 100.0 0.0 205/70P 100 100 96 95 100 100 98.5 2.3 205/70Q 100 100 96 97 100 100 98.8 1.8 205/70R 100 100 90 97 100 100 97.8 205/70S 100 100 100 93 100 100 98.8 2.9 205/70T 100 100 98 100 100 100 99.7 0.8 WO 2006/007438 PCT/US2005/021520 [082] Aqueous Carrier Embodiments.

The following series 45, 85, and 69 represent RTM adhesives according to the present invention in which water is used as a carrier and the solids are dispersed using wetting aid and dispersant. Bonded rubber-to-metal assemblies were prepared using standard procedures. Some coated coupons are exposed to prebake precure heat conditions. When prebaked for a specified time, the adhesive coated parts are exposed to the molding temperature for that specified time in minutes before the rubber is injected into the cavity. This simulates actual production conditions and helps determine if the adhesive remains active enough to successfully bond the rubber compound.

Adhesives were tested using multiple trials for primary adhesion, hot tear, boiling water, and salt spray resistance with and without prebake.

Elastomer tested: 40-45 A durometer sulfur cured NR cured at 320°F for 16 min.

Hot Tear was measured after 15 min 300 OF (149 oC) Adhesive DFT was 0.65 0.80 mils Bonding was done by compression Molding semi EV natural rubber compound (HC- 106) (t90 or Boiling Water test- parts were stressed for 2 hours.

For Salt Spray 7 day stressed Primary Adhesion was measured using a peel rate of Commercial primer used for each examples in series 45 A-J was Chemlok® 8121 The dry film thickness of the primer was 0.25 0.35 mils Commercial covercoat control was Chemlok® 8007 Prebake was 0 and 4 min.

The substrate was zinc phosphatized steel 3 ppt Failure modes were noted as follows: SB stock break, R Rubber cohesive; RC Rubber-to-cement; CM cement-to-metal, and CP Cement to primer failure.

WO 2006/007438 PCT/US2005/021520 [083] Series 45 aqueous adhesive examples Masterbatch_________ Raw TSC 45A 45B 45C 45D 45E 45F 45G 45H 451 Materials DNB Wetcake 84.6 30.13 19.60 22.62 21.13 18.49 18.49 18.49 18.49 18.49 18.49 C. Black 1 100 15.97 10.36 11.95 11.15 9.78 9.78 9.78 9.78 9.78 9.78 Wetting agent 33 0.48 0.32 0.38 0.35 0.29 0.29 0.29 0.29 0.29 0.29 Lignosulfate 100 0.48 0.32 0.38 0.35 0.29 0.29 0.29 0.29 0.29 0.29 ZnO 100 0.00 20.00 10.00 15.00 20.00 20.00 20.00 20.00 20.00 20.00 spheres 100 0.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 Dl Water 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TSC 29.51% 51.16% 53.02% 52.03% 48.54% 47.28% 46.08% 48.54% 47.28% 46.08% DryWt 47 66 60 63 64 64 64 64 64 64 Adhes Raw TSC 45A 45B 45C 45D 45E 45F 45G 45H 451 Materials_______ DCD 37 42.61 27.70 31.93 29.80 26.16 21.16 16.16 26.16 21.16 16.16 Terpolymer DCD 35 10.32 6.70 7.74 7.22 0.00 0.00 0.00 0.00 0.00 0.00 Homopolymer SBR Latex 50 0.00 0.00 0.00 0.00 10.00 15.00 20.00 0.00 0.00 0.00 HYP 605 50 0.00 0.00 0.00 0.00 0.00 0.00 0.00 10.00 15.00 20.00 Latex Dl Water 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TSC 31.00% 45.00% 45.00% 45.00% 45.00% 45.00% 45.00% 45.00% 45.00% 45.00% Dry Wt 53 34 40 37 36 36 36 36 36 36 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Dry Wt% [084] Series 45 performance testing of bond area and type of failure) I I I I I I I I I I I I I Testing: Hot Tear 15 mrin 300°F Prebake: Adhesive System lbs SB R RC CM Adhesive System Ibs SB R RC CM Primer Cover coat 36 0 100 0 0 65 1 100 0 0 CH 8007/CH 8121 37 0 100 0 0 CH 8007 45A 67 0 100 0 0 39 0 100 0 0 73 0 100 0 0 AVG: 37 0 100 0 0 AVG: 68 0 100 0 0 STD: 2 0 0 0 0 1 STD: 4 1 0 0 0 41 1 100 0 0 36 0 100 0 0 CH 8007 45B 44 0 100 0 0 CH 8007 45C 36 0 100 0 0 46 0 100 0 0 39 0 100 0 0 AVG: 44 0 100 0 0 AVG: 37 0 100 0 0 STD: 3 1 0 0 0 STD: 2 0 0 0 0 44 0 100 0 0 35 0 100 0 0 CH8007 456D 46 0 100 0 0 CH 8007 45E 36 0 100 0 0 47 0 100 0 0 39 0 100 0 0 AVG: 46 0 100 0 0 AVG: 37 0 100 0 0 STD: 2 0 0 0 0 STD: 2 0 0 0 0 ~411 100 0 0 31 0 100 0 0 CH 8007 45F 24 0 100 0 0 CH 8007 45G 32 0 100 0 0 37 0 100 0 0 32 0 100 0 0 AVG: 34 0 100 0 0 AVG: 32 0 100 0 0 STD: 9 1 0 0 0 STD: 1 0 0 0 0 WO 2006/007438 PCT/US2005/021520 37 1 100 0 0 -33 0 100 0 0 CH8007 /45H 34 0 100 0 0 CH 8007/ 451 33 0 100 0 0 37 1 100 0 0 38 0 100 0 0 AVG: 36 1 100 0 0 AVG: 35 0 100 0 0 STD: 2 1 0 0 0 1STD: 3 0 0 0 0 33 0 100 0 0 CH8007/45J 33 0 100 0 0 0 100 AVG: 33 0 100 0 0 STD: 1 0 0 0 0 [085] I I I I I I I I 1 Prebake. 4' Prbk Adhesive System Lbs SB R RC CM Adhesive lbs SB R RC CM System______ Primer/Cover coat 39 1 100 0 0 1 100 0 0 CH8007/CH8121 39 0 100 0 0 CH 8007 45A 51 1 100 0 0 34 0 100 0 0 1 100 0 0 AVG: 37 0 100 0 0 AVG: 51 1 100 0 0 STD: 3 1 0 0 0 STD: 1 0 0 0 0 39 0 100 0 0 37 0 100 0 0 CH8007/45B 36 0 100 0 0 CH 8007 45C 41 0 100 0 0 36 0 100 0 0 42 0 100 0 0 AVG: 37 0 100 0 0 AVG: 40 0 100 0 0 STD: 2 0 0 0 0 STD: 3 0 0 0 0 39 0 100 0 0 0 0 0 100 0 CH8007 I 45D 41 0 100 0 0 CH 8007 45E 0 0 0 100 0 41 0 100 0 0 0 0 0 100 0 AVG: 0 0 100 0 0 AVG: 0 0 0 100 0 STD: 1 0 0 0 0 STD: 0 0 0 0 0 0 0 0 100 0 0 0 0 100 0 CH8007 1 45F 0 0 0 100 0 CH 8007 45G 0 0 0 100 0 0 0 ,0 100 0 0 0 100 0 AVG: 0 0 0 100 0 AVG: 0 0 0 100 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 100 0 0 31 0 100 0 0 CH8007 45H 31 0 100 0 0 CH 8007 451 37 0 100 0 0 33 0 100 0 0 34 0 100 0 0 AVG: 31 0 100 0 0 AVG: 34 0 100 0 0 STD: 2 0 0 0 0 STD: 3 0 0 0 0 28 0 30 70 0 CH 8007 45J 32 0 30 70 0 0 30 701 0 AVG: 32 0 30 STD: 4 0 000 WO 2006/007438 PCT/US2005/021520 [086] Elastomer: 45-55 A durometer sulfur cured NR cured@ 320°F- 16' Testing: Boiling Water 2hrs stressed in Prebake: 0' Adhesive System R TR RC CM CP Adhesive System R TR RC CM CP Primer/Cover coat 70 30 0 0 0 -80 20 0 0 0 CH 8007 CH 8121 50 50 0 0 0 CH8007/45A 90 10 0 0 0 Control 70 30 0 0 0 -90 10 0 0 0 AVG: 63 37 0 0 0 -AVG: 87 13 0 0 0 STD: 12 12 0 0 0 STD: 6 6 0 0 0 0 100 0 0 0 5 95 0 0 0 CH8007 45B 0 100 0 0 0 CH8007/45C 5 95 0 0 0 0 100 0 0 0 5 95 0 0 0 AVG: 0 100 0 0 0 AVG: 6 95 0 0 0 STD: 0 0 I 0 0 0 STD: 0 0 0 0 0 0 100 0 0 0 0 70 30 0 0 CH8007/45D 0 100 0 0 0 CH8007/45E 0 70 30 0 0 0 100 0 0 0 0 70 30 0 0 AVG: 0 100 0 0 0 AVG: 0 70 30 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 40 60 0 0 0 15 85 0 0 CH8007/ 45F 0 40 60 0 0 CH8007/45G 0 10 90 0 0 0 40 60 0 0 0 5 95 0 0 AVG: 0 40 60 0 0 AVG: 0 10 90 0 0 STD: 0 0 0 0 0 *STD: 0 5 5 0 0 0 90 10 0 0 0 70 30 0 0 CH 8007 45H 0 80 20 0 0 CH 80071/451 0 60 40 0 0 0 70 30 0 0 0 60 40 0 0 AVG: 0 80 20 0 0 AVG: 0 63 37 0 0 STD: 0 10 10 0 0 STD: 0 6 6 0 0 0 60 40 0 0 CH 8007 45J 0 55 45 0 0 I 0 60 40 0 0 I AVG: 0 58 42 0 0 STD: 0 3 3 0 0 Prebake 4' Primary Adhesion_____ Adhesive System R TR RC C CP Adhesive System R TR RC CM CP 50 50 0 0O0 70 30 0 0 0 Control 65 35 0 0 0 CH8007/45A 70 30 0 0 0 Primer+ Cover 25 75 0 0 0 70 30 0 0 0 AVG: 47 53 0 0 0 AVG: 70 30 0 0 0 [STD: 20 20 0 0 0 -STD: 0 0 0 0 0 S 5 95 0 0 0 40 60 0 0 0 CH8007/45B 5 95 0 0 0 CH 8007/45C 40 60 0 0 0 95 0 0 0 10 90 0 0 0 AVG: 5 95 0 0 AVG: 30 70 0 0 0 STD: 0 0 0 0 0 -STD: 17 17 0 0 0 100 0 0 0 0 0 100 0 0 CH8007/45D 0 100 0 0 0 CH8007/45E 0 0 100 0 0 95 0 0 0 0 0 100 0 0 AVG: 2 98 0 0 0 AVG: 0 0 100 0 0 STD: 3 3 0 0 0 STD: 0 0 0 0

I

0 0 100 0 0 0 0 100 0 0 CH8007/45F 0 0 100 0 0 CH8007/45G 0 0 100 0 0 WO 2006/007438 PCT/US2005/021520 0 0 100 0 0 0 0 100 0 0 AVG: 0 0 100 0 0 ~AVG: 0 0 100 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 0 100 0 0 0 40 60 0 0 CH8007/45H 0 0 100 0 0 CH 8007 1451 0 50 50 0 0 0 0 100 0 0 0 70 30 0 0 AVG: 0 0 100 0 0 AVG: 0 53 47 0 0 STD: 0 0 0 0 0 STD: 0 15 15 0 0 0 0 100 0o 0 CH8007/45J 0 0 100 0 0 0 0 100 0 0 AVG: 0 0 100 0 STD: 0 0 00 Elastomer:: 45-55 A durorneter sulfur cured NR cured 320 0 F 16'cure [I Testing: Salt Spray 7 days stressed I I !I i I I I Prebake 0' Adhesive System R TR RC CM CP Adhesive R TR RC CM CP System Primer/cover coat 95 0 5 0 0 95 0 5 0 0 CH 8007/CH 8121 95 0 5 0 0 CH 95 0 5 0 0 0 5 0 0 95 0 5 0 0 AVG: 95 0 5 0 0 AVG: 95 0 5 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 10 0 0 85 0 15 0 0 CH8007/45B 75 0 25 0 0 CH 85 0 15 0 0 0 25 0 0 85 0 15 0 0 AVG: 80 0 20 0 0 AVG: 85 0 15 0 0 STD: 9 0 9 0 0 STD: 0 0 0 0 0 0 10 0 0 25 0 75 0 0 CH8007/45D 90 0 10 0 0 CH 25 0 75 0 0 8007/45E 90 0 10 0 0 25 0 75 0 0 AVG: 90 0 10 0 0 AVG: 25 0 75 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 75 0 0 0 0 100 0 0 CH 8007/45F 25 0 75 0 0 OH 0 0 100 0 0 0 75 0 0 0 0 100 0 0 AVG: 25 0 75 0 0 AVG: 0 0 1 00 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 40 0 0 60 0 40 0 0 CH8007/45H 40 0 60 0 0 CH 70 0 30 0 0 0 45 0 0 1 80 0 20 0 0 AVG: 52 0 48 0 0 AVG: 70 0 30 0 0 STD: 10 0 10 0 0 STD: 10 0 10 0 0 0 60 0 0 OH 8007/45J 45 0 55 0 0 0 50 0 0 AVG: 45 0 55 0 0 WO 2006/007438 PCT/US2005/021520 STD: 5 0 5 0 0 Prebake: 4' Adhesive System R TR RC CM CP Adhesive R TR RC CM CP System 100 0 0 0 0 80 0 20 0 0 CH8007/CH8121 95 0 5 0 0 CH 80 0 20 0 0 8007145A 0 10 0 0 90 0 10 0 0 AVG: 95 0 5 0 0 AVG: 83 0 17 0 0 STD: 5 0 5 0 0 STD: 6 0 6 0 0 0 15 0 0 40 0 60 0 0 CH 8007/45B 85 0 15 0 0 CH 50 0 50 0 0 8007/45C 0 10 0 0 60 0 40 0 0 AVG: 87 0 13 0 0 AVG: 50 0 50 0 0 STD: 3 0 3 0 0 STD: 10 0 10 0 0 0 40 0 0 0 0 100 0 0 CH 8007/45D 80 0 20 0 0 CH 0 0 100 0 0 18007/45E 0 15 0 0 0 0 100 0 0 AVG: 75 0 25 0 0 AVG: 0 0 100 0 0 STD: 13 0 13 0 0 STD: 0 0 0 0 0 0 0 100 0 0 0 0 100 0 0 CH 8007/45F 0 0 100 0 0 CH 0 0 100 0 0 0 0 100 0 0 0 0 100 0 0 AVG: 0 0 100 0 0 AVG: 0 0 100 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 0 100 0 0 10 0 90 0 0 CH 8007/45H 0 0 100 0 0 OH 20 0 80 0 0 0 0 100 0 0 20 0 80 0 0 AVG: 0 0 100 0 0 AVG: 1t7 0 83 D 0 STD: 0 0 0 0 0 STD: 6 0 6 0 0 0 75 0 0 CH 8007/45J 0 0 100 0 0 0 75 0 0 AVG: 17 0 83 0 0 STD: 14 0 14 0 0 WO 2006/007438 PCT/US2005/021520 [087] Elastomer:: 45-55 A durometer sulfur cured NR cured 320 0 F- 16'cure Testing: Primary Adhesion "mmin Prebake: 0' Adhesive Ibs SB R RC CM Adhesive Ibs SB R RC CM System System 49 0 100 0 0 1 78 0 100 0 0 CH 8007/CH 53 0 100 0 0 CH 8007/45A 80 1 100 0 0 54 0 100 0 0 87 0 100 0 0 AVG: 52 0 100 0 0 AVG: 82 0 100 0 0 STD: 3 0 0 0 0 STD: 5 1 0 0 0 0 100 0 0 47 0 100 0 0 CH8007/45B 51 0 100 0 0 CH 8007/45C 53 0 100 0 0 51 0 100 0 0 57 0 100 0 0 AVG: 51 0 100 0 0 AVG: 52 0 100 0 0 STD: 1 0 0 0 0 STD: 5 0 0 0 0 51 0 100 0 0 44 0 100 0 0 CH 8007/45D 51 0 100 0 0 CH 8007/45E 47 0 100 0 0 58 0 100 0 0 -51 0 100 0 0 AVG: 53 0 100 0 0 AVG: 47 0 100 0 0 STD: 4 0 0 0 0 STD: 4 0 0 0 0 47 0 100 0 0 29 0 100 0 0 CH 8007/45F 55 0 100 0 0 CH 8007/45G 30 0 100 0 0 57 0 100 0 0 30 0 100 0 0 AVG: 53 0 100 0 0 AVG: 30 0 100 0 0 STD: 5 0 0 0 0 STD: 1 0 0 0 0 69 0 100 0 0 53 0 100 0 0 CH 8007/45H 64 0 100 0 0 CH 8007/451 60 0 100 0 0 61 1 100 0 0 -61 0 100 0 0 AVG: 65 0 100 0 0 AVG: 58 0 100 0 0 STD: 4 1 0 0 0 STD: 4 0 0 0 0 56 0 100 0 0 CH 8007/45J 60 0 100 0 0 0 100 0 0 AVG: 60 0 100 0 0 STD: 4 0 0 0 Prebake: 4' Adhesive Ibs SB R RC CM Adhesive Ibs SB R RC CM System System 0 100 0 0 160 1 100 0 0 CH 8007/CH 56 0 100 0 0 CH 8007/45A 65 0 100 0 0 57 0 100 0 0 77 0 100 0 0 AVG: 54 0 100 0 0 AVG: 67 0 100 0 0 STD: 4 0 0 0 0 STD: 9 1 0 0 0 62 1 100 0 0 56 1 100 0 0 OH 8007/45B 63 0 100 0 0 CH 8007/45C 58 0 100 0 0 63 0 100 0 0 -60 I 0 100 0 0 AVG: 63 0 100 0 0 AVG: 58 0 100 0 0 STD: 1 1 0 0 0 STD: 2 1 0 0 0 0 100 0 0 0 0 0 100 0 CH 8007/45D 53 0 100 0 0 CH 8007/45E 0 0 0 100 0 56 0 100 0 0 0 0 100 0 AVG: 51 0 100 0 0 1 AVG: 0 0 0 100 0 WO 2006/007438 PCT/US2005!021520 STD: 6 0 0 0 0 j STD: 0 0 0 0 0 0 0 01 00 0 0 0 0 100 0 OH 6007/45F 0 0 0 100 0 OH 8007/45G 0 0 0 100 0 0 0 0 100 0 0 0 0 100 0 AVG: 0- 0 0 100 0 AVG: 0 0 0 100 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 36 0 40 60 0 35 0 25 75 0 CH 8007/45H 37 0 40 60 0 OH 8007/451 52 0 100 0 0 0 50 50 0 38 0 60 40 0 AVG: 38 0 43 57 0 AVG: 42 0 62 38 0 STD: 2 0 6 6 0 STD: 9 0 38 38 0 0 30 70 0 CH 8007/45J 28 0 30 70 0 0 30 70 0 AVG: 33 0 30 70 0 STD: 4 0 0 0 0 WO 2006/007438 WO 206/07438PCT/US2005!021520 [088] Example Series 85 aqueous RTM adhesives Masterbatch Raw Materials DNB Wetcake Carbon black Wetting aid Dispersant ZnO DCD Terpolymer spheres DI Water TSC I 86A 1855 1 85C I 85D 84.6 30.13 25.60 22.60 19.60 100 15.97 13.56 11.96 10.36 33 0.48 0.42 0.38 0.32 100 0.48 0.42 0.38 0.32 100 0.00 0.00 10.00 20.00 37 0.00 18.11 0.00 0.00 100 0.00 15.00 15.00 15.00 0 0.00 0.00 0.00 0.00 TSC 29.61% 58.04% 65.88% 61.89% Dry Wt 47 7.3 60 66 85E I 85F I 85G I 22.60 11.96 0.36 0.38 0.00 15.97 25.00 0.00 56.63% 76 19.60 10.36 0.32 0.32 10.00 0.00 25.00 0.00 61.89% 66 16.58 8.76 0.26 0.26 20.00 0.00 25.00 0.00 58.84% 71 Adhesive Raw Materials TSC I 85A I85B I85C 85D 85E 85F DCD Terpolymer 37 42.61 16.11 31.94 27.70 15.97 27.70 23.44 DOD Homnopolymer 35 10.32 8.78 7.74 6.70 7.74 6.70 6.66 DI Water D 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TSC 31 .00% 50.00% 50.0% 50.00% 50.00% 50.00% 50.00% Dry At% 53 27 40 34 24 34 29 Total Dry Wt%/ 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Application: Spray 1 50'F ElastomerslCures Adhesives: DFT 0. 65 -0.80 mils Elastomer: 45-55 A durometer sulfur cured NR Cured 320F 16' Compression Molded (t90 Control adhesive: Chemlok@ 8121 Hot Tear 15 min 300OF Boiling Water 2 hrs stressed Salt Spray 7 day stressed Primer., Primary Adhesion DFT 0. 25 0.35 mils Commercial primer: Chemlok 8007 Prebake: 0 and 4 minute Substrate ZPS Coupon 3ppt WO 2006/007438 PCT/US2005/021520 [089] Physical Properties (Units) 85A 85B 85C 85D 85E 85F Viscosity (2 30rpm) cPs 14 117 43.5 48.2 55 50.7 64.6 Density Lb/gal 9.1 9.3 10.7 11 10.4 11.3 11.2 Solids (3C) %-107°C 28.97 49.41 49.44 50.44 49.42 49.78 50.73 Grind mils Adhesive DFT mils 0.23 0.32 0.42 0.67 1.3 1.98 2.4 [090] Series 85 performance testing of bond area and type of failure) Elastomer: 45-55 A Durometer sulfur cured NR 130 320°F 16'cure I I I I I I I I I I I Testing: Hot Tear- 15 min 300°F Prebake 0' Adhesive System Ibs SB R RC CM Adhesive System Ibs SB R RC CM 41 1 100 0 0 38 1 100 0 0 CH 8007/CH 8121 48 1 100 0 0 CH 8007185A 42 1 100 0 0 54 1 100 0 0 46 1 100 0 0 AVG: 48 1 100 0 0 AVG: 42 1 100 0 0 STD: 7 0 0 0 0 STD: 4 0 0 0 0 39 0 100 0 0 34 O 100 0 0 CH 8007/85B 39 0 100 0 0 CH 8007185C 36 0 100 0 0 41 0 100 0 0 36 0 100 0 0 AVG: 40 0 100 0 0 AVG: 35 0 100 0 0 STD: 1 0 0 0 0 STD: 1 0 0 0 0 41 0 100 0 0 39 0 100 0 0 OH 8007/85D 42 1 100 0 0 CH 8007185E 40 0 100 0 0 43 1 100 0 0 42 1 100 0 0 AVG: 42 1 100 0 0 AVG: 40 0 100 0 0 STD: 1 1 0 0 0 STD: 2 1 0 0 0 28 0 100 0 0 32 0 100 0 0 CH 8007/85F 29 0 100 0 0 CH 8007/85G 32 0 100 0 0 33 0 100 0 0 32 0 100 0 0 AVG: 30 0 100 0 0 AVG: 32 0 100 0 0 STD: 3 0 0 0 0 STD: 0 0 0 0 0 Prebake: 4' Adhesive System Ibs SB R RC CM Adhesive System Ibs SB R RC CM 42 0 100 T0 0 43 1 100 0 0 CH8007/CH8121 43 0 100 0 0 CH 8007/85A 47 1 100 0 0 (NAo PVA) 44 0 100 0 0 48 1 100 0 0 WO 2006/007438 PCT/US2005/021520 AVG: 43 0 100 0 0 AVG:46 1 100 0 0 STD: 1 0 0 0 0 STD: 3 0 0 0 0 0 100 0 0 33 0 100 0 0 CH 8007/85B 35 0 100 0 0 CH 8007/85C 34 0 100 0 0 37 0 100 0 0 36 0 100 0 0 AVG: 36 0 100 0 0 AVG: 34 0 100 0 0 STD: 1 0 0 0 0 STD: 2 0 0 0 0 33 1 100 0 0 34 0 100o 0 0 CH 8007/85D 37 0 100 0 0 CH 8007/85E 38 0 100 0 0 38 0 100 0 0 37 1 100 0 0 AVG: 36 0 100 0 0 AVG: 36 0 100 0 0 STD: 3 1 0 0 0 STD: 2 1 0 0 0 26 0 100 0 0 28 0 100 0 0 CH 8007/85F 27 0 100 0 0 CH 8007/85G 29 0 100 0 0 28 0 100 0 0 30 0 100 0 0 AVG: 27 0 100 0 0 o AVG: 29 0 100 0 0 STD: 1 0 0 0 0 STD: 1 0 0 0 0 Testing: Boiling Water- 2hrs stressed in jig I _I _I I II_ I I I I_ Prebake: 0' Adhesive System R TR RC CM CP Adhesive System R TR RC CM CP 20 0 0 0 60 40 0 0 0 OH 8007/CH 8121 55 45 0 0 0 CH 8007/85A 40 60 0 0 0 (No PVA) 75 25 0 0 0 10 20 70 0 0 AVG: 70 30 0 0 0 AVG: 37 40 23 0 0 STD: 13 13 0 0 0 STD: 25 20 40 0 0 20 0 0 0 90 10 0 0 0 OH 8007/85B 40 60 0 0 0 CH 8007185C 15 85 0 0 0 20 0 0 0 90 10 0 0 0 AVG: 67 33 0 0 0 AVG: 65 35 0 0 0 STD: 23 23 0 0 0 STD: 43 43 0 0 0 10 0 0 0 100 0 0 0 0 CH 8007/85D 95 5 0 0 0 CH 8007f85E 20 80 0 0 0 20 0 0 0 95 5 0 0 0 AVG: 88 12 0 0 0 AVG: 72 28 0 0 0 STD: 8 8 0 0 0 STD: 45 45 0 0 0 95 0 0 0 95 0 5 0 0 OH 8007/85F 10 90 0 0 0 CH 8007/85G 85 0 15 0 0 95 0 0 0 80 0 20 0 0 AVG: 7 93 0 0 0 AVG: 87 0 13 0 0 STD: 3 3 0 0 0 STD: 8 0 8 0 0 Prebake :4' WO 2006/007438 PCT/US2005/021520 Adhesive System R TR RC CM CP Adhesive System R TR RC CM CP 40 0 0 0 15 85 0 0 0 CH 8007/CH 8121 80 20 0 0 0 CH 8007185A 60 40 0 0 0 (No PVA) 70 30 0 0 0 30 70 0 0 0 AVG: 70 30 0 0 0 AVG: 35 65 0 0 0 STD: 10 10 0 0 0 STD: 23 23 0 0 0 100 0 0 0 0 100 0 0 0 0 CH 8007/85B 30 70 0 0 0 CH 8007/85C 10 90 0 0 0 100 0 0 0 0 70 30 0 0 0 AVG: 77 23 0 0 0 AVG: 60 40 0 0 0 STD: 40 40 0 0 0 STD: 46 46 0 0 0 30 0 0 0 80 20 0 0 0 CH 8007/85D 20 80 0 0 0 CH 8007/85E 95 5 0 0 0 80 0 0 0 95 5 0 0 0 AVG: 37 63 0 0 0 AVG: 90 10 0 0 0 STD: 29 29 0 0 0 STD: 9 9 0 0 0 10 0 0 0 50 50 0 0 0 CH 8007/85F 55 45 0 0 0 CH 8007/85G 60 40 0 0 0 10 0 0 0 60 40 0 0 0 AVG: 78 22 0 0 0 AVG: 57 43 0 0 0 STD: 20 20 0 0 0 STD: 6 3 0 0 0 Testing: Salt Spray 7 days stressed Prebake: 0' Adhesive System R TR RC CM CP Adhesive System R TR RC CM CP 100 0 0 0 0 100 0 0 0 0 CH 8007/CH 8121 100 0 0 0 0 CH 8007/85A 100 0 0 0 0 (No PVA) 100 0 0 0 0 100 0 0 0 0 AVG: 100 0 0 0 0 AVG: 100 0 0 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 10 0 0 80 0 20 0 0 CH 8007/85B 80 0 20 0 0 CH 80071850 80 0 20 0 0 0 10 0 0 90 0 10 0 0 AVG: 87 0 13 0 0 AVG: 83 0 17 0 0 STD: 6 0 6 0 0 STD: 6 0 6 0 0 0 20 0 0 90 0 10 0 0 CH 8007/85D 80 0 20 0 0 CH 8007/85E 90 0 10 0 0 0 20 0 0 90 0 10 0 0 AVG: 80 0 20 0 0 AVG: 90 0 10 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 0 25 0 0 70 0 30 0 0 CH 8007/85F 75 0 25 0 0 OH 8007/85G 70 0 30 0 0 WO 2006/007438 PCT/US2005/021520 0 10 0 0 80 0 20 0 0 AVG: 80 0 20 0 0 AVG: 73 0 27 0 0 STD: 9 0 9 0 0 STD: 6 0 6 0 0 Prebake 4' Adhesive System R TR RC CM CP Adhesive System R TR RC CM CP 0 10 0 0 100 0 0 0 0 CH 80071CH 8121 90 0 10 0 0 CH 8007185A 100 0 0 0 0 (No PVA) 90 0 10 0 0 100 0 0 0 0 AVG: 90 0 10 0 0 AVG: 100 0 0 0 0 STD: 0 0 0 0 0 STD: 0 0 0 0 0 100 0 0 0 0 90 0 10 0 0 CH 8007185B 100 0 0 0 0 CH 8007185C 90 0 10 0 0 100 0 0 0 0 80 0 20 0 0 AVG: 100 0 0 0 0 AVG: 87 0 13 0 0 STD: 0 0 0 0 0 STD: 6 0 6 0 0 0 55 0 0 65 0 35 0 0 CH 8007/85D 60 0 40 0 0 CH 8007185E 80 0 20 0 0 0 40 0 0 70 0 30. 0 0 AVG: 55 0 45 0 0 AVG: 72 D 28 0 0 STD: 9 0 9 0 0 STD: 8 0 8 0 0 0 30 0 0 70 0 30 0 0 CH 8007/85F 70 0 30 0 0 CH 8007/85G 60 0 40 0 0 0 40 0 0 70 0 30 0 0 AVG: 67 0 33 0 0 AVG: 67 0 33 0 0 STD: 6 0 6 0 0 STD: 6 0 6 0 0 Testing: Primary Adhesion I I I I I_ Prebake: 0' Adhesive System Ibs SB R RC CM Adhesive System Ibs SB R RC CM 74 0 100 0 0 62 0 100 0 0 CH 8007/CH 8121 76 0 100 0 0 CH 8007/85A 77 1 100 0 0 (No PVA) 78 0 100 0 0 65 1 100 0 0 AVG: 76 0 100 0 0 AVG: 68 1 100 0 0 STD: 2 0 0 0 0 STD: 8 1 0 0 0 53 0 100 0 0 49 0 100 0 0 CH 8007/85B 54 0 100 0 0 CH 8007/85C 51 0 100 0 0 57 0 100 0 0 53 0 100 0 0 AVG: 55 0 100 0 0 AVG: 51 0 100 0 0 STD: 2 0 0 0 0 STD: 2 0 0 0 0 56 0 100 0 0 57 0 100 0 0 CH 8007/85D 62 0 100 0 0 CH 8007/85E 61 0 100 0 0 71 0 100 0 0 63 0 100 0 0 WO 2006/007438 PCT/US2005/021520 AVG: 63 0 100 0 0 AVG: 60 0 100 0 0 STD: 8 0 0 0 0 STD: 3 0 0 0 0 41 0 100 0 0 53 0 100 0 0 CH 8007/85F 49 0 100 0 0 CH 8007/85G 48 0 100 0 0 0 100 0 0 50 0 100 0 0-- AVG: 48 0 100 0 0 AVG: 50 0 100 0 0 STD: 7 0 0 0 0 STD: 3 0 0 0 0 Prebake 4' Adhesive System Ibs SB R RC CM Adhesive System Ibs SB R RC CM 0 100 0 0 68 1 100 0 0 CH8007/CH 8121 71 1 100 0 0 CH 8007/85A 76 1 1CO 0 0 74 1 100 0 0 78 1 100 0 0 AVG: 67 1 100 0 0 AVG: 74 1 100 0 0 STD: 10 1 0 0 0 STD: 5 0 0 0 0 39 0 100 0 0 49 0 100 0 0 CH 8007/85B 46 0 100 0 0 CH 8007185C 43 0 100 0 0 49 0 100 0 0 45 0 100 0 0 AVG: 45 0 100 0 0 AVG: 46 0 100 0 0 ISTD: 5 0 0 0 0 STD: 3 0 0 0 0 49 0 100 0 0 43 0 100 0 0 CH 8007/85D 55 0 100 0 0 CH 8007/85E 49 0 100 0 0 58 0 100 0 0 55 0 100 0 0 AVG: 54 0 100 0 0 AVG: 49 0 100 0 0 STD: 5 0 0 0 0 STD: 6 0 0 0 0 0 100 0 0 47 0 100 0 0 CH 8007/85F 49 0 100 0 0 CH 8007/85G 49 0 100 0 0 0 100 0 0 52 0 100 0 0 AVG: 46 0 100 0 0 AVG: 49 0 100 0 0 STD: 6 0 0 0 0 STD: 3 0 0 0 0 [091] Examples from 69 series aqueous RTM adhesive.

Masterbatch Raw TSC 69A 69B 69C 69D 69E 69F 69G 69H 691 69J M a t e r i a l s9 J 6TG 1 6 .5 1 3 .5 7 DNB Wetcake 82.5 30.13 25.60 22.60 19.60 22.60 19.60 16.75 19.60 16.57 13.57 Carbon black -100 15.97 13.58 11.98 10.38 11.98 10.38 8.77 10.38 8.77 7.17 Wetting aid 33 0.48 0.41 0.36 0.31 0.36 0.31 0.26 0.31 0.26 0.22 Dispersant 100 0.48 0.41 0.36 0.31 0.36 0.31 0.26 0.31 0.26 0.22 ZnO 100 0.00 0.00 10.00 20.00 0.00 10.00 20.00 0.00 10.00 20.00 spheres 100 0.00 15.00 15.00 15.00 25.00 25.00 25.00 35.00 35.00 35.00 DI Water 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TSC%: 30.00% 28.11% 28.00% 28.00% 28.00 28.00% 28.00% 28.00% 28.00% 28.00% Dry WI 47 55 60 66 60 66 71 66 71 76 r_______Adhesive WO 2006/007438 PCT/US2005/021520 Raw TSC 69A 69B 69C 69D 69E 69F 69G 69H 691 69J Materials DCD 37 42.61 36.23 31.95 27.70 31.95 27.70 23.45 27.70 23.45 19.17 Terpolymer DCD 35 10.32 8.78 7.75 6.70 7.75 6.70 5.67 6.70 5.67 4.65 Homopolymer DI Water 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TSC%: 31.00% 40.00% 40.00% 40.00% 40.00 40.00% 40.00% 40.00% 40.00% 40.00% DryWt 53 45 40 34 40 34 29 34 29 24 Dry 100 100 100 100 100 100 100 100 100 100 Wt% [092] Application: Sprayed adhesive temperature of 150°F Rubber type and cure:: 45-55 A durometer sulfur cured NR cured 320 °F (160 16' Compression Molded (t90 Hot Tear 15 min 300°F Adhesive DFT 0.65 0.80 mils Boiling Water 2 hrs stressed Salt Spray 7 day stressed Primary Adhesion peeled at Control commercial adhesive: Chemlok 8121 Primer DFT 0.25 0.35 mils Commercial primer: Chemlok 8007 Prebake: 0 and 4 min.

Substrate: zinc phosphatized steel [093] _Physical (Units) 69A 69B 69C 69D 69E 69F 69G 69H 691 69J Viscosity (2 cPs 15 22 17.5 18.8 16.1 14.6 13 13.1 14.2 15.1 Density Ib/gal 9.4 10 10.2 9.9 9.6 10.2 10.3 10.2 10.1 10.2 Solids (3B) %-68°C 29.8 39.3 40.13 39.24 39.55 41..94 36.67 35.56 38.73 40.22 Grind mils 0.5 0 0 0 0 0 0 0 0 0 WO 2006/007438 PCT/US2005/021520 [094] Series 69 performance testing of bond area and type of failure) Performance Adhesive System lbs SB R RC 49 0 100 0 CH8007/CH8121 42 1 100 0 51 1 100 0 AVG: 47 1 100 0 STD: 5 1 0 0 36 1 100 0 CH8007/69A 42 1 100 0 51 1 100 0 AVG: 43 1 100 0 STD: 8 0 0 0 42 1 100 0 CH 8007/69C 44 1 100 0 46 1 100 0 AVG: 44 1 100 0 STD: 2 0 0 0 1 100 0 CH8007/69E 43 1 100 0 44 1 100 0 AVG: 42 1 100 0 STD: 2 0 0 0 1 100 0 CH 8007/69G 45 1 100 0 48 1 100 0 AVG: 46 1 100 0 STD: 2 0 0 0 44 1 100 0 OH 8007/69I 45 1 100 0 47 1 100 0 AVG: 45 1 100 0 STD: 2 0 0 0 Adhesive System Ibs 41 OH 8007/CH 8121 44 (No PVA) 44 AVG: 43 STD: 2 45 OH 8007(69B 48 54 AVG: 49 STD: 5 46 CH 8007f69D 48 48 AVG: 47 STD: 1 41 CH 8007169F 46 47 AVG: 45 STD: 3 40 CH 8007f69H 45 50 AVG: 45 STD: 5 39 OH 8007/69J 41 43 AVG: 41 STD: 2 SB R RG 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 0 100 0 1 100 0 1 100 0 1 100 0 1 0 0 Prebake: 4' Adhesive System Ibs SB R RC 0 100 0 OH8007/CH8121 45 1 100 0 46 1 100 0 AVG: 45 1 100 0 STD: 1 1 0 0 42 1 100 0 CH8007/69A 43 1 100 0 44 1 100 0 AVG: 43 1 100 0 STD: 1 0 0 0 43 1 100 0 CH 8007/69C 44 1 100 0 1 100 0 AVG: 44 1 100 0 STD: 1 0 0 0 41 1 100 0 CH 8007/69E 41 1 100 0 411 1 100 0 AVG: 164 1 100 0 STD: 214 0 0 0 0 100 0 OH B007/69G 27 0 100 0 Adhesive System lbs 45 CH 8007/CH 8121 47 (No PVA) 47 AVG: 45 STD: 1 3B CH 8007/69B 43 44 AVG: 42 STD: 3 33 CH 8007,69D 35 40 AVG: 36 STD: 4 31 CH 8007/69F 35 43 AVG: 36 STD: 6 38 CH 8007/69H 37 SB R RC 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 1 100 0 1 100 0 1 100 0 1 100 0 0 0 0 0 100 0 1 100 0 1 100 0 1 100 0 1 0 0 1 100 0 1 100 0 WO 2006/007438 PCT/US2005/021520 1 100 0 0 AVG: 29 0 100 0 0 STD: 5 1 0 0 0 0 100 0 0 CH 8007/091 36 0 100 0 0 37 1 100 0 0 AVG: 36 0 100 0 0 STD: 1 1 0 0 0 41 1 100 0 0 AVG: 39 1 100 0 0 STD: 2 0 0 0 0 35 0 100 0 0 CH 8007/69J 36 1 100 0 0 38 1 100 0 0 AVG: 36 1 100 0 0 STD: 2 1 0 0 0 Elastomer: 45-55 A durometer sulfur cured NR Cured 320 OF (160 OC) 16' Testing: Boiling Water 2hrs stressed in jig Prebake 0' Adhesive System R TR RC 30 0 CH 8007/CH 8121 70 30 0 85 0 AVG: 52 48 0 STD: 32 32 0 25 0 CH 80071/69A 75 25 0 25 0 AVG: 75 25 0 STD: 0 0 0 0 100 0 CH 8007/69C 0 100 0 0 100 0 AVG: 0 100 0 STD: 0 0 0 80 0 CH 8007/69E 30 70 0 80 0 AVG: 23 77 0 STD: 6 6 0 80 0 CH 8007169G 0 100 0 0 100 0 AVG: 7 93 0 STD: 12 12 0 Adhesive System R TR RC 60 40 0 CH 8007/CH 8121 50 50 0 (No PVA) 40 60 0 AVG: 50 50 0 STD: 10 10 0 10 90 0 CH 8007/69B 10 90 0 5 9E 0 AVG: 8 92 0 STD: 3 3 0 0 100 0 CH 8007169D 0 100 0 0 100 0 AVG: 0 100 0 STD: 0 0 0 15 85 0 CH 8007/69F 30 70 0 25 75 0 AVG: 23 77 0 STD: 8 8 0 0 100 0 CH 8007169H 0 100 0 0 100 0 AVG: 0 100 0 STD: 0 0 0 100 0 CH 8007/691 100 0 100 0 AVG: 100 0 STD: 0 0 100 0 CH 8007f69J 100 0 100 0 AVG: 100 0 STD: 0 0 Prebake 4' Adhesive System R TR RC 70 0 CH 8007/CH 8121 50 50 0 30 0 AVG: 50 50 0 STD: 20 20 0 40 0 CH 8007/69A 50 50 0 60 0 AVG: 50 50 0 STD: 10 10 0 Adhesive System R TR RC 30 70 0 CH 8007/CH 8121 60 40 0 (No PVA) 60 40 0 AVG: 50 50 0 STD: 17 17 0 30 70 0 CH 8007)69B 30 70 0 30 70 0 AVG: 30 70 0 STD: 0 0 0 WO 2006/007438 PCT/US2005/021520 95 0 CH 8007/69C 0 100 0 0 100 0 AVG: 2 98 0 STD: 3 3 0 0 100 0 CH 8007/69E 30 70 0 80 0 AVG: 17 83 0 STD: 15 15 0 0 100 0 CH 8007/69G 0 100 0 0 100 0 AVG: 0 100 0 STD: 0 0 0 0 100 0 CH 8007/691 0 100 0 0 100 0 AVG: 0 100 0 STD: 0 0 0 0 100 0 CH 8007/69D 0 100 0 0 100 0 AVG: 0 100 0 STD: 0 0 0 30 70 0 CH 8007/69F 10 90 0 15 85 0 AVG: 18 82 0 STD: 10 10 0 0 100 0 CH 8007/69H 0 100 0 0 100 0 AVG: 0 100 0 STD: 0 0 0 0 100 0 CH 8007169J 0 100 0 0 100 0 AVG: 0 100 0 STD: D 0 0 Elastomer: 45-55 A durometer sulfur cured NR cured 320 0 F 16' Testing: Salt Spray 7 days stressed Prebake 0' Adhesive System R TR RC CM 0 10 0 CH 8007/CH 8121 95 0 5 0 0 5 0 AVG: 93 0 7 0 STD: 3 0 3 0 0 5 0 CH 8007/69A 95 0 5 0 0 5 0 AVG: 95 0 5 0 STD: 0 0 0 0 0 15 0 CH 8007/690 85 0 15 0 0 20 0 AVG: 83 0 17 0 STD: 3 0 3 0 0 10 0 CH 8007/69E 85 0 15 0 0 10 0 AVG: 88 0 12 0 STD: 3 0 3 0 0 40 0 CH 8007/69G 60 0 40 0 0 40 0 AVG: 60 0 40 0 STD: 0 0 0 0 0 50 0 CH 8007/691 50 0 50 0 0 70 0 AVG: 43 0 57 0 STD: 12 0 12 0 Adhesive System R TR 95 0 CH 8007/CH 8121 95 0 (No PVA) 95 0 AVO: 95 0 STD: 0 0 90 0 CH 8007(69B, 90 0 90 0 AVG: 90 0 STD: 0 0 80 0 CH 8007!69D 70 0 70 0 AVG: 73 0 STD: 6 0 90 0 CH 8007169F 75 0 80 0 AVG: 82 0 STD: 8 0 4D 0 CH 8007169H 86 0 40 0 AVG: 47 0 STD: 12 0 25 0 CH 8007'69J 20 0 20 0 AVG: 22 0 STD: 3 0 RC CM 5 0 5 0 5 0 5 0 0 0 10 0 10 0 10 0 10 0 0 0 20 0 30 0 30 0 27 0 6 0 10 0 25 0 20 0 18 0 8 0 60 0 40 0 60 0 53 0 12 0 75 0 80 0 80 0 78 0 3 0 Prebake 4' Adhesive CP System R TR Adhesive System R TR RC CM RC CM CP WO 2006/007438 PCT/US2005/021520 100 0 0 CH 8007/CH 8121 95 0 5 0 5 AVG: 97 0 3 STD: 3 0 3 0 5 CH 8007/69A 95 0 5 0 10 AVG: 93 0 7 STD: 3 0 3 0 20 CH 8007/89C 85 0 15 0 20 AVG: 82 0 18 STD: 3 0 3 0 10 CH8007169E 85 0 15 0 10 AVG: 88 0 12 STD: 3 0 3 0 20 CH 8007169G 50 0 50 0 75 AVG: 52 0 48 STD: 28 0 28 0 55 OH 8007/691 40 0 60 0 70 AVG: 38 0 62 STD: 8 0 8 95 0 CH 8007/CH 8121 95 0 (No PVA) 95 0 AVG: 95 0 STD: 0 0 80 0 CH 8007/69B 85 0 80 0 AVG: 82 0 STD: 3 0 60 0 CH 8007/69D 75 0 75 0 AVG: 70 0 STD: 9 0 85 0 CH 800769F 85 0 85 0 AVG: 85 0 STD: 0 0 50 0 CH 8007/69H 40 0 65 0 AVG: 52 0 STD: 13 0 25 0 CH 8007/69J 20 0 0 0 AVG: 15 0 STD: 13 0 Elastomer: 45-55 A durometer sulfur cured NR cured 320 OF (160 16' Testing: Primary Adhesion Prebake 0' Adhesive System lbs SB R RC 77 1 100 0 CH 8007/CH8121 60 0 100 0 63 0 100 0 AVG: 67 0 100 0 STD: 9 1 0 0 77 0 100 0 CH8007169A 75 1 100 0 1 100 0 AVG: 77 1 100 0 STD: 3 1 0 0 67 1 100 0 CH 8007/69C 67 0 100 0 69 0 100 0 AVG: 68 0 100 0 STD: 1 1 0 0 0 100 0 CH8007/69E 62 1 100 0 63 1 100 0 AVG: 65 1 100 0 STD: 4 1 0 0 63 1 100 0 CH8007/69G 63 0 100 0 67 0 100 0 Adhesive System Ibs SB R RC 56 0 100 0 CH 8007/CH 8121 70 0 100 0 (No PVA) 72 0 100 0 AVG: 66 0 100 0 STD: 9 0 0 0 69 0 100 0 CH 8007169B 71 0 100 0 64 1 100 0 AVG: 68 0 100 0 STD: 4 1 0 0 60 0 100 0 CH8007,69D 77 0 100 0 69 1 100 0 AVG: 69 0 100 0 STD: 9 1 0 0 71 1 100 0 CH800769F 76 0 100 0 74 0 100 0 AVG: 74 0 100 0 STD: 3 1 0 0 66 0 100 0 CH8007/69H 68 0 100 0 67 1 100 0 WO 2006/007438 AVG: 64 STD: 2 54 CH 80071691 54 61 AVG: 56 STD: 4 Adhesive System Ibs CH 8007/CH 8121 62 AVG: 62 STO: 3 64 OH 8007/69A 67 66 AVG: 66 STD: 2 66 CH 8007/69C 69 AVG: 68 STD: 2 49 CH 8007/69E 51 57 .AVG: 52 STD: 4 58 CH 8007/69G 71 AVG: 68 STD: 9 58 OH 8007/691 58 61 AVG: 59 STD: 2 0 100 0 1 0 0 0 100 0 0 100 0 0 100 0 0 100 0 0 0 0 SB R RC 0 100 0 0 100 0 0 100 0 0 100 0 0 0 0 0 100 0 0 100 0 1 100 0 0 100 0 1 0 0 0 100 0 0 100 0 0 100 0 0 100 0 0 0 0 0 100 0 0 100 0 0 100 0 0 100 0 0 0 0 0 100 0 0 100 0 1 100 0 0 100 0 1 0 0 0 100 0 0 100 0 0 100 0 0 100 0 0 0 0 0 AVG: 67 0 STD: 1 0 56 0 CH 8007/69J 59 0 55 0 AVG: 60 0 STD: 5 Prebake 4' Adhesive CM System Ibs 0 64 CH 8D07/CH 0 8121 76 0 (No PVA) 72 0 AVG: 71 0 STD: 6 0 58 0 OH 8007/69B 69 0 69 0 AVG: 65 0 STD: 6 0 64 0 OH 8007/69D 65 0 68 0 AVG: 66 0 STD: 2 0 67 0 CH 8007/69F 76 0 77 0 AVG: 73 0 STD: 6 0 61 0 CH 8007/69H 72 0 71 0 AVG: 68 0 STD: 6 0 52 0 CH 8007/69J 53 0 58 0 AVG: 54 0 STD: 3 PCT/US2005/021520 0 100 0 1 0 0 1 100 0 0 100 0 0 100 0 0 100 0 1 0 0 SB R RC 0 100 0 a 100 0 1 100 0 0 100 0 1 0 0 0 100 0 0 100 0 1 100 0 0 100 0 1 0 0 0 100 0 0 100 0 0 100 0 0 100 0 0 0 0 1 100 0 0 100 0 0 100 0 0 100 0 1 0 0 0 100 0 0 100 0 1 100 0 0 100 0 1 0 0 0 100 0 0 100 0 0 100 0 0 100 0 0 0 0 [095] The invention includes a rubber to metal adhesive for bonding an elastomer to a metal. The sprayable rubber to metal adhesive includes a plurality of microspheres with the adhesive having a weight percent concentration of at least one percent of the microspheres. The rubber to metal adhesive preferably has a viscosity less than 500 cps (Brookfield LVT 2 30 rpm). The sprayable rubber to metal adhesive is comprised of a plurality of nonsolubable spheroidal particle microspheres.

The sprayable rubber to metal adhesive has a weight percent concentration of at least one percent of the microspheres wherein the adhesive has a sprayable viscosity less than 500 cps (Brookfield LVT 2 30 rpm). Preferably the rubber to metal adhesive includes -5 wt. of the microspheres, more preferably >10 wt. of the 48 WO 2006/007438 PCT/US2005/021520 microspheres. Preferably the rubber to metal adhesive includes 5 40 wt. of the microspheres, more preferably 5 35 wt. Preferably the rubber to metal adhesive has a microsphere range of about 5 to 35 wt. more preferably a microsphere range of about 15 to 30 wt. and most preferably a microsphere range of about 19 to 26 wt. Preferably the rubber to metal adhesive viscosity is in the range of 50 to 500 cps (Brookfield LVT 2 30 rpm). Preferably the microspheres have a surface area less than 20m 2 /cc, more preferably 5 15m 2 /cc, more preferably 5 10m 2 /cc, more preferably 5 9m 2 /cc, most preferably 5 8m 2 /cc. Preferably the microspheres are ceramic microspheres with the microspheres comprised of a ceramic. Preferably the microspheres are comprised of hollow spheres, preferably ceramic hollow spheres with relatively thick walls as compared to the sphere outer dimension diameter wherein the hollow spheres are incompressible with a crush strength of at least 20,000 Preferably the microspheres are comprised of a silica alumina ceramic.

Preferably the microspheres are comprised of aluminum oxide. Preferably the microspheres are comprised of silicon dioxide. Preferably the microspheres are zeeospheres. Preferably the microspheres have a density in the range of about 2 to 2.6 (gm/cc).

[096] The invention includes a method of making the elastomer to metal adhesive for bonding an elastomer to a metal. The method includes providing an elastomer to metal adhesive fluid composition, providing a plurality of microspheres, and adding the plurality of microspheres to the elastomer to metal adhesive fluid to provide an elastomer to metal adhesive having a viscosity less than than 500 cps (Brookfield LVT 2 30 rpm) The method of making the sprayable elastomer rubber to metal adhesive for bonding an elastomer to a metal includes providing an rubber elastomer to metal adhesive fluid composition. Preferably the provided rubber to metal adhesive composition includes DNB. The method includes providing a plurality of microspheres, adding the plurality of microspheres to the elastomer to metal adhesive fluid composition to provide a sprayable elastomer to metal adhesive having a viscosity less than than 500 cps (Brookfield LVT 2 30 rpm). Preferably the microspheres are added to provide a viscosity of from 50 to 500 cps (Brookfield LVT 2 30 rpm). Preferably the method includes adding at least one percent by weight of the microspheres to the elastomer to metal adhesive fluid, more preferably -5 wt. of WO 2006/007438 PCT/US2005/021520 the microspheres, most preferably -10 wt. of the microspheres. Preferably the method includes adding 40 wt. of the microspheres, more preferably 35 wt..

Preferably the method includes adding microspheres to the elastomer to metal adhesive in the range of about 5 to 35 wt. microspheres, more preferably a range of about 15 to 30 wt. and most preferably a range of about 19 to 26 wt. Preferably the rubber to metal adhesive viscosity is in the range of 50 to 490 cps (Brookfield LVT 2 30 rpm). Preferably the microspheres have a surface area less than 20m 2 /cc, more preferably 5 15m 2 /CC, more preferably 5 10m 2 /cc, more preferably 5 9m 2 /cc, most preferably 5 8m 2 /cc. Preferably the microspheres are ceramic microspheres with the microspheres comprised of a ceramic. Preferably the microspheres are comprised of hollow spheres, preferably ceramic hollow spheres with relatively thick walls as compared to the sphere outer dimension diameter wherein the hollow spheres are incompressible with a crush strength of at least 20,000 Preferably the microspheres are comprised of a silica alumina ceramic. Preferably the microspheres are comprised of aluminum oxide. Preferably the microspheres are comprised of silicon dioxide. Preferably the microspheres are zeeospheres. Preferably the microspheres have a density in the range of about 2 to 2.6 (gm/cc). Preferably the microspheres are added to provide a sprayable viscosity greater than 50 cps (Brookfield LVT 2 30 rpm) preferably a viscosity in range of 60 to 450 cps (Brookfield LVT 2 30 rpm). Preferably the elastomer to metal adhesive fluid composition includes DNB, CNR, an acid scavenger, a maleimide, and a chlorosulfonated polyethylene.

WO 2006/007438 PCT/US2005/021520 [097] Preferred Composition Ranges Preferred Material Low DNB 15 acid 10 scavenger maleimide 5 carbon black 0 Zeeosphere 5 *Hypalon 5 *CNR 5 High 25 30 15 10 35 45 45 More Preferred Low 17 10 5 3 20 15 15 High 23 15 10 8 25 20 20 Preferred Composition 4 16 *50:50 with low HYP:low

CNR

*50:50 with high HYP:high

CNR

*66.6:33,3 with high HYP:Iow

CNR

[098] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims

1. An adhesive composition having a pigment grind of 0-2 mils (0 to 0.05 mm) measured by the Hegman® gauge, said adhesive is sprayable at a total solids concentration of 25 2 has a viscosity of from 50 to 500 cps (Brookfield LVT 2 30 rpm) and comprises a nitroso compound, film-forming halogenated polyolefin, acid acceptor and from 5% to 35 dry wt.% of inert, incompressible, spheroidal particles having a BET surface area of from 0.1 to 10 m2/g and a 50 th percentile particle diameter (D50) of to 25 pm.

2. The adhesive composition according to claim 1, wherein said nitroso compound is present at 15 to 25 dry wt

3. The adhesive composition according to claim 1 or 2, wherein said film- forming halogenated polyolefin is present at from 0.1 to 15 dry wt.

4. The adhesive composition according to any one of claims 1 to 3, wherein said nitroso compound is present at from 17 to 23 dry wt.

5. The adhesive composition according to any one of claims 1 to 4, wherein said film-forming halogenated polyolefin is a 40-60 to 60-40 wt. ratio blend of chlorosulfonated polyethylene to chlorinated rubber.

6. The adhesive composition according to any one of claims 1 to 4, wherein said film-forming halogenated polyolefin comprises a 60-70 to 40-30 wt. ratio blend of chlorosulfonated polyethylene and chlorinated natural rubber.

7. The adhesive composition according to any one of claims 1 to 6, wherein acid acceptor is present at from 10 to 15 dry wt.%.

8. The adhesive composition according to any one of claims 1 to 4 or 7, wherein said film-forming halogenated polyolefin is selected from the group consisting of chlorinated natural rubber, chlorinated polychloroprene, chlorinated polybutadiene, chlorinated poly(butadiene styrene), chlorinated poly(ethylene propylene), chlorinated poly(ethylene propylene non-conjugated diene), chlorinated polyethylene, chlorosulfonated polyethylene, poly(a-chloroacrylonitrile 2,3-dichloro-l,3-butadiene), brominated poly(2,3-dichloro-1,3-butadiene), and mixtures thereof.

9. The adhesive composition according to any one of claims 1 to 8, wherein said nitroso compound is selected from the group consisting of m-dinitrosobenzene, p-dinitrosobenzene, m-dinitrosonaphthalene, p-dinitrosonaphthalene, cymeme, 2-methyl-1,4-dinitrosobenzene, 2-methyl-5-chloro-l,4-dinitrosobenzene, 2- fluoro- 1,4-dinitrosobenzene, 2-methoxy-1,3-dinitrosobenzene, 5-chloro-1,3- A1121(911549_1)AAK 53 dinitrosobenzene, 2-benzyl- ,4-dinitrosobenzene, 2-cyclohexyl-1,4-dinitrosobenzene and combinations thereof.

An adhesive composition comprising a nitroso compound, a film-forming halogenated polyolefin, an acid acceptor and spheroidal particles, substantially as hereinbefore described with reference to any one of the examples.

11. A method for spray applying a rubber-to-metal adhesive according to any one of claims 1 to 10 comprising spraying onto a metal surface in an amount to provide a dry film thickness of from 0.0003 to 0.002 inch (0.007 to 0.0508 mm) 0.0001 to 0.0003 (0.0025 to 0.0076 mm) in one or two sprayed layers.

12. A method of bonding an elastomer to a metal surface, said method comprised of: providing a metal surface, providing a rubber to metal adhesive including a nitroso compound, a film-forming halogenated polyolefin, an acid acceptor and from 5% to dry wt.% of spheroidal particles having a BET surface area of from 0.1 to 10 m 2 /g and a 0 t h percentile particle diameter (D50) of 5 to 25 upm, said rubber to metal adhesive is having a viscosity of from 50 to 500 cps (Brookfield LVT 2 30 rpm), and spraying said provided rubber to metal adhesive onto said metal surface.

13. The method according to claim 12 including spraying said provided rubber to metal adhesive onto said metal surface in an amount to provide a dry film thickness of from 0.0003 to 0.002 inch (0.007 to 0.0508 mm) 0.0001 to 0.0003 (0.0025 to 0.0076 mm) in one or two sprayed layers.

14. A rubber to metal adhesive comprised of a nitroso compound, a film-forming halogenated polyolefin, an acid acceptor and a plurality of microspheres, said adhesive having a weight percent concentration of at least one percent of said microspheres, wherein said adhesive has a viscosity less than 500 cps (Brookfield LVT 2 30 rpm).

15. The rubber to metal adhesive according to claim 14, wherein said microspheres have a surface area less than 20 m 2 /cc.

16. A method of making an elastomer to metal adhesive, said method comprising: providing an elastomer to metal adhesive fluid composition, said fluid composition comprising a nitroso compound, a film-forming halogenated polyolefin, and an acid acceptor, providing a plurality of microspheres, adding said plurality of microspheres to said elastomer to metal adhesive fluid to provide an elastomer to metal adhesive having a viscosity less than 500 cps (Brookfield LVT 2 30 rpm). AH21(911549_1) AAK

17. The method according to claim 16, including adding at least one percent by Nweight of said microspheres to said elastomer to metal adhesive fluid.

S18. The method according to claim 16 or 17, wherein said microspheres have a surface area less than 20m 2 /cc.

19. A method of making an elastomer to metal adhesive, substantially as hereinbefore described with reference to any one of the examples. An elastomer to metal adhesive prepared according to the method of any one of claims 16 to 19. SDated 16 August, 2007 Lord Corporation Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON AH21(911549_1)AAK