JP2005520016A - Flexible paint for elastomer substrate - Google Patents

Abstract

A radiation coating composition for an elastomer bonded to a flexible substrate, preferably an elastomer or metal.
The coating composition is produced by mixing part (a) and part (b). Part (a) is an organic solution or aqueous dispersion of a functional group-containing polymer or copolymer. It consists of a liquid and a thermally conductive filler; part (b) consists of a liquid curing component such as polyisocyanate, carbodiimide, or amino resin. The coating composition is applied to the substrate before or after vulcanizing the substrate. The coating composition can be cured at ambient temperature and provides heat dissipation over extended use at elevated temperatures.

Description

  The present invention relates to a weatherable coating applied to the outer surface of a flexible (elastic) substrate product, in particular an elastomer or rubber product or a substrate comprising such a material. In addition to the protective film properties, the weather resistant paint of the present invention reduces heat generation by releasing heat from the product (heat dissipation). The coating can be applied to the elastomeric substrate before or after vulcanizing the substrate.

  Engineered elastomer products are designed to damp forces including bending and bending, distortion and recovery, and / or repeated torques or vibrations during their useful life, and are utilized in numerous industrial applications. For example, elastomeric materials are used in tires, hoses, seals, fixtures such as engine mounts, dampers, and insulation devices to exhibit hysteresis losses and to withstand heat, to name a few design areas. Designed to. These and other products molded into countless products have many established uses such as industrial machinery and automotive parts. Many elastomer products come in contact with heat from various sources, such as from an internal combustion engine. Recent increases in operating temperatures and reductions in the size of automobile engine compartments are due to heat sources, rubber hoses, plastic housings, belts, various mounts, shrouds, seals, grommets, washers, spacers, covers, and housings, etc. This creates a closer proximity to the molded part. Some of these products are heat vulcanized, others are vulcanized at room temperature, and others are cured in different ways, exhibiting the bending, elongation and rubber elasticity characteristic of thermoplastics or thermoset materials.

  All polymeric materials degrade due to exposure to heat, light, oxygen, ozone, solvents, oils, and / or fuels. Elastomeric materials, and natural and / or synthetic vulcanizates are known to degrade, particularly when exposed to these agents, and continuing research is underway to provide elastomeric products that are resistant to such degrading elements. In the world.

  US Pat. No. 6,022,626 discloses a paint suitable for covering an engine mount to protect the rubber substrate from oxygen, ozone and / or UV light, especially when the temperature reached is 104 ° C. or higher. doing. The paint provides a polymer barrier from chemical or UV penetration. In exposure to the thermal environment, the polymer taught in US Pat. No. 6,022,626 provides an initial barrier to oxygen, ozone and UV radiation, but is resistant to repeated flexing over time. Lack. Once the adhesion is poor or the coating is cracked, the degradation action begins again. The paint taught in the US patent also does not provide radiation and does not dissipate heat.

  Roberts et al., US Pat. No. 5,314,741, whose title is “Rubber Product with Protective Coating”, is a polymer product coated with hydrogenated synthetic rubber or a polymer of 1,3-butadiene and The present invention relates to a polymer obtained by hydrogenating an unsaturated polymer which is optionally one or more monoethylenically unsaturated polymers.

  Conventional polymer stabilizers, UV absorbers, etc. are used in rubber products coated on them, and excellent aging resistance is necessary even considering the more severe operating conditions. Achieving sufficient permanent adhesion to the underlying rubber that experiences repeated flexing and stretching over a long lifetime requires further improvement.

  Alkyd, urethane, and enamel metallic paint finishes are well known to provide a glossy metallic effect. The substrate is primarily a metal or hard plastic part, with limited flexing or the paint is expected to crack upon severe impact. A speckled pattern metallic paint is commonly provided for metal body panels, whereby less than 1% of the metallic pigment is interspersed with the colored pigment and the transparent finish is overcoated. Similarly, aluminized spray coatings have been provided for applying furniture, metal products, etc., but the film-forming material utilized cures to form a very limited stretch coating. And since it is not long after an arrangement | positioning in bending crack and use of a coating film, it is unsuitable as a coating material on an elastic base material like an industrial rubber product. Metal flake effect paints provide visual aesthetics to external parts, but do not provide thermal radiation properties to a degree useful to extend the useful long-term use of industrial rubber products in thermal environments.

  One way to make the elastomeric material corrosion resistant is to apply a protective coating to the elastomeric material. Various corrosion resistant coatings utilized so far for both soft substrates (eg, elastomeric substrates) and hard substrates (eg, steel, stainless steel, aluminum or plastics) include polyurethanes, polysulfides and fluorocarbon elastomers. . It has been found that conventional corrosion resistant paints such as fluorocarbon elastomers provide excellent resistance to oils and fuels when applied to hard substrates. However, fluorocarbon elastomers suffer from low fatigue resistance, low temperature properties, and low adhesion to these substrates when applied to elastic elastomeric substrates composed of natural rubber and / or diene elastomers and mixtures.

  Elastomers based on low molecular weight polyolefins or polyisoolefins containing low levels of chemical bonding functionality such as hydroxyl or amine containing groups are known for introduction into urethane foam. Such elastomers are mixed with an unblocked or blocked polyisocyanate and cured. For example, US Pat. No. 4,939,184 describes the preparation of a flexible polyurethane made by reacting a low molecular weight polyisobutylene having 2 or 3 terminal hydroxy groups with a polyisocyanate in the presence of a blowing agent. Is disclosed.

  Odam U.S. Pat. No. 4,132,219 relates to two methods of applying polyurethane paint to vulcanized rubber parts.

U.S. Pat. No. 4,670,496 discloses a stripping coating for tire sidewalls as a dye-like color indication, and preferably the metal particles contain non-vulcanized diene rubber and rubber vulcanization accelerator. It is processed in the form of a containing solution. Crosslinkable silicone and / or modified EPDM are also treated in the form of a solution. The accelerator is essential to scavenge sulfur from the vulcanized rubber substrate to provide automatic vulcanization of the coating rubber. In order to provide adequate adhesion for long-term use as a coating for rubber products, diene polymers containing 10% or more residual unsaturation after curing must always degrade and become brittle and break long before the substrate breaks To do.

EPA325
In order to cure a copolymer of modified styrene and isobutylene containing tertiary amino alcohol groups in No. 997, diisocyanates containing isocyanate free radicals have also been proposed so far. EPA325
No. 997 discloses diisocyanate curing of a polymer having a molecular weight of 700-200,000, a weight average molecular weight (Mw) of about 30,000 and a number average molecular weight of about 8,600 as measured by gel permeation chromatography. A mixture of (Mn) is illustrated.

  Various bulk isocyanate cured rubbers and mastics were disclosed in the 1950s and 1960s. The isocyanate reactive functional groups present in the elastomer are easily cured with the NCO groups of the diisocyanate. As an example, US Pat. No. 6,087,454 describes an elastomeric polymer having a Mw of 60,000 or higher and containing a hydroxyl and / or amine functional group and a temperature below the temperature at which the blocked polyisoanato is unblocked. Disclosed is a method for producing a cured bulk elastomer comprising mixing at temperature. The mixture is cured by heating at a temperature above that which causes the polyisocyanate to unblock. This reaction can be carried out at room temperature by the use of unblocked isocyanate. Low molecular weight polyisobutylene having hydroxy functionality is cured with poiisocyanate in the presence of a blowing agent as disclosed in US Pat. No. 4,939,184.

U.S. Pat. No. 4,774,288 discloses a hydrogenated copolymer of a conjugated diene and an [alpha], [beta] -unsaturated nitrile containing an active phenol-formaldehyde resin vulcanization system. The disclosure relates to bulk vulcanized rubber, which is characterized by having good compression set properties and good oil resistance, good oxidative attack resistance in air at high temperature aging under oxidizing conditions, but useful There is no suggestion of coatings that can be formed on natural elastomers and elastic elastomeric substrates such as polybutadiene that can provide properties.

U.S. Pat. No. 5,314,955 discloses a coating composition comprising (a) a hydrogenated acrylonitrile-butadiene copolymer, (b) a phenolic resin, (c) a curing component, and (d) a solvent. . This paint solves many problems of adhesion to rubber substrates that combine fatigue resistance and fuel resistance. One of the disadvantages of this coating composition is that it requires a high temperature bake to promote curing of the coating and adhesion to adjacent metal surfaces. High temperature baking conditions for paints require heating and soaking the entire product to be coated. Certain parts, such as helicopter rotor bearings, are damaged by high temperature bake, so paints as taught in US Pat. No. 5,314,955 are not applicable. High temperature baking, time delays and extra handling of parts add to production costs. Thus, excellent protective coatings for elastic elastomeric substrates consisting of typical natural rubber and / or diene elastomers that are fatigue resistant over a wide temperature range, exhibit effective adhesion to the substrate, and can be cured at room temperature There is still a need for.

U.S. Pat. No. 6,156,379 discloses a conventional primer transparent coating on a metal surface that contains metal flakes in the primer. The novel difference is based on luster pigments derived from finely ground vapor deposited metal. The metal paint composition is applied on the undercoat layer, and a transparent finish paint is applied on the metal paint layer. The metal coating composition is defined as consisting essentially of a luster pigment and a solvent, which is an additive or resin such that the coating composition contains no components other than flakes, or the resin or pigment weight concentration is 95% or more. Means a small amount. Binders such as acrylics, polyamides, vinyl chloride copolymers are suggested. Such binders are not recognized as suitable for elastic substrate paints because they do not exhibit 100% elongation and break from flex cracks and loss of adhesion after placement in use.

US Pat. No. 5,314,741 discloses a coating composition comprising a latex of a highly saturated polymer, highly saturated styrene / butadiene copolymer, hydrogenated polybutadiene, or hydrogenated styrene / vinyl pyridine / terpolymer, such as hydrogenated nitrile rubber. We are disclosing things. The paint is applied to the substrate and cured there to obtain the required coated product reporting ozone, oxygen and UV light resistance. A suitable curing agent taught is a zinc-sulfur cure package. High temperatures are required to cure these paints. Moreover, conventional vulcanization systems have a high sulfur content known to those skilled in the art and a low vulcanization accelerator content. Hofmann, Kautschuk-Technology, Genter Verlag, Stuttgart, 1980 p. 64 and 254-255, but has some drawbacks. Conventional vulcanized paints provide vulcanized rubber with good dynamic stress (flex life) resistance, but are extremely sensitive to aging and reversion. Semi-efficient vulcanization systems generally have low dynamic stress resistance, but instead they are somewhat stable in aging and reversion (RN Datt and WF Helt, Rubber World, August 1997, p. .24, et seq.).
US Pat. No. 4,939,198 US Pat. No. 4,136,219 U.S. Pat. No. 4,670,469 EPA 325997 US Pat. No. 6,087,454 U.S. Pat. No. 4,939,184 U.S. Pat. No. 4,774,288 US Pat. No. 5,314,955 US Pat. No. 6,156,379 US Pat. No. 5,314,741

  Paints based on highly saturated elastomers utilizing vulcanization chemistry adhere to substrates such as blends of natural rubber and diene elastomers widely used in rubber products in the above products, especially automobile tires, hoses, etc. It has been observed by the inventor to suffer losses. An excellent elastomer protective coating for flexible (elastic) elastomeric substrates that provides excellent adhesion to the surface of the elastomer, excellent bending resistance, and thermal radiation properties that can reduce the heat conducted to the underlying polymer substrate There is still a demand. Under long-term use in industrial products, the stress level from heat is time and temperature dependent. Reduced heat of absorption and increased heat release within the elastomer can significantly extend product use / performance life. In order to extend the useful life of these products, it is industrially important to reduce the heat absorption rate and increase the heat dissipation rate.

  One embodiment of the present invention relates to a non-radiative coating composition that is resistant to long-term fatigue and temperature changes and provides excellent adhesion to a flexible elastomeric substrate. The paint cures at room temperature. The paint consists of a film former polymer containing 10% or less of ethylenic unsaturation before curing. In a preferred embodiment, the coating composition of the present invention comprises (A) carboxylated, hydrogenated acrylonitrile-butadiene copolymer (X-HNBR), (B) at least one isocyanate group and a group that forms a crosslink. It consists of a curing component to be contained, and (C) a solvent. The paint exhibits a cure elongation of at least 100% and remains adhered to the substrate after prolonged outdoor exposure. The preferred coating composition comprises (a) a carboxylated, hydrogenated copolymer consisting of repeating units from conjugated dienes, unsaturated nitriles, and carboxyl monomers, and (b) at least one isocyanate group and a crosslink. From 3 to 30% by weight of the curing component containing another group to form and (c) a solvent.

  In another aspect, the invention applies the solution-type paint to the surface of a vulcanized rubber substrate that is bonded to a metal, dries the paint, cures the dried paint under ambient conditions, and optionally heats It is related with the method of coat | covering the base material characterized by including the process to make. It is also desirable to provide a coating on the exposed metal portion around the elastomer. The present invention provides a coating for a composite of an elastomer and a metal, and provides a coating having excellent adhesion to an elastomer substrate, resistance to corrosive materials, and bending-fatigue resistance over a high temperature range.

Further, in another paint embodiment, an opaque, metal filled heat radiating elastomer paint that does not contain a vulcanization accelerator and cures at ambient temperature is provided. The paint is a two-part type that is mixed together when applied to the substrate. The first part represents the 0 ℃ following T _g, flexible film-forming polymer obtained by introducing a reactive functional group or functional group is an active hydrogen-containing group to the active hydrogen-containing curing agent, and a liquid carrier . The second part or another part is a hardener component having active hydrogen and a crosslinkable group, or a hardener component containing a group reactive with active hydrogen and a crosslinkable group, and a carrier liquid, and (a) film formation It consists of 10 to 100 parts by weight of thermally conductive metal particles having an average particle size of 2 to 10 μm per 100 parts by weight of the elastomer, or (b) 20 to 150 parts by weight of thermally conductive particles having an average particle size of 20 to 60 microns.

  The paints disclosed herein cure at ambient conditions and are solvent and fuel resistant and ozone resistant. The coating consists of a film-forming polymer and a specific amount of fine metal filler. The film former provides a film having a light transmission of at least 90% in the cured state and has no more than about 90% unsaturation after curing. Its film-forming matrix with a light transmission of 90% or more provides low loss heat reflectivity and heat transfer properties from reflective metal particulate fillers.

  The paint significantly reflects heat from the conductive particles underlying the paint, while the paint is permanently bonded and resistant to stress or environmental cracking or embrittlement. Such paints are molded rubber, TPE and plastic products, such as pneumatic tires, non-pneumatic tires, hoses, belts, mounts, shrouds, deflector panels, etc., especially engine blocks or other industrial components that emit heat. Durablely adheres to objects used in high temperature object comparison. The cured paint is scratch resistant.

  The paint cures to a dry film thickness (DFT) of typically about 12.7 to 508 μm under ambient conditions after application to an elastic substrate. The paint is substantially devoid of water depending on the curing agent and film former selected, or is applied in liquid form using an aqueous or organic carrier as an aqueous dispersion. Depending on the effectiveness of the curing conditions, rapid curing can be obtained under high temperature conditions with or without the application of light energy. An advantage of the present invention having ambient cure is that the final assembled rubber product does not need to be heated to cure the paint. The physical properties of metal-filled cured coatings include flex-fatigue resistance over a wide operating temperature range (-40 ° C to 150 ° C), degradation resistance to prolonged exposure to high temperatures and ozone, and elastomeric elastomer bases. Includes excellent adhesion to materials. The coating composition after curing at room temperature exhibits an elongation of about 50% or more without distortion, typically without adhesion loss, cracking, distortion or separation or distortion from the underlying flexure of the elastomer substrate. Extends to 100%, 200% or 300%. The heat reflective surface maintains its binding properties against repeated bending and the thermally conductive particles remain providing a heat radiating surface.

  The coating composition contains at least one film former polymer or prepolymer containing a functional group as a curing site for a curing agent without the use of a vulcanizing agent. The curing agent is typically utilized in an amount of 5 to 100 (phr) per 100 parts of film former polymer. The thermally conductive metal particles are identified below by weight based on the average particle size of the metal particles.

  Examples of useful film-forming polymers having active hydrogen functional groups are disclosed herein. Also disclosed are polymers containing functional groups that react with the active hydrogen-containing curing agent. Suitable film-forming polymers here are α-olefin elastomers, conjugated diene elastomers, hydrogenated diene elastomers, fluoroelastomers, ethylene-carboxylates, ethylene-propylene-diene elastomers, functionalized ethylene-vinyl acetate, SB-diblock. SBS- and SIBS-triblock copolymers and their hydrogenated variants, including acrylic rubbers, and polyurethanes are suitable for use herein. The functional group can be provided to the film former by a comonomer in the polymer or by known post-polymerization methods. Chemical cross-linking between the curing agent and the film-forming polymer is an essential feature of the present invention for ambient cure, substrate adhesion and durability.

  In a preferred embodiment, the coating composition of the present invention comprises a functionalized hydrogenated acrylonitrile-butadiene copolymer (A), at least one isocyanate group, preferably a polyisocyanate, or an isocyanate-functional prepolymer. , Or isocyanate silane, or at least one polyfunctional compound having an isocyanate group and a group that forms a cross-linking bond, an oligomer, a curing agent (B) including a prepolymer, and a solvent. It is an important feature of the present invention that the coating composition can be based on water or hydrocarbons. An aqueous paint containing low levels of volatile organic compounds (VOC) is provided.

  The paint of the present invention is applied to the elastomer substrate before or after vulcanization of the elastomer substrate. In one aspect, the present invention shows a method for applying a substrate comprising applying a paint to the surface of an unvulcanized rubber substrate, drying the paint at ambient or elevated temperature, and thereby curing the paint.

  In another aspect of the present invention, a step of applying a paint to the surface of a vulcanized rubber substrate that itself is optionally bonded to a metal component, drying the paint and curing the dried paint at ambient conditions ( There is provided a method for applying a substrate comprising a step of optionally applying heat, light or radiation. When necessary, it is desirable to provide paint on portions of exposed metal around the circumference of the elastomer.

  The present invention provides external paints for shaped or molded polymer products such as elastomeric materials and composites of elastomers and metals to provide excellent adhesion, corrosion resistance, heat generation resistance, and wide temperature range for elastomeric substrates. Gives bending-fatigue resistance over.

  A film is formed by the mixture of the two liquid parts when applied to the substrate. Part A of the two-part paint contains a liquid solution or dispersion of the functionalized polymer, and part B contains a liquid curing agent. When both parts are mixed, the ambient temperature curable embodiment has a typical pot life of 30 minutes to 1 hour. The curable paint mixture of Part A and Part B contains 2-20% solids. Its viscosity is controlled depending on the components selected and is below 20,000 cps (Type B viscosity) so that the paint can be sprayed, brushed or dipped.

Polymerized Functionalization Methods The functionalized elastomeric film formers used herein can be modified by several means to modify the film-forming polymer by, for example, a copolymerization method and incorporating functional groups into the polymer after polymerization. Can be provided by the method. The term “functionalized” means that the moiety with active hydrogen as part of the ethylenically unsaturated comonomer is copolymerized or has active hydrogen but is grafted and post-polymerized. The comonomer or grafting compound is covalently bonded to the polymer structure to provide a group that can react with the ambient temperature curing agent.

  The film-forming agent may convert a compound having a functional group into an appropriate functional group precursor when it is achieved via an ene reaction when the elastomer is in a solution or in a molten state, or by direct introduction of an appropriate precursor. Prepared using conventional methods that incorporate functional groups with active hydrogens into a non-polymerized non-functional elastomer, whereby acrylic hydrogen is transferred to the enol olophile, followed by coupling between two unsaturated ends Or continues via free radical addition between carbon-carbon double bonds in a molten state or dilute solution in a solvent. However, when the polymer is in the molten state, the necessary reaction to incorporate the functional group to be converted or directly incorporate the appropriate precursor radical using means that can provide mechanical high shear such as an extruder. Let On the other hand, when a functional group that is converted to a suitable precursor or a precursor radical that is directly incorporated is incorporated by a method such as metallization followed by reaction with a suitable electrophile, the incorporation should be done in solution polymer. Is desirable.

  Among several methods available to incorporate functional groups or functional group precursors, a single functional group or functional group precursor is used at each site of incorporation with minimal coupling of the elastomeric polymer, such as an ene reaction. Methods that tend to incorporate and methods that involve metallization with reaction with electrophiles are desirable. When a functional group that is converted to a suitable precursor is incorporated into the elastomer, the conversion of the functional group to the precursor is also generally obtained with the polymer in solution. In general, any known solvent useful for the preparation of such an elastomer in solution can be used for these reactions or conversions.

  Various post-polymerization functionalization techniques for providing non-functional addition polymers having bonded cross-linked curing sites for use in the present invention have been known. The hydroxyl group is a useful functional group that undergoes a crosslinking reaction with the curing agent used herein. U.S. Pat. No. 4,118,427 ozonizes a high molecular weight saturated hydrocarbon polymer such as polyisobutylene or ethylene-propylene rubber, followed by the ozonation material, such as dibutyl aluminum hydroxide. A hydroxyl-containing curable liquid hydrocarbon prepolymer is disclosed that is reduced using a reducing agent to produce the hydroxyl-containing liquid prepolymer having a substantially lower molecular weight than the starting polymer.

( A) Functionalized monomer The curable film-forming polymer used here can be produced by copolymerizing an elastomer-forming monomer together with a functionalized comonomer, or by reacting a functional group-containing monomer or reactive compound with a polymer. . The incorporated reactive group then cures the polymer by reaction of the curing components described herein. The curing method utilizes the reaction of an active hydrogen reactive functional group or copolymer or an active hydrogen reactive group that crosslinks with a corresponding reactive functional group on the copolymer pendant and a crosslinker. Various methods such as free radical addition copolymerization, anionic addition polymerization, free radical grafting, metathesis grafting, and hydrolysis grafting are known in the art. The functional group-containing polymer or copolymer is an α-olefin elastomer, a diene elastomer, a hydrogenated diene elastomer, a functionalized fluoroelastomer, a crosslinkable α-olefin copolymer elastomer, a functionalized acrylate or methacrylate copolymer, and Polymers characterized by their main components such as ethylene-carboxylates, etc. are included.

  Suitable examples of rubbery copolymer elastomers include, but are not limited to, anionically polymerized olefin elastomers. Examples of anionically polymerized olefin rubbers are optionally copolymerized with ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, polyisobutylene, or “butyl rubber”, or conjugated dienes (such as isoprene), optionally 30 wt% Other polymers of isoolefins containing up to, or α, β-ethylenically unsaturated nitriles and / or styrene comonomers (such as styrene and / or alkyl-substituted styrene), and the like. Particularly desirable elastomers include isobutylene-isoprene copolymers, isobutylene-paramethylstyrene copolymers, and the like.

  Suitable pendant active hydrogen functional groups are provided by a method for producing amine-functionalized ethylene propylene diene monomer rubber (EPDM) by the method disclosed in US Pat. No. 4,987,200. Similarly, high molecular weight isobutylene polymers functionalized with hydroxyl groups can be prepared using the methods described in EPA 325 997. In addition, polymers based on commercially available halogenated isobutylene containing low levels of halogen, typically 0.5-2.0 mol%, can be combined with alkylamines or aminoalcohols to provide amine or hydroxyl functionality, respectively. Groups can be generated.

  Functionalized elastomers having a weight average molecular weight of 1000 to 200,000 and containing hydroxyl and / or amine functional groups are known. Hydroxy-terminated polyisobutylene is usually prepared by introducing a hydroxyl group at the terminal position of cationically polymerized isobutylene by dehydrochlorination, hydroboration and oxidation of chlorine-terminated polyisobutylene. Chlorine-terminated polyisobutylenes obtained by cationic polymerization of isobutylene monomers are known (Fast and Kennedy in, “Living Carbochemical Polymerization: III. Demonstration of the Living Polymerization. 15”). : 317-23 (1986)).

  The living polymerization process is described in US Pat. Nos. 5,350,819; 5,169,914; and 4,910,321, and is a desirable technique for producing film-forming polymers. General conditions under which living polymerization can be achieved using, for example, isobutylene are (1) initiators such as tertiary alkyl halides, tertiary alkyl ethers, tertiary alkyl esters, etc .; (2 ) Lewis acid coinitiators typically consisting of halides of titanium, boron or aluminum; (3) proton scavengers and / or electron children; and (4) Lewis acid and known cations with a relative dielectric constant of the solvent. It includes a solvent selected in view of the polymerization system and the choice of monomer consistent with the monomer.

End functional polymer active hydrogen groups or groups reactive with active hydrogen groups can be incorporated at the ends of the film former polymers useful herein. US Pat. No. 5,448,100 describes an “inifer” (initiator-transfer agent) initiated carbocationic polymerization of isobutylene with a Lewis acid followed by a final quench and steam stripping with acetyl sulfate or methanol, ethanol, isopropyl alcohol, Alternatively, sulfonated telechelic polyisobutylene prepared by precipitation with acetone is disclosed. The polymerization preferably occurs in a chlorinated solvent, optimally a mixture of solvents such as methylene chloride, methyl chloride, or aliphatic or cycloaliphatic compounds having 5 to 10 carbon atoms. It should occur in. The Lewis acid can be, for example, boron trichloride or titanium tetrachloride, or other metal halide (including tin tetrachloride, aluminum chloride, or alkylaluminum). Although the final quenching preferably occurs at a temperature of −90 ° C. to 0 ° C., the polymerization temperature or the decomposition temperature of the complex is optimal. The molar ratio of polyisocyanate: acetyl sulfate is preferably 1: 1 or more.

  Film-forming polymers such as polyisobutylene can contain terminal silane groups with hydroxy and / or alkoxy groups. These can be obtained by known methods consisting of dehydrohalogenation of polyisobutylene polymers containing tertiary carbon-chlorine groups followed by addition reaction with ethylenically unsaturated silanes. For example, chlorobutyl rubber having a tertiary carbon-chlorine bond reacts with alkyl and mimethylsilane to give polyisobutylene having an unsaturated group, and then the addition conditions with a platinum catalyst using a hydrosilane compound of the general formula React below:

R ² in the formula is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or the formula (R ′) _3. SiO _−— (wherein each R ′ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms separately), each X is independently a hydroxyl group or a well-known group A represents 0, 1, 2 or 3; Alternatively, polymeric hydrosilane-terminated siloxanes can be used. Known hydrosilane compounds include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane; trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, and the like. Alkoxysilanes; acrylosilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, and the like; and ketoximate silanes such as bis (dimethylketoxymate) methylsilane, bis (cyclohexylketoxymate) methylsilane, and the like. This method is described in, for example, JP-A-4-69659, JP-A-7-108928, JP-A-63-254149, JP-A-64-22904, and Japanese Patent 2539445.

The functionalized hydrogenated diene copolymer suitable for use herein as the functionalized hydrogenated diene elastomer film-forming polymer is preferably about 50,000 or more, more typically 200,000 to 500,000. The solvent-soluble polymer having a molecular weight of 10% by weight or less and containing 10% by weight or less of a conjugated diene segment. These polymers are different from reactive end groups, functional liquid polymers, eg liquids such as ATBN and CTBN, functionalized oligomers. The unsaturated, functionalized polymer from which the halogenated coating polymer is prepared is typically 50-85 wt% conjugated diene monomer units, 5-50 wt% one or more nonconjugated, ethylenically unsaturated monomers. It consists of 1 to 20% by weight of a functional comonomer or graft-binding compound having a body unit and a reactive crosslinking site. The preferred conjugated diene monomer units are derived from 1,3-butadiene monomers and the non-conjugated, ethylenically unsaturated monomer units are such as unsaturated acrylic esters, methacrylic esters, acrylonitrile and methacrylonitrile. Derived from one or more ethylenically unsaturated monomers selected from nitriles, monovinyl aromatic hydrocarbons such as styrene and alkyl styrene, and vinylidene comonomers. Desirably, divinyl aromatic hydrocarbons such as divinylbenzene and dialkenyl aromatic hydrocarbons such as diisopropenylbenzene are not present. Other comonomers include methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or methacrylate, alkyl (meth) acrylates such as vinyl pyridine, and vinyl esters such as vinyl acetate. Suitable functional comonomers are selected from unsaturated carboxylic acids and esters thereof such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid. The functionalized diene elastomer film former must be -10 ° C or less, preferably -25 ° C or less, to provide acceptable flex-crack / bend-fatigue resistance in thermally conductive particle-filled coatings.

Carboxyl end groups contain -C-CH = CH-C-type unsaturation by a chain scission method in which rubber ozonides are produced and aldehyde end groups are oxidized to carboxyl groups using peroxides or peracids. Diene elastomer high polymer can be formed. Alternatively, the hydroxyl end groups of rubber ozonides can be formed by catalytic hydroreduction or metal hydrides or borohydrides (see, eg, British Patent No. 884,448). Similarly, U.S. Pat. No. 4,118,427 ozonates high molecular weight saturated hydrocarbon polymers such as polyisobutylene or ethylene-propylene rubber and then, for example, a reducing agent, preferably dibutyl hydrogenation. A liquid hydroxyl-containing curable liquid hydrocarbon prepolymer is disclosed by reducing the ozonated material using aluminum to produce the hydroxyl-containing liquid prepolymer having a lower molecular weight than the starting polymer. Modification of the film-forming polymer by incorporation of a mercapto alcohol or mercaptocarboxylate graft compound provides a film-forming agent useful in the present invention. Suitable hydroxy mercaptans and / or mercaptocarboxylic esters contain hydroxyl. HS-R-OH compound (R is a linear, a branched, or cyclic C ₁ -C ₃₆ alkyl group, it may be optionally substituted with or more hydroxyl groups to 6, or a nitrogen, oxygen or sulfur atom including those that can be interrupted _{.HS- (CHR 2) n - (} C (O) oR 3 OH) is _{m (R 2} hydrogen or _C 1 -C ₆ alkyl group in the formula, _{R 3} is a linear, branched a is or cyclic C ₂ -C ₃₆ alkyl group, which may substituted with optionally up to 6 or more hydroxyl groups, or nitrogen, can be interrupted by an oxygen or sulfur atom, -OH is preferably a primary, n represents A mercaptocarboxylate represented by the following formula is suitable: an integer of 1 to 5 and m is an integer of 1 to 2.

Suitable hydroxy mercaptans are mercaptoethanol, 1-mercapto-3-propanol, 1-mercapto-4-butanol, α-mercapto-ω-hydroxyoligoethylene oxide, such as α-mercapto-ω-hydroxyoctaethylene glycol, or the corresponding Ethylene oxide / propylene oxide copolyether. Mercaptoethanol and α-mercapto-ω-hydroxy oligoethylene oxide are preferred. Suitable mercaptocarboxylic acids containing hydroxyl groups are esters of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and N-methyldiethanolamine tomercaptoacetic acid, mercaptopropionic acid and mercaptobutyric acid. . The corresponding esters of mercaptoacetic acid and mercaptopropionic acid are particularly desirable. Suitable types of elastomer film former-based polymers that react with mercapto compounds are isobutylene, chloroprene, polybutadiene, isobutylene / isoprene, butadiene / acrylonitrile, butadiene-acrylate copolymer, SB copolymer, butadiene-vinylidene. A chloride-acrylate type copolymer (however, the degree of unsaturation is 10% or less). Methods for incorporating mercapto compounds are described in US Pat. No. 6,252,008 and are suitable for use herein as functional film-forming polymers. The rubber contains bound hydroxyl groups in the range of 0.1 to 5 weight percent. The molecular weight of the solution polymerized diene rubber containing hydroxyl groups incorporated according to the method of US Pat. No. 6,252,008 is in the range to obtain a dilute solution of 5-15% solids, 10,000-200,000.
It should be sprayable, brushable or dipping, such as M _n (gel permeation chromatography).

  There are other known methods of incorporating OH groups into suitable film forming polymers for use herein, such as addition reaction with formaldehyde, reaction with carbon monoxide with hydrogenation, and hydroboration with hydrolysis. is there. Copolymerization using silanes containing ethylenically unsaturated groups is a suitable method. Exemplary silane comonomers include vinyl silane or allyl silane with reactive silicon. Examples are vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldi. Including chlorosilane, diallyldimethoxysilane, γ-methacrylooxypropyltrimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane.

  Functionalized diene elastomers are described below with respect to nitrile copolymers as the optimum film former embodiment of the present invention. Functionalized butadiene acrylonitrile copolymers provide beneficial film properties such as low temperature flexibility, oil, fuel and solvent resistance, and good abrasion and water resistance.

  The present invention is best practiced with functionalized hydrogenated nitrile rubber (HNBR). The functionalization of HNBR with reactive functionality provides a way to crosslink the coating composition to obtain an essential level of adhesion to the elastomeric substrate. Without proper adhesion to the elastomeric substrate, the film exhibits premature flex-cracking and / or delamination. The functional group of HNBR can generally be classified as containing an active hydrogen group, an ethylenically unsaturated group or a hydrolyzable group.

  HNBR can be cured through addition of the cross-linking component, exposure to moisture, heat (infrared, heating), UV radiation, or electron beam radiation. Depending on the reactive functionality, it is incorporated into the diene copolymer. Some of the functionalized HNBR embodiments listed below are self-curing without the addition of a crosslinker and are all, but not limited to, dinitrobenzene, ZnO, γ-POM, phenol resole, polyfunctional amines, poly It can be cured with suitable crosslinking components added to the functionalized HNBR, such as isocyanates, polyacrylates, dicyandiamides, dicarboximides, and formaldehyde (or UF, MF) resins.

  Functionalized HNBR can be prepared by various methods known in the art. Functional groups can be functionalized by use of functional group-containing comonomers, or graft-bonding, functional group-containing compounds, and use of metathesis, followed by hydrogenation of modified NBR, or reaction of methylolated phenol with NBR. This can then be incorporated by a reaction to give a functionalized HNBR by hydrogenation of the reformed NBR.

  Functionalized HNBR having an active hydrogen-containing functional group is a suitable crosslinkable film-forming agent in a curable radiation coating composition. The presence of unsaturated groups (ie vinyls, nitriles, olefins) in the NBR provides reactive sites to which reactive functionality can be combined to be used for further cross-linking, post-polymer functionalization, and flawed reactions. . These reactive sites can be modified through catalytic or non-catalytic chemistry. Such modification can introduce some number of active hydrogen functional groups such as epoxides by epoxidation of olefinic sites. Epoxides are easily converted to functional groups via ring-opening reactions. In addition, epoxides serve as crosslinkable sites using chemistry available to those skilled in the art. Many other functional groups include main chain olefin reactions: hydroformation (aldehyde, alcohol, carboxylic acid), hydrocarboxylation (carboxylic acid), hydroesterification (ester), hydrosilylation (silane), hydroamination (amine) ), Halogenated (halogen), chlorosulfonated (chlorine, sulfonic acid), hydroborated (borane, alcohol, amine). Such transformation is described by Tremont (McGrath, MP; Sall, ED; Tremont, S. J. “Functionalization of Polymers by Metal-Mediated Processes,” Chem. Rev. 1995, 95, 381). Has been. The nitrile group of the NBR elastomer is also converted to an amide by reaction with an alcohol in an acid catalyzed process, and converted to a carboxylic acid by hydrolysis.

  Crosslinking can be performed via addition of crosslinking components, addition of moisture, heat, UV radiation or electron beam radiation. Depending on the reactive functionality attached to the HNBR and its intended use, suitable cross-linking components may be dinitrosobenzene, ZnO, γ-POM, resole, polyfunctional amines, isocyanates, acrylates, and dicyandiamides. Can be added to such functionalized HNBR. Particularly desirable crosslinking components are those components known in the art for obtaining good bonds to elastomeric products. These components include DNB, ZnO, and QDO and can be added to enhance the adhesion of the functionalized HNBR to a wide range of elastomeric materials.

  The reactive functionality incorporated into the diene elastomer includes, but is not limited to, phenol OH, aliphatic OH, amine, isocyanate, epoxy, acrylate, silyl ether, silyl chloride, anhydride, maleimide, and Diels in the functional groups -Includes Alder dienefill.

  Suitable curing components and curing reaction aids are described in R.I. F. Are well known in the prior art and patents in the field of adhesives and paints for curing. For example, when the functional group of the polymer is phenol, isocyanates, dicarboximides, formaldehyde sources, and resoles are useful to crosslink phenol-functionalized HNBR. Similarly, amine functionalized HNBR can be crosslinked using, for example, isocyanates, dicarboximides, formaldehyde sources, and resoles. Epoxy functionalized HNBR can be crosslinked and cured with suitable amine and dicyandiamine components as is known in the art of epoxy adhesives and paints. Isocyanate functionalized HNBR is of particular interest because it can be crosslinked or cured by the addition of moisture or other curing agents such as amines or polyols. The incorporation of isocyanate as part of HNBR is particularly desirable because it reduces the amount of free monomer, and thus volatile isocyanate, and reports health and safety issues. Latent isocyanate functionalized HNBR can be prepared by reacting amine functionalized HNBR (or NBR) with diallyl carbonate to give urethane functionalized HNBR (or NBR). Thermal cracking of urethane produces isocyanate functionalized HNBR (or NBR) (see, for example, Kothandaraman, K ,; -Pure applied Chem. 1995, A32, 1009; Wicks, DA; Wicks, ZW. S .; Krishnamurti, N. "Synthes s and thermal Debloking of Blocked Diisocyanate Adducts ", referring to the Eu.Polm.J.1998,34,77). Maleimide functionalized HNBR can be cross-linked by addition of free radical initiator or Michael addition reaction. Maleimide is a known cross-linking agent. Acrylate functionalized HNBR is capable of both free radical, UV and electron beam curing. The anhydride functionality can be cured using components described in the amine and anhydride-epoxy adhesive arts. Silyl ethers and chlorosilanes can be used in the moisture-curing embodiment at room temperature. Diels-Alder adducts are due to the addition of self-curing or metathesis-type catalysts.

  Detailed examples of the grafting method for introducing functional groups into a film-forming elastomer include a polyfunctional graph such as a polyfunctional acrylate, a polybutadiene maleate, and a metal salt of a difunctional acrylate and a melt film formation with a binding material. Elastomer melt processing. For example, an olefin elastomer such as EPDM is kneaded in a two-stage roll with 5 parts of an acid scavenger such as zinc oxide, 1 part of stearic acid, an antioxidant, and a peroxide followed by trimethylolpropane triacrylate. Add 5 to 10 parts of a polyethylenically unsaturated compound such as maleic acid liquid polybutadiene or zinc diacrylate to the flux roll.

  Functionalized HNBR can be prepared by metathesis, followed by hydrogenation of the reformed NBR to give functionalized HNBR, and (2) functionalized HNBR by reaction of methylolated phenol with NBR followed by hydrogenation of the reformed NBR give.

Novel methods for introducing reactive pendant functional groups such as carboxy, anhydride, hydroxy functionality are described below:
Direct functionalization of suitable unsaturated film-forming polymers that can be used here, particularly NBR, is achieved via olefin metathesis chemistry. The olefin C = C double bond reacts with the catalyst and monomer. The olefin metathesis catalyst must be able to catalyze the metathesis reaction in the presence of nitrile functional groups. The monomer can be an olefin metathesis reaction (eg, cycloolefin, olefin, or α, which can undergo ring-opening metathesis polymerization “ROMP”, cross-metathesis, ring-opening-cross metathesis, and allyldiene metathesis polymerization “ADET”, These monomers can be functional groups such as carboxylic acids, amides, esters, anhydrides, epoxies, isocyanates, silyls, halogens, Diels-Alder dienes and dienophiles. , Etc.) to provide a cure site for the secondary crosslinking reaction of the cured film, or to give the polymer a new property, kinetically, the metathesis catalyst appears to attack the vinyl C═C bond first. However, low levels in the HNBR copolymer antagonize and attack with the main chain C = C double bond. May cause a decrease in the molecular weight of NBR, but the extent of such a process can be minimized by the use of high NBR relative to the catalyst level, for example, after reducing the reformed NBR using catalytic hydrogenation, the reactive reformed HNBR heavy The polymer can be crosslinked using moisture, a selected curing agent, or an external energy source (UV or electron beam) A particularly desirable advantage of metathesis catalysts is the mild conditions in water or solvent. This is a unique means of introducing reactive functionality into NBR under the NBR latex, even through the metathesis catalyst, can be modified with reactive functionality without destabilizing the latex. Or allows the functionalization of various commercially known NBR polymers as aqueous dispersions, and latexes (aqueous polymers) are hydrogenated and functionalized Resulting in NBR.

Diene polymer having hydrogenated protonic group as a terminal group Diene polymer having hydrogenated hydroxy or carboxy as a terminal group may be used alone or as a mixture with another high molecular weight (10,000 Mn or more) film-forming polymer. Is also suitable as a curable film-forming agent used in the radiation coating of the present invention. Substantially saturated polyhydroxylated polydiene polymers are known and commercially available. These represent anionically polymerized conjugated diene hydrocarbons such as butadiene or isoprene, which are lithium initiators terminated with OH groups. The process steps are described in US Pat. No. 4,039,593; Re. No. 27,145; and 5,376,745, all of which are hereby incorporated by reference for disclosure of polyhydroxylated polydiene polymers. Such polymers have been made with dilithium initiators such as compounds produced by the reaction of 2 moles of sec-butyllithium with 1 mole of diisopropylbenzene. Such butadiene polymerization has been carried out in a solvent consisting of 90% by weight cyclohexane and 10% by weight diethyl ether. The molar ratio of di-initiator: monomer determines the molecular weight of the polymer. The polymer capped 2 moles of ethylene oxide to give dihydroxy polybutadiene terminated with 2 moles of methanol. The hydroxylated polydiene polymer is hydrogenated and substantially all of the carbon-carbon double bonds are saturated. Hydrogenation is accomplished by those skilled in the art by established methods including hydrogenation in the presence of noble metals such as Raney nickel, platinum, catalysts such as soluble transition metals and titanium catalysts as in US Pat. No. 5,039,755. Has been implemented. Suitable polyhydroxylated polydienes are commercially available under various trade names. High molecular weight polymers suitable for blending with hydrogenated hydroxylated butadiene polymers are not limited, such as the above carboxy modified chlorinated polyethylene, chlorinated polyethylene, epichlorohydrin polymer, ethylene-acrylic copolymer. Copolymers, SBR, SBS, nitrile rubber (NBR), SIBS, EPDM, EPM, polyacrylates, halogenated polyisobutylene, polypropylene oxide, and the like are known. The weight ratio of liquid hydrogenated polybutadiene: high molecular weight film former is limited such that the total% unsaturation is 10% or less of the total. Thus, when the mixture of hydrogenated polydiene polyols is made of an unsaturated polymer such as SBR, NBR, etc., the proportion of unsaturated polymer is limited to maintain the overall saturation at least 90%. The Modified chlorinated polyolefins can include those modified with acid or anhydride groups. Some examples of modified chlorinated polyolefins are described in U.S. Pat. No. 4,997,882 (column 1, line 26 to column 4, line 63); 5,319,032 (column 1, line 53 to number 1). 2 column 68 line); and 5,397,602 (first column 53 line to second column 68 line). The chlorinated polyolefin preferably has a chlorine content of about 10-40% by weight, more preferably about 10-30% by weight, based on the weight of the starting polyolefin. Suitable examples of modified chlorinated polyolefins have a chlorine content of about 10-30% by weight, based on the weight of the polyolefin (which is not neutralized with amines), and have an acid number in the range of about 50-100. It is a modified chlorinated polyolefin.

Hydrogenated block copolymers Suitable film formers that can be adapted according to the present invention are hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, which are chlorinated polyethylenes. The block copolymer is provided with curing functionality for interaction with the curing agent. Several elastomeric block copolymers containing carboxyl groups are commercially available. Those block copolymers containing unsaturation can be hydrogenated according to known hydrogenation methods including those cited herein.

Functionalization of HNBR with phenol functional elastomeric phenol functionality can be performed by mixing methylolated phenol and NBR followed by hydrogenation of the phenol modified NBR intermediate. Methylolated phenols can form covalent bonds with NBR and NBR copolymers by various chemical reactions as reported in the following literature: Knop and L.M. Pilato, “Phenolic Resins Chemistry and Applications and Performance” Springer-Verlag, New York 1985, Chapter 19pg 288-297.

  Various known isocyanate-reactive functional groups can be introduced into the functionalized elastomeric film-forming polymer. The carboxy-functional, hydroxy-functional and amine-functional elastomers are most easily adaptable. Functional comonomers, such as carboxy-functional comonomers, are readily adaptable to the production of carboxylated hydrogenated nitrile rubber copolymers. For the purposes of the present invention, functionalized hydrogenated nitrile rubber can be defined as a polymer comprising at least one diene monomer, a nitrile monomer, and a comonomer or graft-binding compound containing functional groups or combinations thereof. As used herein, the abbreviation HNBR means a rubber containing a diene monomer other than 1,3 butadiene and a comonomer other than acrylonitrile unless otherwise specified. It is also important to recognize that the addition monomer is polymerized with the diene monomer or grafted to the diene monomer to produce a functionalized HNBR. The addition monomer can, for example, provide at least one functional group to promote crosslinking.

  Functionalization of HNBR with phenol functionality can be achieved with unsaturated unhydrogenated polymers, or partially hydrogenated XHNBR polymers (80-97% hydrogenation level) with heat and optionally catalyzed by a suitable Lewis acid. This can be done by addition of phenol or ether derivatives. It is desirable to provide an ether blocking group to the methylol phenol compound to facilitate ease of post-reaction hydrogenation. Addition can be via a nitrile or carboxyl group by formation of an ester, or by said addition at the allyl moiety. The metathesis reaction of an ethylenically unsaturated compound having a phenol group is desirably performed in a solvent or water. Also, the ethylene-containing methylolated phenol ether or phenol is metathesized with NBR and then hydrogenated. The phenol functionalized NBR is then hydrogenated. The methylolation reaction can be performed using formaldehyde and phenol functional NBR or HNBR to generate methylolated phenol functionality in NBR or HNBR. Methylolated phenols can form covalent bonds with NBR and NBR copolymers by various chemical reactions as reported in the literature (A. Knop and L. Pilato, “Phenolic Resins Chemistry and Applications and Performance“ Springer- Verlag, New York 198, Chapter 19, pg. 288-297). The following structural diagram illustrates functionalization with representative phenol-containing compounds:

  Although any methylolated phenol can be combined with NBR, monomethylolated phenol is particularly desirable. The combination of monomethylolated phenol and NBR yields a stable phenol functionalized NBR product. After hydrogenation of phenol-modified NBR according to methods known in the art (eg, catalytic hydrogenation), a phenol-functionalized HNBR copolymer is obtained which is a stable phenol-modified HNBR copolymer comprising dicarboximide, isocyanate And various well-known crosslinking agents for phenolic resins including those selected from formaldehyde sources (paraformaldehyde, γ-POM, hexamethyleneamine, phenolic resole or etherified phenol).

  Methylolated phenol functionalized nitrile rubber (NBR) or halogenated variant (HBNR) can be prepared by methods known in the art. Phenol functionalized NBR / HBNR can be prepared by metathesis involving monomethylolated phenol or unsaturated NBR and unsaturated monomers. The methylolated phenol functionalized NBR / HBNR prepared by metathesis utilizes a methylolated phenol monomer and NBR. These materials include not only paints according to the present invention, but also elastomer-metal adhesives, self-adhesive materials, RFL dipping, and reactive enhancers that utilize unique curing, film formation, metal adhesion and compatibility (eg, It is also useful as a component of (epoxy adhesive). The methylolated phenol functionalized NBR / HBNR can be self-curing (ie, without an external curing agent). Derivatives of methylolated phenol functionalized NBR / HBNR can be cured with paint components such as phenol novolac, active hydrogen, active hydrogen containing crosslinkers and rubber / elastomer tougheners. The methylolated phenol functional HBNR can be used with known vulcanizing agents for rubber. The vulcanization reaction is based on the formation of quinone methide or benzyl carbenium, which is caused by thermal or catalytic activation of methylolated phenol. The quinone methide intermediate reacts by abstracting allyl hydrogen. Methylolated phenol also generates reactive benzylcarbenium ions under acidic catalyzed conditions that react with the unsaturated polymer in the substrate.

  When the reactive functional group of HNBR is phenol, isocyanates, dicarboximides, formaldehyde sources, and resol curing agents are useful for crosslinking the phenol-functionalized HNBR to the elastomeric substrate. Similarly, amine-functionalized HNBR can be crosslinked using, for example, isocyanates or dicarboximides, formaldehyde sources, and / or resoles. Epoxy-functionalized HNBR can be crosslinked and cured with known curing agents well known in the epoxy adhesive art, such as amines, amidoamines, and / or dicyandiamides.

  The isocyanate-functionalized HNBR can be crosslinked or cured by the addition of moisture or other curing agents such as amines or polyols. The introduction of isocyanate as part of HNBR is particularly desirable because it reduces the amount of free monomer and thus volatile isocyanate and its health and safety issues. Maleimide functionalized HNBR can be crosslinked by the addition of free radicals or by Michael addition reaction. Ethylenically unsaturated acrylate-functionalized HNBR is capable of both free radical, UV and electron beam curing. Anhydride functionalized HNBR can be cured using the components described in amines and anhydride-epoxy adhesives. Silyl ethers and chlorides are moisture cured. Diels-Alder adducts are self-curing or with known metathesis catalysts.

  In order to provide an ethylenically unsaturated nitrile-conjugated diene rubber having at least 90% saturation, the nitrile rubber is hydrogenated by conventional means. In general, any of a number of known hydrogenation methods can be utilized, including but not limited to solution hydrogenation and oxidation / reduction hydrogenation. Hydrogenation helps to saturate at least 90% of the rubber unsaturated bonds. When the saturation is 90% or less, the heat resistance of the rubber is low. The preferred saturation of the rubber is 95-99.99%.

  Suitable conjugated diene monomers useful for the preparation of carboxylated acrylonitrile-butadiene copolymers that are further hydrogenated are well-known conjugated dienes, including, but not limited to, dienes having about 4 to 10 carbon atoms. 1,3-butadiene; 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene; 1,3-pentadiene; 1,3-hexadiene; 1,3-heptadiene; piperylene; and isoprene (1,3-butadiene is currently preferred).

  The unsaturated nitrile monomer that is copolymerized to produce the carboxylated acrylonitrile-diene copolymer typically corresponds to the following formula:

Each A in the formula is hydrogen or a hydrocarbyl group having 1 to about 10 carbon atoms. Examples of A groups are alkyl and cycloalkyl such as methyl, ethyl, isopropyl, t-butyl, octyl, decyl, cyclopentyl, cyclohexyl, etc., and phenyl, tolyl, xylyl, ethylphenyl, t-butylphenyl, etc. Including aryl. Acrylonitrile and methacrylonitrile are presently preferred unsaturated nitrites.

The HNBR of the present invention also includes a functional group-containing monomer that is polymerized in the main chain of the HNBR, or a functional group-containing compound that is grafted to the HNBR, or a mixture thereof.
A carboxy group-containing monomer is optionally used in the film-forming elastomer used in the present invention. The carboxy group is an α, β-unsaturated monocarboxylic acid monomer having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid and crotonic acid, and / or is not limited to 4 to 5 carbon atoms. Or 6 α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid and itaconic acid, and their anhydrides. The bound unsaturated carboxylic acid is present in an amount of about 1-10% by weight of the copolymer, this amount replacing the corresponding amount of conjugated diolefin. The monomer is preferably an unsaturated mono- or di-carboxylic acid derivative (eg, ester, amide, etc.). The function of the carboxyl group-containing monomer serves as a cross-linking site and includes promotion of adhesion.

  In addition, other functional comonomers are copolymerized into the backbone of the HNBR copolymer. Examples of functional ethylenically unsaturated monomers that can be copolymerized with nitrile monomers and conjugated diene monomers include hydrazyl group-containing ethylenically unsaturated monomers, amino group-containing ethylenically unsaturated monomers, thiol group-containing Unsaturated monomers such as unsaturated ethylenically unsaturated monomers, unsaturated carboxylic acids (eg acrylic acid, methacrylic acid, itaconic acid and maleic acid and their salts), eg various acrylates such as methyl acrylate and butyl acrylate Alkyl esters of saturated carboxylic acids; alkoxyalkyls of unsaturated carboxylic acids such as methoxy acrylate, ethoxy acrylate, methoxyethyl acrylate, acrylamide, and methacrylamide.

  The functional comonomers also include various classes of monomers such as N, N-disubstituted-aminoalkyl acrylates; N, N-disubstituted-aminoalkyl methacrylates; N, N-disubstituted-aminoalkyl acrylates. N, N-disubstituted-aminoalkylmethacrylamide; hydroxyl-substituted-alkyl acrylate and hydroxyl-substituted-alkyl methacrylate, N-substituted methylolacrylamide, N, N'-dimethylolacrylamide and N-ethoxymethylolacrylamide N-alkylol substituted acrylamides such as: N-methylol methacrylamide, N-substituted methacrylamide, N-N'-dimethylol methacrylamide and N-substituted methacrylamides such as N-ethoxymethyl methacrylamide (especially free radicals) Starting weight Is formed in the presence of an alkyl thiol compound having 12 to 16 carbon atoms and three tertiary carbon atoms).

  Specific examples of hydroxy-substituted-alkyl acrylate and hydroxy-substituted-alkyl acrylate comonomers include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 3-phonoxy-2-hydroxypropyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate and 3-phonoxy-2-hydroxypropyl Mention may be made of methacrylates. Of these, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, hydroxymethyl methacrylate, and 2-hydroxyethyl methacrylate are desirable.

  The NBR copolymer is polymerized by reaction of any of the above exemplified conjugated dienes, unsaturated nitriles, and unsaturated functional group-containing comonomers in the presence of a free radical initiator by methods well known to those skilled in the art. Suitable free radical initiators are beyond the scope of this disclosure and are typically organic oxides, peroxides, hydroperoxides, and azo compounds, such as hydrogen peroxide, benzoyl peroxide, cumene hydro Peroxide, di-t-butyl peroxide, alkali dol, acetyl peroxide, t-butyl hydroperoxide, trimethylamine oxide, dimethylaniline oxide, peracetic acid, nitrate, chlorate, perchlorate, azobisisobutyronitrile, etc. .

  The hydrogenation of nitrile rubber is known technically and in the literature. For example, a suitable commercial X-HNBR (carboxylated-HNBR) is made from a carboxylated nitrile-diene copolymer and hydrogenated in two steps. The C—C double bonds of 1,2-vinyl-conjugated butadiene units in NBR are hydrogenated very rapidly to 1,4-cis conjugated units. 1,4-trans conjugated butadiene units are hydrogenated relatively slowly. The NBR products used for hydrogenation are distinguished by a significant proportion of 1,4-conjugated transconjugated double bonds.

  In known two-stage hydrogenation processes, the carbon-carbon double bond is first reduced, followed by the reduction of the carbon-nitrogen bond. Other techniques for hydrogenating acrylonitrile-butadiene copolymers are disclosed, for example, in US Pat. Nos. 4,581,417; 4,631,315; and 4,795,788.

  Partially or fully hydrogenated nitrile rubber (HNBR) is described in a few specifications (for example DE-OS No. (German Published Specification) 2,539,132; 3,329,973; 3,046,008 and 3,046,251 are also disclosed.

  The hydrogenation of the X-HNBR latex can be carried out by known conventional methods. Carboxylated NBR latex conventionally made using anionic surfactants is selected from (1) an oxidant selected from the group consisting of oxygen, air and hydroperoxide; (2) selected from hydrazine and its hydrates Mixed with the metal ion activator; and the mixture is heated from 0 ° C. to the reflux temperature of the reaction mixture. This technique is taught in US Pat. No. 4,452,950.

Optimal acrylonitrile-butadiene copolymers are hydrogenated so that the final product has an unsaturation level of about 1 to 10 mol%, preferably about 1 to 5 mol%.
A suitable carboxylate hydrogenated nitrile rubber (X-HNBR) is manufactured by Bayer under the trade name “Therban”, eg, Therban KA8889. X-HNBR preferably has an iodine number of about 50% or less, more preferably 3-40%, optimally about 8-30%.

  The crosslinker-reactive functional group of the film former provided by the method can be provided before or after hydrogenation. Examples of the unsaturated compound having a functional group include a vinyl compound having a functional group and a cycloolefin having a functional group. The introduction of the functional group by the graft modification method can be carried out by reaction of HNBR with a functional group-containing unsaturated compound in the presence of an organic oxide. There is no particular limitation on the functional group-containing unsaturated compound. Epoxy group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, silyl group-containing unsaturated compounds, unsaturated organosilicon compounds, etc. can be applied to a substrate with a crosslinking density and low modification rate. Listed for adhesive reasons.

  Epoxy group-containing unsaturated compounds or epoxy group-containing cycloolefins are glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate, glycidyl methacrylate and glycidyl p-styryl-carboxylate; endo-cis-bicyclo [2,2, 1] Unsaturated polycarboxylic acids such as hept-5-ene-2,3-dicarboxylic acid and endo-cis-bicyclo [2,2,1] hept-5-en-2-methyl-2,3-dicarboxylic acid Mono- or polyglycidyl esters of acids; unsaturated such as allyl glycidyl ether, 2-methyl-allyl-glycidyl ether, O-allylphenol noglycidyl ether, glycidyl ether of m-allylphenol and glycidyl ether of p-allylphenol Glycidyl ether; and 2- (vinyl Phenyl) ethylene oxide, 2- (p-vinylphenyl) ethylene oxide, 2- (o-allylphenyl) ethylene oxide, 2- (p-allylphenyl) ethylene oxide, 2- (p-allylphenyl) propylene oxide, p-glycidylstyrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6- Including epoxy-1-hexene, vinylcyclohexene monoxide and allyl-2,3-epoxycyclopentyl ether. These epoxy group-containing unsaturated compounds are used alone or in combination.

  Examples of the saturated compound containing a carboxyl group include compounds described in JP-A-5-271356, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and α-ethylacrylic acid; maleic acid, fumaric acid Acid, itaconic acid, endo-cis-bicyclo- [2.2.1] hept-5-ene 2,3-dicarboxylic acid and methyl-endo-cis-bicyclo- [2.2.1] hept-5-ene Mention may be made of unsaturated dicarboxylic acids such as 2,3-dicarboxylic acids. Furthermore, examples of unsaturated carboxylic acid derivatives include anhydrides, esters, halides, amides and imides of unsaturated carboxylic acids. Specific examples include anhydrides such as maleic anhydride, chloromaleic anhydride, butene succinic anhydride, tetrahydrophthalic anhydride and citraconic anhydride; esters such as monomethyl maleate, dimethyl maleate and glycidyl maleate. Maleic anhydride and itaconic anhydride are particularly desirable because the unsaturated dicarboxylic acids and anhydrides described above are desirable because of the ease with which functional groups can be introduced by reaction with the graph.

  Examples of hydroxyl group-containing unsaturated compounds to be introduced into the film-forming polymer are allyl alcohol, 2-allyl-6-methoxyphenol, 4-alkoxy-2-hydroxybenzophenone, 3-alkoxy-1,2-propanediol, 2 -Allyldiphenol, 3-buten-1-ol, 4-buten-1-ol and 5-hexen-1-ol. Examples of silyl group-containing unsaturated compounds to be introduced into the film-forming polymer are chlorodimethylvinylsilane, trimethylsilylacetylene, 5-trimethylsilyl-1,3-cyclopentadiene, 3-trimethylsilylallyl alcohol, trimethylsilyl methacrylate, 1-trimethylsilyloxy-1 , 3-butadiene, 1-trimethylsilyloxycyclopentene, 2-trimethylsilyloxyethyl methacrylate, 2-trimethylsilyloxyfuran, 2-trimethylsilyloxypropene, allyloxy-t-butyldimethylsilane and allyloxymethylsilane.

  Examples of the unsaturated organosilicon compound to be introduced include trisalkoxyvinylsilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and tris (methoxyethoxy) vinylsilane. The alkoxy group in such an unsaturated organosilicon compound is hydrolyzed to a silanol group.

Examples of unsaturated sulfonic acid or phosphorus ester groups are 2- (meth) acrylamide-methyl-1-propanesulfonic acid, 3-sulfopropyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, and 2-phosphoethyl (meta ) Acrylate. Various vinyl with 0 ℃ below T _g of the film-forming polymer - acrylates, these comonomers introduced into acrylate or other flexible polymers, epoxy resins, isocyanates, carbodiimides, amino resins, aminosilanes, and other Curing in the presence of acidic groups. A flexible, low _Tg comonomer having an acid number of at least about 2 mol% sulfur and / or phosphorus containing acid groups and having an acid number of 5-100, preferably 10-80, optimally 10-30 is included in the present invention. Therefore, it is a useful film forming agent.

  The graft-modified HNBR according to the present invention is obtained by graft-reacting one of the above-mentioned ethylenically unsaturated compounds having a functional group with HNBR under the generation of radicals. Examples of methods for generating radicals include (1) a method using an organic oxide, (2) a method using a photo-induced radical generator, (3) an energy beam irradiation method, and (4) a heating method. Can do.

(1) Method of using organic peroxide: As the organic peroxide, it is desirable to use, for example, an organic peroxide, an organic peroxide ester, or the like. Specific examples of such organic peroxides include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne- 3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxide) hexyne-3,2, 5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-s-octoate, t-butyl Mention may be made of perpivalate, cumyl perpivalate, and t-butyl perdiethyl acetate. In the present invention, an azo compound can also be used as the organic peroxide. Specific examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate. Among these, benzoyl peroxide and dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (1,4-bis (t-butylperoxyisopropyl) ) Benzene t-butyl peroxide), di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide) hexyne-3,2,5-dimethyl-2,5-di (t -Butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.

  These organic oxides are used alone or in combination. The proportion of organic peroxide used is generally 0.001 to about 10 parts by weight, preferably about 0.01 to 5 parts by weight, optimally about 0.1 to 2 parts per 100 parts by weight of unmodified HNBR. Within the range of 5 parts by weight. When the proportion of organic peroxide is within this range, the reaction rate of the functional group-containing unsaturated compound and the various properties of the resulting functional group-containing polymer balance each other at a high level. Therefore, it is desirable to use an organic peroxide within such a range.

  The graft modification reaction is not particularly limited, and the reaction can be performed according to a method known in the art. The grafting reaction can generally be carried out at temperatures up to 400 ° C, preferably 60-350 ° C. The reaction time is generally in the range of 1 minute to 24 hours, preferably in the range of 30 minutes to 10 hours. After completion of the reaction, a large amount of solvent such as methanol is added to the reaction system to precipitate the polymer formed, and the polymer is collected by filtration, washed and then dried under reduced pressure.

  (2) Method of using a photoinduced radical generator: The method of using a photoinduced radical generator is a method of generating radicals by applying the mixture obtained after the addition of the photoinduced radical generator to ultraviolet rays, Conventional known methods can be used. The photo-induced radical generator may be any substance as long as it is activated by irradiation with ultraviolet light. Specific examples are benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, 2,2-dimethoxy-2-phenylacetophenone, α-hydroxycyclohexyl phenyl ketone, p-isopropyl. , Α-hydroxyisobutylphenone, α-dichloro-4-phenoxyacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4-bis (dimethylaminophenone) and 1-phenyl-1,2-propanedione Carbonyl compounds such as 2- (o-ethoxycarbonyl) oxime; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobisiso Azo compounds such as tyronitrile and azobis-2,4-dimethylvaleronitrile; peroxide compounds such as benzoyl peroxide and di (t-butyl) peroxide; of 2,4,6-trimethylbenzoylphenylphosphine oxide Such acylphosphine oxides. The proportion of photoinduced radical generator used is generally in the range of 0.001 to about 10 parts by weight, preferably about 0.01 to 5 parts by weight, optimally about 0.1 to 2.5 parts by weight. is there.

  (3) Irradiation method: The irradiation method of energy rays is a publicly known method, and a radical is generated by irradiating active energy rays such as α-ray, β-ray and γ-ray. In particular, it is desirable to use ultraviolet rays from the viewpoints of efficiency, practicality, and profitability.

  [4] Heating method: The radical generation method by heating is performed by heating in a temperature range of 100 to 390 ° C. Both known solution methods and melting and kneading methods are used. Among these, a melting and kneading method using an extruder to which a shear stress is applied during heating is desirable from the viewpoint of reaction efficiency.

  There is no particular limitation on the method for introducing a functional group into the film-forming polymer. Examples include (a) a method by oxidation of an unsaturated bond, (b) the method by addition reaction of a compound containing at least one functional group in the molecule with respect to the unsaturated bond, (c) an epoxy group, a carboxyl group. , The method of introducing hydroxyl groups, or the reaction of NBR or HNBR with olefinic bonds and unsaturated, preferably monounsaturated, carboxylic acid reactants, and addition of end groups to living cation-initiated polymers. The polymer can also be halogenated using chlorine or bromine containing compounds. The halogenated polymer can then be reacted with a monounsaturated carboxylic acid. The polymer and monounsaturated carboxylic reactant can also be contacted at elevated temperatures to produce the thermal “ene” reaction. Monounsaturated carboxylic acids can also be reacted with polymers by free radical induced grafting. The functionalized elastomers of the present invention can be functionalized by contact with a hydroxyaromatic compound in the presence of an effective amount of at least one acidic alkylation catalyst. The alkylated hydroxyaromatic compound is then further reacted to form a derivative by Mannich base condensation with an aldehyde and amine reagent to provide Mannich base condensation. In yet another means of functionalizing the polymer, the polymer is contacted with carbon monoxide in the presence of an acid catalyst under Koch reaction conditions to yield a polymer substituted with carboxylic acid groups. In addition to the above functionalization method, the polymer of the present invention can be functionalized by air oxidation, ozonolysis, hydroformylation, epoxidation and chloroamination, or other methods (for example, JP-A-6-172423). .

Fluoroelastomer film formers Fluorocarbon elastomers (fluoroelastomers) as useful film-forming polymers herein are derived from hydrocarbons including vinylidene fluoride and hexafluoropropylene and are commercially available from a number of suppliers. A detailed discussion of the various types of fluoroelastomers can be found in the magazine “Rubber Chemistry and Technology” (Volume 46, pp. 619-652) published in July 1973. G. Arnold, A.M. L. Barney and D. C. Included in a paper by Thompson. Fluoroelastomers are distinguished from thermoplastic fluoropolymers mainly by whether or not plastic deformation occurs when stressing the fluoroelastomer to give 100% elongation. Fluororesin deforms with 100% elongation and is unsuitable as a coating material for elastic substrates according to the present invention.

  Typical fluoroelastomers used here are 1,1-dihydroperfluorobutyl acrylate; vinylidene fluoride and chlorotrifluoroethylene; vinylidene fluoride and hexafluoropropylene; vinylidene fluoride and hexafluoropropylene; vinylidene fluoride and Hydropentafluoropropylene; copolymers of tetrafluoroethylene and propylene; and vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene; vinylidene fluoride, hexafluoropropylene and propylene; vinylidene fluoride and hydropentafluoropropylene and tetrafluoroethylene Including polymers derived from one or more fluorinated monomers including Optimal fluoroelastomers modified by the present invention are commercially available under the name Viton, such as a copolymer of vinylidene fluoride and hexafluoropropylene, or a terpolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene. it can. Other suitable fluoroelastomers are available from Dyneon under the trade name FLOREL and from Ausimont under the trade name TECHNIFLON.

  The film-forming agent of the graft-functionalized fluoroelastomer embodiment utilized herein comprises at least a bond formation to the fluoroelastomer polymer and one of the graft bonding groups covalently bonded to the fluoroelastomer and the reactive group of the curing agent. A reaction product with a grafting agent containing one active hydrogen-containing group, such as a hydroxyl, thiol, or carboxyl group. The graft modified fluoroelastomer is mixed with the curing agent in the mixture within the pot life of the mixture at the time of applying the elastomeric substrate.

The grafting agent for the fluoroelastomer contains one graft-linking group and one active hydrogen-containing group. Suitable grafting agents contain primary amine groups and one active hydrogen-containing group. Examples are hydroxyamines, amino isocyanates such as (R ₂ ) ₂ NCH ₂ CH ₂ NCO (wherein R ₂ is, for example, hydrogen or a hydrocarbyl group), hydroxyalkylamines, aminocarboxylates, aminosilanes, Including aminosilanol, aminothiol, and the like. Other suitable grafting agents that do not contain primary amines as graft-linking groups are mercaptohydroxys such as mercaptoalcohol and mercaptosilanol, mercaptothiol, and the like. Suitable grafting agents are grafted to the fluoroelastomer at a relatively moderate temperature (<60 ° C.) and can be monomeric, oligomeric or polymeric, with at least one active hydrogen-containing group and no more than one It contains primary amine groups, but can optionally contain secondary or tertiary amine groups or other groups that cannot graft and crosslink fluoroelastomers. Specific examples of grafting agents include various hydroxyalkylamines such as 3-amino-1-propaneol, aminoalkylsilanols such as aminoalkylsilanetriol or alkoxysilane groups that catalyze the hydrolysis of reactive silanetriols. Precursor aminoalkyl-alkoxysilanes containing at least one basic nitrogen that can be formed in each molecule; amine-N-oxides, amino (hydroxy) carboxylic acids, amido (hydroxy) amines, polyoxyalkylene polyether mono (primary Primary) amines and amine-terminated polyols. Such amine-terminated polyols can be prepared by known amination methods in which alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, dodecyl oxide or styrene oxide are polyadded onto amino-starting compounds. In general, polyols such as polyether polyols are aminated with ammonia in the presence of a nickel-containing catalyst, such as a Ni / Cu / Cr catalyst. The known methods are described in U.S. Pat. No. 4,960,942; U.S. Pat. No. 4,973,761; U.S. Pat. No. 5,003,107; U.S. Pat. No. 5,352,835; No. 5,457,147; U.S. Pat. No. 5,457,147. The starting compound used is a compound containing ammonia or an amine group and the reaction product does not contain more than one primary amino group, for example ethylenediamine, ethylenediamine oligomers (for example diethylenetriamine, triethylenetetraamine or pentane). Aliphatic polyamines such as ethylenehexamine), ethanolamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-hexa Methylenediamine, etc. are provided. Suitable polyether blocks for polyether-monoamines include polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, poly (1,2-brylene glycol), and poly (tetremethylene glycol). .

  Preferred amino-hydroxy grafting compounds are those having a molecular weight of about 1000 or less, preferably 500 or less, and optimally 250 or less. More desirable amino-hydroxy grafting agents have 2 to 16 carbon atoms. In the case of a grafting agent having a molecular weight of about 1000 or more, the softness and solvent resistance of the coating are lowered. Examples of further desirable grafting agents include 3-amino-1-propanol, 2- (2-aminoethylamine) ethanol, and aminoalkylsilanols such as aminopropylsilanetriol. The effective amount of graph and agent used relative to the weight of the fluoroelastomer is 1-20% by weight, preferably 2-10% by weight, optimally 3-7% by weight.

  Although less desirable, other exemplary grafting agents that provide hydroxyl-functionalized fluoroelastomers include hydroxyl-functional ethylenically unsaturated compounds via a graft addition reaction. The mercaptohydroxy and mercaptocarboxy compounds are suitable. Hydroxy or carboxy group-containing ethylenically unsaturated monomers are suitable, including but not limited to, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, By techniques known in the art for reactive processing of polymers, including 2-hydroxyethyl vinyl ether, N-methylol (meth) allylamide, methacrylic acid, and maleic anhydride, and widely practiced in thermoplastics such as polyolefins It can be grafted to a fluoroelastomer in the presence of a free radical initiator.

  In another embodiment, the fluorocarbon elastomer is graft-functionalized by an addition reaction with a hydroxy (alkyl) mercaptan, aminothiol, or mercaptocarboxylic acid optionally containing hydroxy groups. Suitable mercaptans that generate bound hydroxyl groups for addition to the fluoroelastomer are mercaptoethanol, hydroxyalkyl mercaptans such as 1-mercapto-3-propanol, mercaptoethanolamine, 1-mercapto-4-butanol, α-mercapto. -Omega-hydroxy oligoethylene oxide, for example alpha-mercapto, omega-hydroxy octaethylene glycol or the corresponding ethylene oxide / propylene oxide copolyether. Mercaptoalkoxy compounds that generate hydroxy groups upon hydrolysis include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyl, to name a few. Contains diethoxysilane. Suitable mercaptocarboxylic acids and corresponding esters are the mercaptoacetic acid and the esters of mercaptoacetic acid, mercaptopropionic acid and esters, mercaptobutyric acid and esters. Esterified compounds containing a hydroxy group are ethylene glycol, propylene glycol, butylene glycolose, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and N-methyldiethanolamine. Including.

  Mercapto compounds, particularly mercapto alcohols, can be grafted to suitable hydrocarbon elastomers in an amount effective for subsequent curing. Mercapto compounds particularly useful for the preparation of functionalized fluoroelastomers can be introduced at moderate or ambient temperatures. The addition of a mercapto compound to graft onto the fluoroelastomer is a free radical initiator in solution at a temperature above the decomposition temperature of the initiator, eg azo initiators such as azobisisobutyronitrile and azobiscyclohexanenitrile Can be optionally carried out in the presence of UV or visible light using peroxides such as dilauryl peroxide, benzpinacol silyl ether, or photoinitiators. Diacyl peroxide, especially dilauroyl peroxide, dibensoyl peroxide are suitable. The effective amount of free radical initiator is 0.510% by weight, based on the weight of mercapto compound. A preferred mercapto compound is a mercapto alcohol such as mercaptoethanol. The effective amount of the starting mercapto compound is 3 to 10% by weight of the fluoroelastomer and is well bound to the fluoroelastomer at a level of 1 to 5% by weight of bound hydroxy groups.

Further desirable fluoroelastomer grafting agents include 2- (2-aminoethylamino) ethanol (NH ₂ —CH ₂ —CH ₂ —NH—CH ₂ —CH ₂ —OH) (CAS # 111-41-1) and, for example, It is grafted onto a fluoroelastomer at room temperature such as aminopropylsilanetriol as supplied by Gelest as SIA0608.0 (CAS # 29159-37-3).

Crosslinkable α-olefin copolymer elastomers Poly (olefin / acrylic ester / carboxylate) copolymer film-forming elastomers include at least one C ₁ -C ₁₈ alkyl (meth) allylate, and polyisocyanates, such as carbodiimides. A comonomer produced by polymerizing at least one α-olefin with a small amount of an unsaturated functional group-containing comonomer accessible to form a crosslink with the material and other agents. The functional group-containing comonomer consists of an ethylenically unsaturated group and a group containing acid, hydroxy, epoxy, isocyanate, amine, oxazoline, diene and other reactive groups. In the absence of such functionalized monomers, crosslinking sites can occur in α-olefin-ester copolymers, for example, by partial hydrolysis of pendant aether groups. Suitable α-olefins for the polymerization of such olefin copolymer film-forming elastomers include ethylene, propylene, butene-1, isobutene, pentene, heptene, octene, and combinations thereof. C ₁ -C ₄ alpha-olefin is preferable, and ethylene is most preferred.

  A functionalized comonomer provides a copolymerized alpha-olefin polymer having active hydrogen, halogen, or a group that can be converted to an active hydrogen-containing group by transamidation or hydrolysis, or vice versa. It contains a crosslinker having a hydrogen group and a reactive group. Alkyl or alkoxy (meth) acrylate acids and esters are exemplary functionalized comonomers. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2- An ethylhexyl group and a decyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neophyll group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexoxy group and octoxy group.
Suitable alkyl or alkoxy (meth) acrylates optionally introducing α-olefins are methyl acrylate, ethyl acrylate, t-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n- Butyl methacrylate, 2-ethyl-hexyl acrylate, methoxy acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, acrylamide, methacrylamide, and the like or mixtures thereof. Examples of functional ethylenically unsaturated monomers copolymerizable with α-olefin monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid and their salts, methyl acrylate and An alkyl ester of an unsaturated carboxylic acid such as butyl acrylate.

Suitable α-olefin-acrylic ester copolymer rubbers are, for example, unsaturated carboxylic acid monomer units such as acid units derived from (meth) acrylic acid or maleic acid, or derived from monoethyl maleate. Consists of anhydride units derived from maleic anhydride or partial ester units. Polymers in a preferred embodiment, terpolymers of _ethylene, C 1 -C ₄ alkyl acrylate and a carboxylic acid are units; further desirable according terpolymer of at least about 30 mole percent ethylene, about 10 to 69.5 mol% Of monoethyl maleate. In all cases, it is desirable that the α-olefin-acrylate rubber be essentially amorphous and have a glass transition temperature (Tg) of room temperature or less, ie, about 20 ° C. or less.

  Other comonomers containing reactive groups for adding functional acids, hydroxy, epoxies, isocyanates, amines, oxazolines, dienes or other reactive functional groups are alkyl diene bornbornene, alkenyl norbornene, dicyclopentadiene, Diene monomers such as methylcyclopentadiene and non-conjugated dienes such as dimers thereof, and conjugated dienes such as butadiene and isoprene are included. Examples of dihydrodicyclopentadienyl group-containing (meth) acrylates include dihydrodicyclopentadienyl (meth) acrylate and dihydrodicyclopentadienyloxyethyl (meth) acrylate.

  Further examples of functional comonomers include N-alkylols and alkoxy amides of α, β-olefin unsaturated carboxylic acids having 4 to 10 carbon atoms, such as N-methylol acrylamide, N-ethanol acrylamide, N-propanol acrylamide. N-methanol methacrylate, N-ethanol methacrylate, n-butoxyacrylamide and isobutoxyacrylamide, N-methylol maleimide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol-p-vinylbenzamide N-alkylolamides of vinyl aromatic acids and the like.

  Other examples of functional comonomers that are reactive with active hydrogen or have groups that themselves contain active hydrogen groups are epoxy group-containing ethylenically unsaturated compounds including allyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate. Examples of active halogen-containing ethylenically unsaturated compounds are vinyl benzyl chloride, vinyl benzyl bromide, 2-chloroethyl vinyl ether, vinyl chloroacetate, vinyl chloropropionate, allyl chloroacetate, allyl chloropropionate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, chloromethyl vinyl ketone, and 2-chloroacetoxymethyl-5-norbornene. Specific examples of common carboxy group-containing ethylenically unsaturated compounds include acrylic acid, methacrylic acid, crotonic acid, 2-pentenonic acid, maleic acid, fumaric acid and itaconic acid.

  Examples of other ethylenically unsaturated (meth) acrylic ester comonomers are: octyl methacrylate; shano-substituted alkyl (meth) acrylates such as 2-shanoethyl acrylate, 3-shanoethyl acrylate, and 4-shanobutyl acrylate; diethylaminoethyl Amino-substituted alkyl (meth) acrylates such as acrylates; fluorine-containing acrylates such as 1,1,1-trifluoroethyl acrylate; hydroxyl group-substituted alkyl (meth) acrylates such as hydroxyethyl acrylate; Alkyl vinyl ketones; vinyl or alkyl ethers such as vinyl ethyl ether and allyl methyl ether; vinyl aromas such as styrene, α-methyl styrene, chlorostyrene and vinyl toluene Compounds, ethylene, propylene, vinyl chloride, include vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, alkyl fumarate, and the like.

  The functionalized acrylate elastomer preferably has a glass transition temperature of −10 ° C. or less, and the main amount of one or more copolymerizable α, β-ethylenically unsaturated ester monomers having the following general structure (total polymer) Defined as an addition polymer derived from 50% by weight or more):

R ₁ in the formula is hydrogen or methyl; CR ₂ is C ₁ -C ₂₀ alkyl, C ₂ -C alkyl, C ₂ -C ₇ alkoxyalkyl, C ₂ -C ₇ alkylthioalkyl,
It represents a C ₂ -C ₇ cyanoalkyl, and is defined as addition polymers derived from a small amount of active hydrogen-containing comonomer or active content based grafting functional site. The acrylate is available from various commercial sources in solid veil and as an emulsion or latex. A small amount of cure or _Tg raising comonomer up to about 35% based on the total acrylate rubber weight can be included, such as methyl methacrylate, acrylonitrile, vinyl acetate, vinylidene chloride, and / or styrene. Functional group-containing comonomers having groups reactive with active hydrogen or active hydrogen-containing curing agents are unsaturated monocarboxylic acids (eg acrylic or methacrylic acid) or polycarboxylic acids (eg itaconic acid, citraconic acid, etc.) or Polycarboxylic anhydride is preferred.

Specific examples of suitable acrylic or methacrylic monomers alone or in combination include methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, ethyl hexyl acrylate, and the like. Suitable copolymers each have the formula 5 and R ₁ is hydrogen; R ₂ is C ₄ -C ₈ alkyl, or C ₂ -C ₈ alkoxyalkyl, both of which are primary, Consists of one or more different copolymerizable monomers having secondary or tertiary C atoms. Examples of more suitable C ₄ -C ₈ alkyl acrylates are n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate There; suitable C ₂ -C ₈ alkoxyalkyl acrylates are methoxy acrylate, and be ethoxyethyl acrylate; preferred alkylthioalkyl acrylate is methyl thio ethyl acrylate; preferred C ₂ -C ₇ cyanoalkyl acrylates, cyanoethyl Acrylate and cyanopropyl acrylate; mixtures of two or more of the foregoing are used.

  Desirable active hydrogen-containing comonomers for acrylic elastomers include many of the above functional comonomers containing active hydrogen, some of which repeat here are carboxylic anhydrides, carbonamides, N-substituted carboxamides, aldehydes, alkyl and aryl keto, Including hydroxyl radical, allyl chlorine radical, methylol, maleimide, bismaleimide, alkyl N-methylol, phenol methylol, triol radical, amino radical, isocyanate radical, alkoxyalkyl radical, oxirane radical, and the like. Preferred are α, β-unsaturated hydroxycarboxylic acid or dicarboxylic acid anhydrides. If the polymer is only a copolymer of acrylate ester and carboxylic acid or an anhydride comonomer, they are about 90-98 mol% repeat units, more preferably about 92-97 or 98 mol% ester from the acrylate ester. And 2-10% carboxylic acid or anhydride, more preferably 3-8% carboxylic acid or anhydride.

  Examples of functional comonomers randomly introduced during the addition polymerization of the film-forming polymer are glycidyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, N-alkylmaleimide, acrylamide, N-isobutoxymethylacrylamide, N -N-alkoxyalkylacrylamides such as hydroxymethylacrylamide, etc., methyl vinyl ketone, acrolein, vinyl isocyanate, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like. Also included are mixtures of two or more of such functional monomers.

Acrylic elastomers include so-called core-shell polymers. Soft shell copolymer useful rubbery copolymer is at least one acrylic monomer of -10 ° C. or less T _g of the homopolymer and the second copolymerizable, copolymerization composition of the functional monomer Including things. These monomers, in a proportion of the low T _g acrylic comonomer selected so as not to raise the T _g of the resulting acrylic copolymer to about -10 ° C. or higher, for example, styrene, acrylonitrile, methyl methacrylate, etc. Polymerization can be carried out in the presence of a small proportion of such monovinyl or vinylidene monomers.

  Although the shell copolymer is an addition polymer and can be varied over a wide composition range, for most purposes the copolymer comprises about 99.9-95% by weight of at least one rubbery monomer and About 0.1 to 5% by weight of the second copolymerizable functional monomer. A preferred shell copolymer is a copolymer of alkyl acrylate and 2-hydroxyethyl methacrylate.

  The elastic coatings of the present invention based on sequential polymerization functionalized addition polymers exhibit two glass transition temperatures, one of which is 0 ° C. or lower and one of which is 0 ° C. or higher. The amount of rubbery shell copolymer component and the ratio of hard component to rubbery component can vary, but for most purposes the ratio of hard copolymer component: rubbery shell copolymer component is 1 or less. The amount of the rubbery component is 50% by weight or more, preferably 60 to 80% by weight.

  Double (halo, carboxy) functionalized acrylic addition polymers are also useful as film formers in organic solvent-containing embodiments of the present invention, from repeating units from acrylic ester monomers or monomer mixtures. They exhibit a glass transition temperature in the elastomer of -20 ° C or lower. The functional group is provided from a combination of about 0.1% to 30% by weight, preferably 0.2 to about 15% by weight of an active halogen-containing comonomer and 0.1% to 20% by weight of a carboxyl group-containing comonomer. Is done. At a preferred level of halogen-containing comonomer, the halogen content is about 0.1% to 5% by weight of the functionalized acrylic rubber. The halogen group of the halogen-containing comonomer can be chlorine, bromine, or iodine. Chlorine-containing comonomers are desirable from an economic, availability and safety perspective.

  Examples of chlorine-containing comonomers are vinyl chloroacetate, vinyl bromoacetate, allyl chloroacetate, vinyl chloropropionate, vinyl chlorobutyrate, vinyl bromobutyrate, 2-chloroethyl acrylate, 3-chloropropyl acrylate, 4-chloro Butyl acrylate, 2-chloroethyl methacrylate, 2-bromoethyl acrylate, 2-iodoethyl acrylate, 2-chloroethyl vinyl ether, chloromethyl vinyl ketone, 4-chloro-2-butenyl acrylate, vinyl benzyl chloride, 5-chloromethyl 2-norbornene, 5-α- (chloroacetoxymethyl) -2-norbornene, 5- (α, β-dichloropropionmethyl) -2-norbornene, and the like. Suitable monomers include vinyl chloroacetate, allyl chloroacetate, 2-chloroethyl acrylate, 2-chloroethyl vinyl ether, vinyl benzyl chloride, 5-chloromethyl-2-norbornene, and 5-chloroacetoxymethyl-2-norbornene It is.

  Suitable active hydrogen-containing comonomers for acrylic rubber are from about 0.1 to 20%, preferably 0.2 to about 10%, optimally 2 to about 6% by weight of at least one carboxyl group-containing comonomer. Exists. The carboxyl comonomer is preferably a monocarboxylic acid, but can also be a polycarboxylic acid. Suitable carboxylic comonomers contain from 3 to about 8 carbon atoms. Examples of such suitable comonomers are acrylic acid, methacrylic acid, ethacrylic acid, β, β-dimethylacrylic acid, crotonic acid, 2-pentenonic acid, 2-hexenonic acid, maleic acid, fumaric acid, sitaconic acid, mesaconic acid, Itaconic acid, 3-butene 1,2,3-tricarboxylic acid, and the like. The optimal carboxyl comonomer is a monocarboxylic acid monomer such as acrylic acid, methacrylic acid, itaconic acid, and the like.

  The functional group-containing comonomer is incorporated such that it is most conveniently introduced during the addition polymerization of the acrylate elastomer. Polymerization by suspension, emulsion, solution, and bulk methods is suitable. These polymerizations are initiated using free radical initiators. The emulsion polymerization method is desirable. Various conventional soaps, emulsifiers and surfactants known in the art and literature can be utilized for the synthesis of emulsion polymerization functional acrylate rubbers. The weight average molecular weight of the dual functionalized acrylate elastomer is generally 100,000 or more. Commercial grade functionalized allyl rubber is available from Zeon Chemical under the trade name HYTEMP.

Α, β-unsaturated C ₂ -C ₈ alkyl ester copolymer latexes containing active hydrogen functional groups are known and are available from various commercial sources. Suitable acrylic rubbery latices are available from Noveon under the trade name HTCAR and from Rohm and Haas under the trade name Rhoplex ex. It indicates 20 ° C. below T _g, a n- butyl acrylate, acrylonitrile, suitable acrylic film formers in emulsion polymerization copolymer of N- methylol acrylamide and itaconic acid is used in embodiments of the aqueous coating.

The crosslinkable α-olefin copolymer poly (olefin / acrylic ester / carboxylate) is a thermoplastic in an uncured state and is flexible (elastic) suitable for use herein. They are primarily accessible to form crosslinks with at least one α-olefin with at least one C ₁ -C ₁₈ alkyl (meth) acrylate and materials such as polyisocyanates, carbodiimides and other curing agents. It is a copolymer produced by polymerizing with a small amount of an unsaturated protonic functional group-containing comonomer. The functional group-containing comonomer consists of an ethylenically unsaturated group and a group having an acid, hydroxy, epoxy, isocyanate, amine, oxazoline, diene or other reactive group. In the absence of such functionalized monomers, cross-linking sites can be generated in the α-olefin ester copolymer, for example, by partial hydrolysis of the pendant ester group. Suitable α-olefins for the polymerization of such olefin copolymer film-forming elastomers include ethylene, propylene, butene-1, isobutylene, pentene, heptene, octene, and combinations thereof. C ₂ -C ₄ alpha-olefin is preferable, and ethylene is most preferred.

  Other examples of functional comonomers having active hydrogen groups are epoxy group-containing ethylenically unsaturated compounds including alkyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate. Specific examples of the active halogen-containing ethylenically unsaturated compound include vinyl benzyl chloride, vinyl benzyl bromide, 2-chloroethyl vinyl ether, vinyl chloroacetate, vinyl chloropropionate, allyl chloroacetate, allyl chloropropionate, 2- Including chloroethyl acrylate, 2-chloroethyl methacrylate, chloromethyl vinyl ketone and 2-chloroacetoxymethyl-5-norbornene. Specific examples of the carboxyl group-containing ethylenically unsaturated compound include acrylic acid, methacrylic acid, crotonic acid, 2-pentenonic acid, maleic acid, fumaric acid, and itaconic acid.

  Examples of ethylenically unsaturated (meth) acrylic ester comonomers are: octyl methacrylate; cyano-substituted alkyl (meth) acrylates such as 2-cyanoethyl acrylate, 3-cyanopropyl acrylate, and 4-cyanobutyl acrylate; Amino-substituted alkyl (meth) acrylates; fluorine-containing acrylates such as 1,1,1-trifluoroethyl acrylate; hydroxyl group-substituted alkyl (meth) acrylates such as hydroxyethyl acrylate; alkyls such as methyl vinyl ketone Vinyl ketones; vinyls or allyl ethers such as vinyl ethyl ether and allyl methyl ether; vinyls such as styrene, α-methyl styrene, chlorostyrene and vinyl toluene Aromatic compounds; vinyl amides such as acrylamide, methacrylamide and N-methylol acrylamide; and ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, alkyl fumarate, and the like.

Suitable olefin / acrylic ester copolymer rubbers are, for example, acid units derived from (meth) acrylic acid or maleic acid, eg, anhydride units derived from partial ester units derived from maleic anhydride or monoethyl maleate. Consists of. In a preferred embodiment, the polymer is a terpolymer of ethylene, C ₁ -C ₄ alkyl acrylate and carboxylic acid monomer units; preferably such terpolymer is at least about 30 mole percent ethylene, about 10-69.5. Consists of mol% monoethyl maleate. In all cases, it is desirable that the α-olefin acrylate rubber be essentially amorphous and have a glass transition temperature (Tg) of about 20 ° C. or less. Ethylene-carboxylate copolymers are commercially available under the trade name VAMAC.

  When acrylic acid and acrylate are part of the backbone of the α-olefin copolymer, the transamidation reaction produces pendant hydroxyl functionality by using an amino alcohol such as 2-amino-1-ethanol. This is done with melt processing techniques known to do. Further reaction with the pendant hydroxyl occurs, ie, another acrylate linkage and transesterification leads to cross-linking, increasing the viscosity of the product.

  A castable film forming agent made of curable urethane can be used as a film forming agent component. The active hydrogen functionalized polymer is a saturated prepolymer and is cured with an aliphatic polyisocyanate. The cured glass transition temperature of the polyurethane is limited to below 0 ° C. and is lightly crosslinked by triol, tetraol or high OH functionality. Thus, chain-extended polyols can be those such as hydroxy-terminated hydrogenated polybutadiene polyol homopolymers and copolymers exhibiting glass transition temperatures below 0 ° C., polyTHF, polyester diols, polypropylene glycols, etc. Limited. Conventional curing agents and catalysts are used. U.S. Pat. No. 4,669,517 discloses a suitable method for applying radiant polyurethane to the surface of a vulcanized rubber after it has been prepared to obtain excellent adhesion of the polyurethane. The method of preparing the post-cured surface can be applied to the application of castable polyurethane radiant paint. Shanulic acid is applied to the rubber surface containing the introduced polybutadiene polyol prior to application of the polyurethane reaction mixture containing thermally conductive metal particles. The polyurethane reaction mixture cures at ambient temperature.

Acrylurethane Urethane modified acrylic materials are also contemplated that meet the film forming agent requirements set forth herein. These are suitable to be cured and activated by moisture, heat or light. Such a urethane-modified acrylate has a glass transition temperature of 0 ° C. or less and must consist of a major amount of C ₂ -C ₈ acrylic or methacrylic ester. Examples of suitable urethane modified acryl resins that can be used in the present invention include 10 to 60 moles of methyl-, ethyl-, or butyl-acrylate in the case of a urethane-modified acrylic resin represented by Formula 5. It is an acrylic copolymer produced by copolymerizing with ˜50 moles of methacrylic acid and 30-80 moles of 2-hydroxymethyl methacrylate. Some or all of the hydroxyl and carboxyl groups are capped in the reaction with α, β-ethylenically unsaturated isocyanates such as methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate). This material is moisture curable and UV curable with the introduction of conventional photoinitiators. In the moisture curable acrylurethane embodiment, it is desirable that at least 10 mole%, preferably at least 50 mole% of hydroxyl groups from 2-hydroxyethyl methacrylate units are reacted with methacryloyloxyethyl isocyanate. . The α, β-ethylenically unsaturated isocyanate is a reaction product of an isocyanate and a hydroxyl-containing monomer, such as N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate are optionally 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane Or 3-aminopropylmethyldiethoxysilane, primary and secondary amines such as N- (2-aminoethyl) -3-aminenopropyltrimethoxysilane, N-methyl- or N-pheny 3-secondary amine, such as aminopropyltriethoxysilane, bis (3-aminopropyl) tetramethoxy or tetraethoxy disiloxane _{NH 2 (CH2) 3 --Si (} OCH 3) 2 --O - ( CH ₃ O) ₂ Si— (CH ₂ ) ₃ NH _2, a polyglycol modified aminosilane as sold under the trademark “Dynasylan TRIAMO” and It can be used with triamino functional propyltrimethoxysilanes such as the trade name “Dynasyan TRIAMO” available from Huls AG. Similar silanes having 2 or 3 silicon atoms can also be used.

Maleate Elastomer Materials Based on polyethylene such as maleate styrene-ethylene-butene-styrene-block copolymer, maleate styrene-butadiene-styrene-block copolymer, maleate ethylene-propylene rubber, and mixtures thereof Various mixtures, alloys and dynamically vulcanized composites of the maleate addition polymers made can be utilized as functionalized film-forming elastomers in accordance with the present invention. The maleate elastomer is dissolved in a suitable organic solvent system and mixed with thermally conductive metal particles that are desirably predispersed in a portion of the solvent used.

Ethylene vinyl ester copolymer film forming, solvent soluble, OH-functional ethylene copolymer, available in various grades containing carboxyl or hydroxyl functional groups, and also suitable as a film forming agent for use herein is there. Usually, some of these polymers are used as crosslinkable hot melt adhesives, but these polymers have a relatively low cohesiveness at high temperatures but are easily adapted for ambient temperature curing radiant coatings here it can. Ethylene vinyl ester polymers containing hydroxyl functionality are suitable for use in radiant paint compositions, cure with unblocked isocyanate, and provide sufficient properties at ambient temperatures that do not exceed the temperature at which the cured paint does not flow . The ethylene vinyl acetate copolymer containing OH groups is based on a polymer having monomeric units of ethylene, vinyl alcohol, and optionally vinyl acetate, and the melt has a viscosity of 4-40 Pa.s at 180 ° C. s is desirable. The ethylene vinyl alcohol copolymer desirably has at least 5% by weight vinyl alcohol units. An example is a terpolymer with 10% vinyl alcohol, 88.75% ethylene and 1.2 wt% vinyl acetate (viscosity at 180 ° C. is 20 Pa.s, 6.4 gm / 10 min at 325 g load at 125 ° C. MFR, melting point 101.5 ° C. (DSC) Another terpolymer contains 13.7 wt% vinyl alcohol, 82.3% ethylene and 4.0 wt% vinyl acetate (at 180 ° C. Of MFR at 5.8 Pa.s, 6.4 gm / 10 min at 325 g load at 125 ° C. (comparative 30.4 gm / 10 min, DSC melting point 91 ° C.)

  Suitable for use herein are partially functionalized polymers, and mixed or osmotic network film formers containing partially non-functionalized polymers. Irregular or block copolymers such as SBS, EBS, EPM and EPDM, halogenated polydiene copolymers, acrylic rubber, and other olefin rubber polymers as film formers can be blended with functionalized polymers. is there. By way of example, the non-functionalized polymer film former can be blended with the partially hydrolyzed ethylene vinyl acetate in a ratio of 10 to 90% by weight: 90 to 10% by weight, respectively, and suitable curing agents disclosed herein. Harden.

Functionalized EPM and EPDM Elastomers Functionalized EPM and EPDM elastomers are suitable film-forming elastomers for use as film-forming agents in radiant paints. These consist of two or more α-monoolefins copolymerized with polyenes, generally non-conjugated diene comonomers. Useful polyenes include: 5-ethylidene-2-norbornene; 1,4-hexadiene; 5-methylene-2-norbornene; 1,6-octadiene; 5-methyl-1,4-hexadiene; 3,7-dimethyl-1, 1,3-cyclopentadiene; 1,4-cyclopentadiene; dicyclopentadiene; 5-vinyl-2-norbornene, etc .; or combinations thereof. Suitable polyenes for functionalized EPM and EPDM elastomers are 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 1,4-hexadiene. Functional groups can be introduced by the conventional means and the metathesis means disclosed herein.

In one aspect of the method disclosed in the present invention, organic acid functionality such as carboxyl functionality, aliphatic or aromatic hydroxyl functionality, etc., and organic acids such as sulfonic acid functionality, phosphoric acid functionality, etc. A particularly useful mode is provided for the production of polymers containing functionality.
One such scheme is described below for EPM and EPDM rubbers to introduce pendant carboxyl, hydroxyl or non-sterically hindered olefin functionality.

式中のｎは、市販のＥＰＤＭの反復エチレン単位の常用数を表し、ｍは反復プロピレン単位の常用数を表し、ｏはジエン単量体反復単位の常用数を表し、及びｐは１〜１００の範囲のマレエートジシクロペンタジエンの反復単位を表わす。
ＥＰＤＭを改質するために上記と同じ方法が、ブタジエン−アクリロニトリル共重合体のような共役ジエン重合体に官能基を導入するために利用できる。

N in the formula represents a common number of repeating ethylene units of commercially available EPDM, m represents a common number of repeating propylene units, o represents a common number of repeating diene monomer units, and p represents 1 to 100. Represents maleate dicyclopentadiene repeating units in the range
The same method as described above for modifying EPDM can be used to introduce functional groups into conjugated diene polymers such as butadiene-acrylonitrile copolymers.

(B) Curing agent component Ambient temperature curing agent includes (1) at least one group having active hydrogen and the same active hydrogen group or a different crosslinking group, or (2) at least reactive with the active hydrogen group. A multifunctional curing component containing one group and a bridging group that is active hydrogen or a group reactive with a different bridging group. In the case of castable polyurethanes or urethane acrylates (acrylo-urethanes), the cure interaction is optionally a polyol with a heterocured polyamine and an ethylenically unsaturated polyisocyanate or polyisocyanate prepolymer and / or an acrylated moiety. Between the group. Its curing components are polyisocyanates, chain-extended polyisocyanates, polymeric isocyanate-polyol adducts, polycarbodiimides, polyfunctional oxazolines, polyfunctional oxazines, polyfunctional imidazolines, phenol novolacs, phenol resoles, amino Selected from resins and amino (alkoxy) silanes. Suitable curing components contain at least one isocyanate group, or a group having an isocyanate group, or a functional group reactive crosslinking group, or a combination thereof. The curing component is generally about 3-30 parts by weight per 100 parts by weight of functionalized addition polymer, desirably about 5-25 parts by weight, preferably about 10-20 parts by weight, or in the case of castable polyurethanes. Used in calculated amounts based on the equivalents of the polyol component.

  Suitable curing components include monomeric polyisocyanates such as aliphatic or aromatic diisocyanates having 2 to 40 carbon atoms. Examples of polyisocyanates are ethylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, ethylidene diisocyanate, cyclopentylene-1,3-diisocyanate. 1,2-1,3- and 1,4-cyclohexylene-1,3-diisocyanate, 1,3- and 1,4-phenylene diisocyanate, diphenylmethane diisocyanate, polymethylene isocyanate, 2 1,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylene diisocyanate, bis (4-isocyanatoethyl) carbonate, 1,8-diisocyanate-p-methane, 1-methyl -2,4-diisocyanate cyclohexane, chlorophenylene diisocyanate, naphthalene-1,5-di Sodium triphenylmethane-4,4 ′, triisocyanate, isopropylbenzene-α-4-diisocyanate, 5,6-bicyclo [2.2.1] hept-2-ene diisocyanate, 5,6- Diisocyanate butyl bicyclo [2.2.1] hept-2-ene. Examples of commercial products are trimethylhexamethylene diisocyanate available from VEBA, heptadecyl (C17) diisocyanate, DDI 1410 aliphatic C-36 diisocyanate available from Henkel, and Isonate 143L available from Upjohn. Diisocyanate, modified diphenylmethane diisocyanate (MDI). Further, the urethane component is isophorone diisocyanate available from VEBA and Desmodur N aliphatic triisocyanate available from Moay. Desmodur N is further defined as a reactive organism of water with 3 moles of hexamethylene diisocyanate and an isocyanate equivalent weight later defined as 191. Other adducts or polyisocyanate prepolymers include Desmodur Mondur CB, an adduct of toluene diisocyanate (TDI).

  Examples of alicyclic polyisocyanates are 1,3-cyclopentene diisocyanate, 1,4-cyclohaesane diisocyanate, 1,3-cyclohaesane diisocyanate, 1-isocyanate-3,3,5- Trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate As well as 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane) and polyisocyanates (eg, 1,3,5-triisocyanatocyclohexane). High molecular isocyanates are more desirable and widely available. The term “liquid” is defined as a liquid at ambient or elevated temperature or as a solution of polyisocyanate in a solvent for polyisocyanates. It contains 10-50% reactive NCO groups and is liquid at ambient temperature. Or polyisocyanates that are liquefied up to about 70 ° C. or that are soluble in a carrier or diluent are suitable for use in the present invention Many types of liquid isocyanates are described, for example, in US Pat. No. 3,883,571; U.S. Pat. No. 4,229,347; No. 4,055,548; No. 4,102,833; No. 4,332,742; No. 4,448,904 No .; and 4,490,301.

  Useful liquid polyisocyanates are prepared via reaction with various hydroxyl functional materials. These reactions are catalyzed using organometallics or tertiary amines. Useful hydroxy compounds are aliphatic alcohols containing about 1 to 36, preferably 4 to 16 carbon atoms. Non-limiting examples of aliphatic alcohols are alicyclic alcohols, aliphatic alcohols containing aromatic groups, groups that do not react with isocyanates, such as aliphatic alcohols containing ether groups and halogens such as bromine and chlorine. is there. Non-limiting specific examples of aliphatic alcohols are 2-methyl-1-propanol, cetyl alcohol, cyclohexanol, 2-methoxyethanol, and 2-bromoethanol. Branched aliphatic alcohols with molecular weights up to 150 are optimal.

  Examples of liquid adducts of isocyanate compounds include solid 4,4′- and / or 2,4′-diphenylmethane diisocyanate and branched aliphatic dihydroxy compounds, dihydroxy compound 0. 2 per mole of diisocyanate. The reaction product is included in a molar ratio of 1 to 0.3 mol. Another example of a compound based on liquid MDI is the reaction product of a mixture of monoalcohol, poly-1,2-propylene ether glycol and triol with MDI. Another example of a liquid polyisocyanate is an alcohol or thiol having an average functionality of about 1.5 to 4 and an average equivalent weight of at least about 500, and at least 2 equivalents of organic polyisocyanate per hydroxyl and / or thiol equivalent. About 20% of the initial urethane or thiourethane groups are converted to allophanate and / or thioalphanate groups.

  Blocked isocyanates are suitable for carrying out the production of paints when a heating process is used to cure the paint. Suitable blocking agents for reaction with organic mono- or polyisocyanates are isocyanate-reactive compounds such as phenols, lactams, oximes, imides, alcohols, pyrazoles, and the like. The reaction between the organic polyisocyanate and the blocking agent can be carried out by a method known in the art. The reaction can be carried out in a bulk or inert solvent, for example at a temperature of 50-120 ° C. The equivalent ratio of isocyanate-reactive group: isocyanate group to fully blocked isocyanate can be used at 1/1 to 2/1 or more. Although it is desirable to use a fully blocked isocyanate, the ratio can be adjusted if only a partially blocked polyisocyanate is required.

  Water-based paints containing functionalized elastomers and dispersed cross-linking agents are used immediately after preparation. In embodiments of aqueous paints using polyisocyanate curing agents, such as by use of aqueous dispersed polyisocyanates, these materials are known and disclosed in, for example, US Pat. No. 5,202,377. ing. An example of an emulsifiable polyisocyanate taught in the patent consists of a hydrophilic tertiary isocyanate functional oligomer that is rendered hydrophilic by partial reaction with a hydrophilic polyether. Other water dispersible isocyanates suitable for aqueous embodiments according to the present invention are known. U.S. Pat. No. 5,202,377 teaches an emulsifiable polyisocyanate mixture consisting of (a) a hydrophilic isocyanate-functional oligomer and (b) a polyisocyanate. Non-limiting examples are reactive organisms of aliphatic polyisocyanates and mono- or polyvalent, nonionic polyalkylene ether alcohols having at least one polyether chain containing at least 10 ethylene oxide units. Preferred water dispersible isocyanates are based on aliphatic and cycloaliphatic isocyanates.

  The coating composition is a mixture of (i) a water dispersible crosslinker such as carboimide or polyisocyanate and (ii) another aqueous solution, emulsion or dispersion of a functionalized elastomeric polymer containing reactive functionality. Can be generated. The aqueous composition containing the functionalized elastomer can also be mixed with another aqueous dispersion containing a crosslinker as taught in US Pat. No. 5,466,745 to the diisocyanate example. The paint can be prepared by mixing an elastomer in an aqueous medium with a non-aqueous emulsifiable composition comprising a non-blocked polyisocyanate crosslinker and a surface active isocyanate-reactive material. This embodiment introduces some volatile organic components when selecting a solvent known as VOC, but there are other solvent diluents that can be used. Known procedures are (i) mixing a non-blocked hydrophobic isocyanate and diluent with a mixture of surface active isocyanate-reactive material and water to produce a water-in-oil emulsion, then (ii) This emulsion is subsequently added to an aqueous medium containing an elastomer at a rate and conditions that convert the isocyanate emulsion to an oil-in-water emulsion.

  Specific examples of commercial diisocyanates include 1,6-hexane diisocyanate (isophorone diisocyanate (eg, commercially available from Huls under the trade name IPDI), tetramethylene diisocyanate (eg, Cytec). Commercially available under the trade name TMXDI), 2-methyl-1,5-pentanediisocyanate, 2,2,4-trimethyl-1,6-hexanediisocyanate, 1,12-dodecanedi Isocyanates and methylene bis (4-cyclohexyl isocyanate) (eg, commercially available from Bayer under the trade name Desmodur W), and high functionality isocyanates, such as biurets of 1,6-hexane diisocyanate (eg, , Commercially available from Bayer under the trade name Desmodur N) 1,6-hexa Isoisocyanurate of diisocyanate (eg commercially available from Bayer under the trade name Desmodur N-3390), isochanurone of isophorone diisocyanate (eg commercial under the trade name Desmodur Z-4370 from Bayer) Reaction product of tetramethylxylene diisocyanate and trimethylolpropane (commercially available from Cytec under the trade name Cythane 3160), and 1 mole of trimethylolpropane and 3 moles of toluene. The reaction product with disiocyanate (for example, commercially available from Bayer under the trade name Desmodur L.) The amount of di- or polyisocyanate included should be 3 to 30 phr. Is preferably 8 to 15 phr.

  Another class of crosslinking components that can be used to cure functionalized film formers and form siloxane crosslinks are various known organosilanes. Bonded to silicon via suitable organosilanes, isocyanate groups and groups capable of forming crosslinks with silanes and / or film formers, such as hydrolyzable groups, hydrazyl, thio, halogen, hydroxy, alkoxy, and carbon atoms Isocyanates containing other co-reactive substituents on the selected groups, such as acyloxy, mercapto, amino, phenol, and one or more groups capable of forming crosslinks with glycids. Silane contains a vinyl group; a vinyl group-containing group; another isocyanate group; another isocyanate group-containing group; a ureido group; a ureido group-containing group; an imidazole group; or an imidazole group-containing group. Such compounds are known in the art.

  The reactive silane curing agent used herein provides an ambient curable, radiant coating in an amount of 25 to 150 parts by weight silane curing agent per 100 parts by weight of the film forming agent, the film forming agent being a curing agent 10% by weight or less of functional groups that are cured with The silane curing agent is a monomer, tetravalent silane or bis, or oligo containing at least two silicon-bonded groups of the same or different co-reactive groups depending on the selected functional group on the film-forming polymer. -It can be a derivative. One such curable group is a group that interacts with a hydrolyzable group or an acidic or basic functional group on the film-forming polymer. The silicon-bonded group is an active hydrogen group that is co-reactive with a functional group on the film-forming polymer, or the silicon-bonded group is co-reactive with an active hydrogen-containing group on the film-forming polymer. These organosilane compounds are known and are available from a number of commercial sources.

  Exemplary suitable hydroxyalkyl group-containing silanes have the following general structure:

R in the formula is a divalent aliphatic, alicyclic or aromatic radical having 1-20, preferably 1-9, optimally 2-4 carbon atoms; R ¹ is a monovalent aliphatic, alicyclic or aromatic radical having 1 to 20 carbon atoms, and an alkyl radical having 1 to 4 carbon atoms, a cycloalkyl radical having 4 to 7 carbon atoms , aryl radicals of the number ring carbon atoms 10 or 14, and optionally carbon atoms is preferably selected from the group consisting of one or more of the substituted alkyl group of 1 to 4; R ² is the number of carbon atoms 1 to 8 monovalent aliphatic, alicyclic or aromatic radicals, methyl, ethyl, propyl and butyl, and the group R ³ —O—R ⁴ (R ³ is an alkylene having 1 to 4 carbon atoms) The group (methyl, ethyl, propyl and butyl) -C = (O) -R, And R ⁴ is an alkyl group having 1 to 4 carbon atoms); and a is 0 or 1, with 0 being preferred.

Amino-functional silanes are desirable for curing carboxy-functional film formers and have the following structure (B):

R, R ¹ , R ² and a in the formula are as defined for the formula (A); R ⁵ is hydrogen, a monovalent aliphatic radical having 1 to 8 carbon atoms, the number of carbon atoms in the ring 4-7 monovalent alicyclic radicals, phenyl containing one or more substituted alkyl groups having 6 carbon atoms and 1 to 4 carbon atoms, alkaryl radicals, and groups R ⁷ —NH—R ⁶ (wherein R ⁶ is selected from the group consisting of divalent aliphatic, alicyclic, and aromatic radicals having 1 to 20 carbon atoms, and at least two carbons separating a nitrogen atom pair) Preferably there are atoms, R ⁶ is preferably an alkylene group having 2 to 9 carbon atoms; R ⁷ is identical to R ⁵ and is preferably hydrogen.

  Mercaptofunctional silanes include those having the following structure (C):

R, R ¹ , R ² and a in the formula are as defined for the formula (A).

  Organosilane compounds useful herein are preferably bonded to a functional group separated from the silicon atom by an organic chain having 1 to 20 carbon atoms as a substituent on the Si atom and a chain of at least 3 consecutive carbon atoms. Includes those containing at least one extractable hydrogen atom.

  The preferred organosilane is isocyanate silane. Examples of suitable commercially available isocyanate to alkoxysilanes here are γ-isocyanatopropyltrimethoxysilane available under the trade name Silquest Y-5187 from OSi Specialties Group, Witco (OSi), and trade name from OSi. Γ-isocyanatopropyltriethoxysilane available as Silquest A-1310.

  Representative names and names of organosilanes containing active hydrogen groups are hydroxypropyltrimethoxysilane, hydroxypropyltriethoxysilane, hydroxybutyltrimethoxysilane, methylaminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminoisobutyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxy Silane, dodecyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyltrimethoxysilane, and the like.

  Hydroxysilanes having (Si—OH bonds) are also suitable as curing agents, optionally as partially neutralized silane diols or silane triols. The term “partial neutralization” here means that at least some of the silanol groups are in the form of mono-, di-, tribasic alkali metal salts, more particularly lithium, sodium or potassium salts. The degree of neutralization suppresses the condensation of the condensable group of silanol to 50% or less, but provides sufficient interaction between the silane and the film-forming polymer to form a bond. The amount is sufficient to prevent the film-forming polymer from gelling when the parts are mixed. The curing agent can be a partially neutralized silanol represented by the following structure D:

Where n is 1, 2, or 3; m is 0, 1, or 2; p is 0 or 1, preferably 0, provided that m + n + p = 3; R is the first M ⁺ is a metal that forms an alkyl salt; Y is a group that contains a nucleophilic moiety; R ′ is a linear, branched, or cyclic C ₁ -C ₈ alkyl group; Methyl or ethyl is preferred, and methyl is more desirable. The linking group in formula (D) is preferably a linear, branched, or cyclic alkylene group, or an arylene group, or combinations thereof, and contains one or more heteroatoms, which are themselves nucleophilic. . More preferably, X is _C 2 -C ₆ alkylene or R '&#8212; NH - R' - a, wherein each R 'is _C 2 -C ₄ alkylene group independently.

  Examples of suitable nucleophilic groups include amines, phenols, mercaptans, and carboxylates, primary and secondary amines and mercaptans are desirable, primary and secondary amines are more desirable, and primary A secondary amine is most suitable. Specific examples of partially neutralized aminosilane triols are typically potassium or sodium salts of 3-aminopropyl-silanetriol and N- (2-aminoethyl) -3-aminopropyl-silanetriol.

More desirable organosilane curing agents have at least one silicone linking group containing a substituted or unsubstituted alkylamino group and an alkoxy group bonded to the silicone that can form a network crosslink in the condensation of the organosilane. The amine group is in a free unblocked form or a blocked amino group. Amino group blocking can be provided by reaction with methyl isobutyl ketone or methyl amino ketone. Suitable groups reactive with the silane compound C ₁ -C ₄ alkoxy group is preferable. Examples of curing components include, but are not limited to, within the class of aminosilanes: aminopropyltriethoxy or -methoxysilane and aminoethylaminopropyltriethoxy or -methoxysilane, 3-aminopropyltriethoxysilane, 3-amino Primary and secondary amines such as propyltrimethoxysilane, 3-aminopropyldimethoxysilane or 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane; silanes containing, N- methyl - or N- phenyl-3-aminopropyltriethoxysilane, bis (3-aminopropyl) condensation aminoalkyl silanes such as tetramethoxy or tetraethoxy _disiloxane, NH 2 _{(CH 2) 3 -Si (OCH 3) 2 -O- (} C H ₃ O) ₂ Si— (CH ₃ ) ₂ NH ₂ , a polyglycol ether-modified aminosilane such as that sold under the trade name “Dynasylan 121” available from Huls AG, and the trade name “Dynasylan TRIAMO”. Such triamino functional propyltrimethoxysilane. Similar silanes having 2 or 3 silicon atoms can be used.

A suitable combination of aminoalkyltrialkoxysilane and fluoroalkyltrialkoxysilane exhibits excellent color stability (non-yellowing) upon heat aging of the cured coating.
Fluoroalkylsilanes useful in mixtures with other silanes containing active hydrogen, optimally in mixtures with aminosilane curing agents in the present invention, generally have the following formula E:

Wherein R ¹ is a monofluorinated, oligofluorinated, or perfluorinated alkyl group or monofluorinated, oligofluorinated, or perfluorinated aryl group having 1 to 20 carbon atoms, and Y is a CH _2, O, or S group. R ² is a linear, branched or cyclic alkyl group or aryl group having 1 to 8 carbon atoms, and R is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or An aryl group, y is 0 or 1, and m is 0 or 1; Some specific examples of representative fluoroalkylsilanes are 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3,3-trifluoropropylcyclohexyldimethyl. Toxylsilane, 3,3,3-trifluoropropylphenyldiethoxysilane, heptadecatrifluorodecyltriethoxysilane CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ).

An amino resin used in an amount of 10% by weight or less based on the weight of the film forming agent is used as a curing component, and acid catalyst heating conditions are used. The amino resin means all materials in a broad class of materials based on the reaction of urea, melamine, benzoguanamine, or acetylguanamine, etc. with formaldehyde. Such compounds are well known and are described, for example, in “Kirk-Othmer Encyclopedia of Chemical Technology”, 3 ^rd Ed. Volume 2, pages 440-469, Wiley-Interscience, 1978 ”.

  Curing agents each containing at least two ethylenically unsaturated double bonds activated by adjacent electron withdrawing groups and capable of Michael addition are suitable, such as maleic dianhydride and fumaric dianhydride Known as

  An example of another suitable curing component is carbodiimide. The polyfunctional carbodiimide exhibits appropriate reactivity with the functional group-containing elastomer used in the present invention. An N-acyl urea group is formed between the carboxylic acid sites. A carbodiimide bond is formed between the carboxyl group and other functional groups contained in the functionalized elastomer, such as hydrazidyl, amino and / or thiol groups. Multifunctional carbodiimides are obtained from polyisocyanates using, for example, the catalytic phospholine oxide described in US Pat. No. 2,941,966. Water dispersible carbodiimides are produced by reacting the reactants in the presence of 0.01 to 3 weight percent Sn catalyst based on the reaction mixture taught in US Pat. No. 4,321,394. Alternatively, it can be produced by the addition of carbodiimides containing polyol and isocyanate groups. The rearranged product can be produced at a low temperature of 25-150 ° C. using a catalyst such as tin (II) acetate or dibutyltin diacetate. Hydroxyl-containing compounds are a preferred hydrophilic group, including polyols containing 2-8 hydroxyl groups, especially those having a molecular weight in the range of 800-10,000. Examples of the polymer polyol include, for example, polyester, polyether, polythioether, and polyacetal. Hydrophilic multifunctional carbodiimides containing hydrolyzable silane groups are also suitable, particularly suitable for aqueous paint embodiments according to the invention taught in US Pat. No. 5,258,481.

  Examples of suitable carbodiimide compounds used in the present invention are N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- (3′-dimethylaminopropyl) carbodiimide, N-ethyl-N ′-(3-dimethylamino). Propyl) -carbodiimide, N′-diisopropyl-carbodiimide, N ′, N′-di-t-butylalbodiimide, 1-cyclo-hexyl-3- (4-diethylaminocyclohexyl) carbodiimide, 1,3-di- (4-diethylaminocyclo-hexyl) -carbodiimide, 1-cyclohexyl-3- (diethylaminoethyl) carbodiimide, 1-cyclohexyl-1-cyclohexyl-3- (2-morpholinyl- (4) -ethyl-carbodiimide, 1-cyclohexyl- 3- (4-Diethyl-aminocyclohex Sil) dicarbodiimide, etc. There are a variety of commercially available solvent soluble and water dispersible carbodiimides, which are commercially available from Union Carbide under the trade designation “UCARLNK”.

(C) The carrier liquid paint is applied with a carrier liquid. The carrier liquid can be one or more organic solvents, or predominantly water, but a small amount can consist of, for example, a small amount of solvent, or co-solvent, with the carrier being predominantly water. As such, it can be included elsewhere for the introduction of materials, auxiliary melting, and dispersion. The coating composition of the present invention is desirably applied to an elastomeric substrate in the form of one or more organic solvent carriers. The term [solvent] in the present invention can be broadly defined as a carrier for other components of the composition, in which case the solvent can maintain or dissolve the components in a substantially dispersed state or mixture. Suitable solvents include aqueous latexes and / or non-HAP (hazardous air pollutants) or non-VOC, or non-HAP, non-VOC organic solvents.

  Non-HAP solvents include methyl acetate, n-butyl acetate, t-butyl acetate, acetone, ethyl acetate, isopropyl acetate, isobutyl acetate, tetrahydrofuran, n-methylpyrrolidone, aliphatic hydrocarbons such as heptane, dimethylformamide , Diisobutyl ketone (DIBK), methyl isoamyl ketone, monochlorotoluene, para-chlorobenzotrifluoride (PCBTF), and vm & p naphtha. The combination of acetone and DIBK is a suitable non-HAP solvent mixture. Acetone, methyl acetate, and para-chlorobenzotrifluoride (PCBTF) alone or in combination are suitable solvents for HAP and VOC compliant paints. Among the HAP solvents, xylene, toluene, MEK and MIBK are photochemically reactive in the atmosphere. Xylene, toluene, MEK and MIBK are preferred solvents when HAP and VOC compliance are not critical.

  One category of solvents useful as carrier vehicles for the coating compositions of the present invention can be essentially organic solvents or other materials known to dissolve acrylonitrile-butadiene copolymers. Examples of organic solvents useful in the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; acetates such as butyl acetate; toluene, xylene and their derivatives; nitropropane; and ethylene dichloride.

  The organic solvent of the solution embodiment according to the present invention is typically used at about 70-97% by weight of the total coating composition (solvent, functionalized HNBR, curing component, thermally conductive particles and optional components). The Suitable solvents have a total non-volatile solid content in the range of about 3-30% by weight, desirably about 5-15% by weight.

  The use of water as a carrier is often highly desirable and environmentally advantageous. The present invention is made possible by emulsion polymerization of the polymer as well as the use of latex polymers prepared with aqueous inversion dispersions. The solid bulk elastomer film former can be converted to a dispersion by dissolving in a suitable organic solvent or mixture of organic solvents. Examples of organic solvents include, but are not limited to, all of the above organic solvents, but methyl ethyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone are preferred. Solvents that can be solvent mixtures have low water solubility, and optionally form an azeotrope with water when the solvent content is greater than or equal to about 50%, or the boiling point is less than or equal to about 95 ° C., and at least below the boiling point of water. It is desirable. The polymer solution as a continuous layer is treated by introducing a surfactant and subsequently adding water. Mixing methods known in the art can use anionic, cationic, nonionic or amphoteric emulsifiers and combinations thereof. The aqueous organic solvent mixture is mixed under high shear and phase inversion occurs and water becomes a continuous phase. The solvent is removed by heating to below the boiling point of water, generally below 95 ° C. Curing components and additional components, if any, are preferably added to the latex immediately prior to application.

  An example of a more suitable method for preparing an aqueous latex of X-HNBR rubber is described in US Pat. No. 4,826.721. The rubber component is dissolved in a solvent such as 3-chloro-toluene. Emulsifiers such as abietic acid (rosin type) derivatives and dehydroabietic acid derivatives can also be added. Water was also added to the composition. The composition is emulsified and the solvent is then liberated, preferably using rotary evaporation under reduced pressure. X-HNBR latex is also available from Nippon Zeon (Japan). The aqueous latex coating composition used in accordance with the present invention generally has a solids content of 30-50% by weight.

  The radiant coating composition of the present invention cures to form a substantially transparent matrix elastomer. Transparency is essential for transferring incident radiant heat to the underlying thermally conductive metal particles, which release the heat through the paint surface. Rather than conducting heat through the coated substrate, a surprising level of thermal reflectance was observed in temperature monitoring below the surface of the product. This radiation property is observed even for low surface area molded substrates, although a decrease in substrate temperature is expected to be directly proportional to the ratio of surface area to volume of the underlying molded article.

  Any colored compounds such as dyes or organic pigments can be introduced at low levels. The colored paint provided in accordance with the present invention provides outstanding color and film physical properties for long term outdoor use. An extensive list of organic pigments suitable for adding radiation to coloration can be found in current books published by Lippincott & Peto publishers and is well known to those skilled in the art of elastomer compounding is there. Typically used organic colorants can be introduced for various coloring effects. Uncolored organic colorants leave the paint clear, but with a color or shade.

  In particular, the finely pulverized inorganic metal oxide pigment (diameter of 0.5 micron or less) can contain up to 2.0 parts by weight per 100 parts by weight of the elastomer film-forming agent. For example, titanium substantially exhibits the radiation of the paint. Can be used without any hindrance. The pigment can be mixed into the solid polymer using a Banbury mixer or a two-stage mill. The rubber containing the pigment is then dissolved in a solvent and then added to the solvated polymer mixture. This is a preferred method for adding aluminum flakes. An example of solvent dispersion of aluminum flakes consists of 50 parts aluminum flakes and a mixture of 55 parts ethylene glycol and 45 parts ethylene glycol monobutyl ether.

In coating embodiments that further have metal conductor particle thermal radiation, a minimum surface coverage is essential to provide effective radiation. The term [particles] includes irregular shapes, granules, leaf shapes or various complex shapes. Heat reflecting pigments are available in many forms, eg fine solids, or leaves, dry powder forms or dispersions or solvents or plasticizers, eg pastes in mineral spirits. Flakes derived from finely ground vapor deposited films are suitable. The thermally conductive metal particles include finely divided irregular particles of brass, titanium, silver or aluminum, or leaf particles. Included are metal-coated particles / metallized coatings that are desirably introduced as leafing or non-leafing aluminum flakes. Leafing flakes such as leafing aluminum particles or flakes are commercially available with paints such as stearic acid, and when applied to a surface, the particles are oriented in an interleaved structure parallel to the surface of the final radiant paint. To do. Metal particles with an average particle size of 5 to 25 microns used at a level of 10 to 100 parts by weight per 100 parts by weight of the film-forming elastomer are effective radiation energy radiation when cast into a 0.01 cm film. And provides sufficient flex-fatigue resistance such that the film is not subject to stress cracking. Stress cracking results in loss of radiation performance. Metal particles having an average particle size of 25-100 microns should be used at a level of at least 20 parts to 150 parts by weight per 100 parts by weight of the film former to provide sufficient radiant heat emissivity without stress cracking. Don't be. Aluminum flakes are typically available with an average particle size of about 300 μm or less in diameter. The dependence characterizing the average particle size is in the supplier's specification. The aluminum flakes should have a number average particle size of about 1 to 100 microns, desirably 5 to 60 microns, optimally 10 to 45 microns. Preferred aluminum particles are flakes having a size such that 99% passes through a 325 mesh screen, i.e., a diameter of about 45 microns or less, preferably an average particle size of 8-35, especially 10-20 microns.

  Leafing metal flakes comprise an aluminum and solvent paste having at least about 40% aluminum flakes, preferably about 60-70% aluminum flakes as described in US Pat. No. 5,045,114. Can also be introduced as dry flakes. The metal particles are used in the above amounts with respect to the film-forming polymer in order to exhibit radiation performance. A suitable amount of metal particles is in the range of 15 to 30 parts by weight per 100 parts by weight of the film forming agent. This proportion includes consideration of surface additives such as surfactants or adhesion promoters such as silane.

  The coating composition of the present invention includes other optional ingredients, such as nitroso compounds, ZnO, QDO, maleimide, antioxidants, and a particulate reinforcing agent having a size of 1 micron or less. The total amount of optional additives should not exceed about 15 parts per 100 parts of the functionalized film-forming polymer. Specific examples of particulate reinforcements useful in the present invention include precipitated silica and fumed silica. Matting agents known in the art are available in amounts effective to control the gloss of the cured film, and include, but are not limited to, silicates. The optional silica has a particle size of 700 nm or less, preferably 20 to 200 nm. The micron-sized fine particle reinforcing agent does not affect the transparency of the film-forming agent for the remarkable effect of reducing the radiation of the paint, and exceeds 20 parts per 100 parts by weight of the functionalized elastomer film-forming polymer. Not available in various quantities.

  The coating composition is prepared by simply mixing the ingredients with a hand with a spatula, or by mechanical mixing or shaking. The coating composition is typically applied to the elastomeric material and / or other substrate by dipping, spraying, smearing, brushing, etc., after which the paint is applied for a period of time, typically about 30 minutes to Dry for 2 hours, preferably about 45 minutes to 1 hour. The coating composition is typically applied to the substrate to form a dry layer having a thickness in the range of about 2.54 μm to 127 μm, preferably about 12.7 μm to 38.1 μm. In a cured, unsupported or support coating, the coating can extend at least 100% of the original length, preferably up to 200%, optimally up to 300%.

The coating composition can be applied to vulcanized or non-vulcanized substrates, or non-cured and co-cured substrates, if necessary, at elevated temperatures.
The gloss of a cured coated substrate that does not significantly reduce transparency can be manipulated at least by the use of various amounts of solvent, the control of the evaporation rate, and / or the introduction of various known pigments and / or polishes. For organic carrier-based paints, relatively rapid evaporation has been shown to give a lower gloss surface than a longer cure rate. The cured paints of the present invention may give the substrate a gloss of about 3% to 70%, generally at a 60 degree angle, as measured using a Byk-Gardner Mico TRI Glossmeter according to ASTM D-523 and D-2457. it can. Gloss demands vary depending on the application, camouflage colors are desirable at low gloss levels, and cosmetic paints are intermediate between high gloss levels. For example, the coating composition can be effectively utilized to give an aesthetically pleasing appearance to a tire sidewall such as a “metallic wet” look. The resulting gloss of the cured coating can be effectively controlled to effectively provide the necessary surface, finish, or appearance for the substrate.

  The coating composition cures within about 2 to 24 hours under ambient air conditions including room temperature. Its curing can be accelerated by exposing the paint to high temperatures (this is not necessary).

(D) Flexible base material The coating composition of the present invention can be applied to a flexible base material such as a myriad of molded elastomer materials under pre-curing or post-curing conditions. The paint is applied to the entire outer surface of the substrate. The coating composition can be applied to molded and shaped articles such as those made from thermoplastic vulcanized rubber or thermoset rubber. The coating composition of the present invention is particularly suitable for coating cured rubber engine mounting parts consisting of vulcanized elastomer parts bonded to metal parts.

  The engine mount structure consists of a base layer molded from natural rubber, optionally bonded and / or molded around one or more metal mounting members to be secured to the vehicle structure and engine housing. The base layer is susceptible to degradation due to heat, oxidation, ozone attack, or ultraviolet radiation. The radiant paint is sprayed or dipped and applied to the contour of the mount, which is fully cured after application to the base layer, and the radiant paint is in use when the operating or parallel temperature in the rubber part of the mount is placed in use. At least 16 ° C., preferably at least 27 ° C., optimally 41.6 ° C.

  Suitable radiation coating compositions are particularly effective as cured elastomer coatings having limited oil and solvent resistance. Such elastomers include natural rubber, styrene butadiene rubber, polybutadiene rubber, ethylene propylene and ethylene propylene diene rubber, polyisobutylene-isoprene rubber, polychloroprene, nitrile-butadiene rubber with a low acrylonitrile content (<35 wt%), and the like. The coating composition can also be used on hard substrates such as metals, plastics, ceramics, and composites. Examples of thermoplastics and / or thermoset substrates include, but are not limited to, soft polyvinyl chloride, PVC-elastomer alloys, as well as PVC-nitriles; adhesion-promoting or modified polyolefins such as compounded polyethylene and polypropylene; PBT, soft or rubbery polyurethanes, polyureas, soft polyesters such as rims; fiber reinforced soft plastics, and cellular vinyl and polyurethane. These paints are particularly useful for adhesive rubber mounts that contain both elastomeric and rigid elements. A substrate is considered flexible when the elongation of the substrate is 25% or more.

  Examples of commonly available flexible substrates to which the coating composition of the present invention is applied include, but are not limited to, tires, bumpers, wiper blades, vibration breakers, rubber mounts, rail track pad fasteners, helicopter rotor bearings, chassis. Includes mounts, wiper frames, gaskets, heels, shoe soles, printing rolls, belts, hoses, fuel tanks, rubber moldings, TPO or TPE moldings, signs, and flexible industrial rubber products. In addition to radiation, these paints have excellent resistance to oils, solvents, oxygen, ozone and UV light.

  The coating composition of the present invention can be applied to one or all sides of a substrate. Often, it should be considered that it is effective for heat dissipation to apply only one side of the substrate oriented to the heat source. As mentioned above, it is advantageous to coat the surface of the substrate that is exposed to light, air, oil and solvent. Obviously, the surface of the substrate that is not in contact with light, air, oil and solvent need not necessarily be applied. The paint is desirably a continuous paint in the form of a film that completely covers the intended surface of the substrate. The thickness of coating that covers the surface that needs to be protected is not significantly thick enough to substantially change the mechanical properties of the substrate.

  Tires can be coated with the composition of the present invention. The coating composition can be used to coat the entire outer and / or inner surface of the tire. Furthermore, it is also necessary to coat only certain parts of the tire such as side walls, treads and the like. A tire is typically a tread, a pair of sidewalls adjacent to the tread at the shoulder, a generally toroidal cloth reinforced rubber carcass and one or more plies for supporting the tread and the sidewalls, and one disposed between the carcass and the tread. It consists of the circumferential fabric reinforcement belt of the above ply. Tires also typically include a pair of circumferentially extending bundles of wire beads that do not substantially extend, with the carcass extending from one bead to another and the side edges wrapped around the bead. The tire preferably also has a hard structure and includes a pair of tip members having a triangular cross-section in the bead region and a pair of hard shuffling members disposed in the bead region. It should be understood that the above-mentioned members of the tire are ordinary ones, and include other members not mentioned, and the above-mentioned members are omitted. The tire also includes an inner liner that is added to the inner surface of the tire to improve air impermeability. All tire members can be coated with the coating composition of the present invention. It is desirable to coat the tread and / or sidewall regions.

Preparation of the elastomeric substrate for application The elastomeric surface or substrate to be applied is optionally pretreated with a chlorinating agent such as sodium hypochlorite and hypochlorous acid. The use of various chlorinating agents to prepare elastomeric materials for application of coating compositions is well known in the art. An example of a chlorinating agent is commercially available from Lord Corporation under the trade name CHEMLOK-7701. The chlorinating agent is applied to the surface of the elastomer material by brushing, dipping, spraying, painting, or the like. Chlorinating agents are extremely volatile and typically dry in seconds or minutes.
The coating composition of the present invention has the surprising ability to form a robust bond to flexible elastomer parts alone and to metal parts (these parts are applied adjacent to the elastomer parts). It is desirable to provide an elastic coating on both the elastomer and the metal so that the interface between the elastomer and the metal can be adequately protected with the coating composition. Thus, the present invention differs from many traditional protective coating compositions that only have the ability to adhere to one type of substrate to be protected.

  The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention as defined by the claims.

Example 1
The following example was prepared using Zetpol 2220, an X-HNBR polymer from Zeon Chemical having a 36% acrylonitrile content with 5 mole percent unsaturation. A suitable commercial substitute is Therban KA8889.

The elastomer paint solution was prepared as follows:
Component explanation PHR
X-HNBR Carboxylated hydrogenated nitrile butadiene 100.0

  This blend was dissolved in methyl isobutyl ketone (MIBK, CAS No. 108-10-1) at a solid content of 12% by weight.

  To 40 g of solution, 53% of bis- [isocyanatophenyl] methane (diisocyanate) in xylene was added at levels of 0.1 g, 0.5 g and 1.0 g. At a level of 0.1 g diisocyanate, the solution cured in less than 16 hours at room temperature. At 0.5 g, the solution cured in 30 minutes.

  To the 40 g solution, 3-isocyanatopropyltriethoxysilane, CAS # 24801-88-5, was added in amounts of 0.3 g, 0.7 g, 1.0 g and 1.3 g. At all levels, the coating composition began to cure within 45 minutes to 1 hour and was fully cured within 16 hours.

The fuel oil resistance test paint was tested on a natural rubber compound (A135Q) with a durometer of 55 treated with Chemlok 7701. The paint was then compared to the commercial fluorocarbon paint PLV-2100, and the commercial HNBR SPE XV taught according to US Pat. No. 5,314,955 and the uncoated control.

When immersed in Jet A fuel for 24 hours at room temperature, the resulting volume% swelling results are as follows:
Control Uncoated 192.9%
Control PLV2100 0.1%
Control HNBR SPE XV 33.6%
Example paint of bis- [isocyanatophenyl] methane
2.2%
Example paint of 3-isocyanatopropyltriethoxysilane 2.3%

Adhesion Test The adhesion of the rubber was tested by gluing two 1 inch (2.54 cm) wide strips together and pulling at 180 ° peel. The rubber strip was made from a commercial natural rubber compound (A135Q) with a durometer of 55 treated with Chemlok 7701. Approximately 2 inches (5.08 cm) long was applied; each strip was placed in contact with each other and a 472 g weight was added to ensure intimate contact. The weight was left for 10 minutes. After 8 days of drying time, each strip was pulled apart on a Tinius Olsen tensile tester. The following table shows the results.

Paint type Peeling result, kgm
Control PLV2100 0.28
Control HNBR SPE XV 1.18
Example paint of bis- [isocyanatophenyl] methane
2.14
Example paint of 3-isocyanatopropyltriethoxysilane 2.91

The metal was bonded to a 2.54 cm wide rubber strip and a 2.54 cm metal coupon with an overlap of 6,54 cm ² and subjected to a shear test. The rubber strip was made from a commercial natural rubber compound (A135Q) with a durometer of 55 treated with Chemlok 7701. The metal coupon was 304 stainless steel. Stainless steel was chosen because it is known to be difficult to bond. After coating, each was placed in contact with each other and 472 g of weight was added to ensure close contact. The weight was left for 10 minutes. After 8 days of drying time, each strip was pulled apart on a Tinius Olsen tensile tester. The following table shows the results.

Paint type Adhesion result, kg / cm ²
Control PLV2100 1.29
Control HNBR SPE XV 1.35
Example paint of bis- [isocyanatophenyl] methane
1.27
Example paint of 3-isocyanatopropyltriethoxysilane 1.29

The ozone resistant ozone test was performed at a temperature of 40 ° C. with 5 pphm ozone using a dynamic ozone test (ASTM-D3395).
The sample was based on a commercial sulfur cured natural rubber / polybutadiene blend of 55 durometer protected with an ozone crack inhibitor wax and an alkyl-arylphenylene-diamine-ozone crack inhibitor (M122N). Under dynamic conditions, the carboxylated hydrogenated paint is more effective as an ozone barrier than the HNBR paint SPE XV.

Time to first crack Control 6.5 hours Control HNBR SPE XV 6.5 hours Example 1 paint of bis- [isocyanatophenyl] methane does not crack in 28 hours.
Example 3 Paint of 3-isocyanatopropyltriethoxysilane does not crack in 28 hours.

  In addition to having a low adhesion value, the PLV2100 coating cracks and bends from the rubber surface. Perforated DeMattia bent samples (made from 55 durometer natural rubber compound) were bent according to ASTM D813 with the same paint applied. The PLV2100 coating was severely cracked and delaminated by exposing the substrate at 4000 cycles or less. Both the baked HNBR SPE XV and Example 1 performed 80,000 cycles, at which point the natural rubber substrate cracked. None of the paints of the examples showed signs of delamination. This base formulation, when provided with an effective amount of thermally conductive metal particles, showed the same good performance as the above test and further provided radiation characteristics.

Example 2
The following example was prepared using an X-HNBR polymer available from Bayer AG under the trademark Therban KA8889. A suitable commercial substitute is Therban KA8889.

The elastomer paint solution was prepared as follows:
Component explanation PHR
X-HNBR Carboxylated hydrogenated nitrile butadiene 100.0

This blend was dissolved in methyl isobutyl ketone (MIBK, CAS No. 108-10-1) at a solid content of 15% by weight.
To the coating solution was added 33 phr of aluminum flakes having an average particle size of 16 microns.
To 97.5 parts by weight of the solution, 2.5 parts by weight of bis- [isocyanatophenyl] methane (diisocyanate) (Casabond TX, 53% in xylene) was added.
A natural rubber cured block (7.6 cm × 7.7 cm × 1.2 cm) having a durometer A of 65 was applied to a dry film thickness of about 0.025 mm.
A 3.8 cm hole was drilled and a thermocouple was inserted to monitor the center temperature of the block. The block was placed 20 cm from the rubber block under a 250 watt infrared lamp. The temperature was recorded at the following time intervals using a Cole-Parmer Dual JTEK thermocouple thermometer 91100-40.

Non-coated rubber block coated rubber block
Time (min) Temperature (° C) Temperature (° C)
First 0 23.2 23.1
10 172.2 36.2
20 101.6 48.1
30 114.7 54.7

The uncoated sample began to smoke within the first 10 minutes of exposure to the heat source.
The DeMattia bent sample was coated with the coating material used in Example 2 according to ASTM D813. After 77,000 cycles, no signs of cracking or delamination were observed in the coating. Cracks occurred in the rubber substrate, and the coating broke when the substrate cracked. Adhesion was excellent and breakage was observed only on the underlying substrate, indicating that the highest level of film bonding was obtained.

  The result shown in FIG. 1 shows that Example 2 was repeated. A 40.6 cm long sample was applied, the fan was moved at a low speed (speed 3), and air was blown into the sample from a distance of 2.9 m. An infrared lamp was placed at a position of 10.1 cm from the center. Tests were performed under simulated air movement in a real car.

Non-coated rubber block coated rubber block
Time (min) Temperature (° C) Temperature (° C)
First 0 22.7 22.7
4 35 25.5
10 55 28.8
20 77.7 33.3
35 82.7 35.5
50 87.2 37.2
120 87.2 37.2

Example 3-Functionalized HNBR aqueous latex An aqueous functionalized HNBR latex was prepared according to the present invention. A 41% solids carboxylated HNBR latex, 404EXPLTX005, sold as Latex B by Zeon Chemical, was also used. The compositions shown in Table 1 below were prepared.

  A DeMattia Flex sample was sprayed with the latex / isocyanate combination. The DeMattia sample was treated with MIBK and Chemlok 7701, and the paint was applied to the sample by spraying. All samples were run for 80,000 cycles with no signs of cracking or delamination. Adhesion was great.

The ozone test was performed at a temperature of 40 ° C. with 5 pphm ozone using a dynamic ozone test (ASTM-D3395).
The sample was based on a commercial sulfur cured natural rubber / polybutadiene blend of 55 durometer protected with an ozone crack inhibitor wax and an alkyl-arylphenylene-diamine-ozone crack inhibitor (M122N). Observations were made at 2-hour intervals.

Time when edge crack was observed Non-coating control 4 hours Apply Chemisat LCH7302
Non-functionalized HNBR 2 hours C.I. Chemistat LCH7302 applied, non-functionalized HNBR
Bayhydur 3028 (1,6-HDI) 5.0 parts per 100 parts by weight 4 hours
D. Carboxylated HNBR 404EXPLTX005
For 10 hours. Apply carboxylated HNBR 404EXPLTX005,
5.0 parts per 100 parts by weight of 1,6-HDI 22 hours Chemisat LCH7302 is a recently manufactured HNBR latex from Zeon Chemical, formerly manufactured by Goodyear Chemical.

Example 4
4E 4F 4G 4A

Silver 1 Silver 2 Silver 3 Green Therban KA8889 ^* 100 100 100 100
Akrosem E2557 Green --- --- --- 2.5
Alglo 400 Al paste ^** 10.0 --- ---
Al paste 586
---
12.5
---
Stapa Metallux 2141 ---
--- 10.0 ---
Al paste

^* Carboxylated HNBR from Bayer Ag.
^** Average diameter 45 microns.

Alglo 400 and Al paste 586 are supplied by Toyal America, and Stapa Metallux 2141 is an Eckert America L.C. P. Al paste 565 and Stapa Metallux 2156, supplied by the company, were also used. Various particle sizes of flake and non-flake aluminum pigments can be used together to obtain various visual effects. Each of the blended elastomers was dissolved in a 10% solid content in a solvent. They can be mixed into color shades by mixing colorants according to known techniques of color matching. On the other hand, a mixture of 90% silver 3 and 10% green gives a silver color with hints of pastel green.

  A blend of copper conductive powder from Caswell and Silver 2 (Example 4) gave a metallic gold color.

Example 5-Control Peroxidation according to U.S. Patent No. 5,314,741 using a paint cure of a hydrogenated copolymer of acrylonitrile and butadiene in an organic solvent using zinc-sulfur cure. The product was applied to a cured natural rubber substrate.

Paint composition
Component Weight part
HNBR 100
Zinc oxide 4.00
Sulfur 1.75
ZMBT ^* (2) 2.00
Zinc dibutyldithiocarbamate 0.75
Total 108.50
^* Zinc 2-mercaptobenzothiazole accelerator

The ingredients except HNBR were mill mixed and then dissolved in a 10% solution in MIBK solvent. The coating composition was prepared by mixing solid rubber with a two-stage mill followed by dissolving HNBR in a solvent. A 2.54 cm wide sample of sulfur cured natural rubber was cleaned with isopropyl alcohol before the coating composition was applied.

  The coating composition was applied to the surface of a natural rubber substrate sample. The coating thickness was about 0.0254 mm dry. Two coated, uncured strips were placed together with the coated surfaces against each other. The paint was dried at room temperature for 24 hours. Some samples were baked in an oven at 152 ° C. for 15 minutes to cure the paint. This gave the product as a coated natural rubber tensile sheet having a paint thickness of about 0.05 mm and bonded together. The bonded samples were pulled apart at the peel and the force required to separate them was recorded.

Uncured coating (dried, unbaked) 0.27 kg peel strength Cured coating (baked at 153 ° C. for 15 minutes) 0.8 kg peel strength

  Their level of adhesion to rubber substrates as cured and uncured paint was unacceptable and low, resulting in bending fatigue and cracking of the elastomeric substrate after bending.

Example 6
The clear primer was made by dissolving X-HNBR elastomer (Therban KA-8889 from Bayer AG) in MIBK at 5 wt% solids. 53% was added to 99.25 parts by weight of the solution to 0.75 parts by weight of bis- [isocyanatophenyl] methane (diisocyanate), xylene (Casabond TX). A heat conductive aluminum pigment was added to the transparent undercoat at various weight percentages based on the weight of the polymer.

A natural rubber cured block (7.6 cm x 7.6 cm x 1.2 cm) having a durometer of 65 was applied to give a dry coating of about 0.025 mm.
A 3.8 cm hole was drilled and a thermocouple was inserted to monitor the center temperature of the block. The block was placed under a 250 watt infrared lamp, 20 cm from the rubber block. The control block was not applied. The temperature was recorded at the following time intervals using a Cole-Parmer Dual JTEK thermocouple thermometer 91100-40. No fan was used in this experiment.

Non-coated rubber block
Time (min) Temperature (℃)
First 0 22
5 36
10 46
15 54
20 63

Example 6A
STAPA Metallux 2156 (Eckart America LP) 70% solids, non-leafing, average diameter of 16 microns.
Coated rubber block using STAP Metallux 2156
10 phr 20 phr
Time (min) Temperature (° C) Temperature (° C)
First 0 22 22
5 30 20
10 41 32
15 49 38
20 54 42
The results are shown graphically in FIG.

Example 6B
Aluminum paste 565 (Toyal America) 65% solids, average diameter of 13 microns.
Coated rubber block using aluminum paste 565
10 phr 20 phr
Time (min) Temperature (° C) Temperature (° C)
First 0 22 22
5 29 27
10 36 34
15 41 38
20 47 43
The results are shown graphically in FIG.

Example 6C
Alglo 400 aluminum paste 565 (Toyal America) 70% solids, non-leafing, average diameter of 45 microns.
Coated rubber block using Alglo 400
10 phr 50 phr
Time (minutes) Temperature (℃) Temperature (℃)
First 0 22 22
5 28 27
10 38 34
15 44 38
20 47 43
The results are shown graphically in FIG.

Example 6D
Sparkle Silverx 760-20-A (Silberline) 80% solids, non-leafing, average diameter of 54 microns.
Coating rubber block using Sparkle Silvex 760-20-A
10 phr 50 phr
Time (min) Temperature (° C) Temperature (° C)
First 0 23 23
5 30 28
10 38 33
15 47 39
20 51 42
The results are shown graphically in FIG.

Example 7
Three similar paints were made using fluoroelastomer, aqueous XHNBR latex, and polyurethane, respectively. The fluoroelastomer primer was mixed with the following formulation, which was then dissolved in MIBK to make a 30% solids solution.

Example 7A
Viton A-100 (DuPon)) 100.0PHR
Magnesium oxide
D) 1.0
Calcium hydroxide industrial brand
2.0
Metallux 2156 (Eckart America) 10.0
Aluminum paste 586 (Toyal America) 5.0

1.8 g N- (2-hydroxyethyl) ethylenediamine was added to 120.0 g dissolved solution. After 4 hours, 5 g 3-isocyanatopropyltriethoxysilane and another 25 g MIBK were added together.

Example 7B
XHNBR latex was made by starting with Latex B (41% solids) from Zeon Chemical. To 100.0 g of Latex B was added 20.0 g Sparkle Silverex 760-20-A (Silberline) and 5.0 g water dispersible polyisocyanate Bayhydrur 302 (Bayer).

Example 7C
The polyurethane was made by adding 7.0 g (21.8 phr of urethane solid) of aluminum paste 586 (Toyal America) to 100.0 g of Chemglaze V021 transparent, moisture curable polurethane at 32 wt% solids, It had a viscosity of 115 cps, a T _g below 0 ° C., a cured tensile strength of about 210 kg / cm 2, and an ultimate elongation of 350%.

  A natural rubber cured block (7.6 cm × 7.6 cm × 1.2 cm) having a durometer A of 65 was applied using the paints of Examples A, B, and C, resulting in a dry coating of about 0.025 mm. .

    A 3.8 cm hole was drilled in the center of the test block and a thermocouple was inserted to monitor the center temperature of the block. The block was placed under a 250 watt infrared lamp and placed 7.5 cm from the top surface of the rubber block. The control block was not applied. The surface temperature was monitored using an Omegascope Model OS530 series non-contact infrared thermometer. The internal temperature was monitored using a Cole-Parmer Dual JTEK thermocouple thermometer model 91100-40. No fan was used in this experiment.

Non-coated rubber block <br/> Time (min) Internal temperature (℃) Surface temperature (℃)
First 0 20.8 20
1 23.3 83
2 33.2 116 (smoke)
3 45.3 131
4 57.2 148
5 68.9 164
6 80 167
8 98.4 178
10 114.4 190

Fluoroelastomer (Example 7A) Coated rubber block Time (min) Internal temperature (C) Surface temperature (C)
First 0 20.9 20
1 23 63
2 31.2 85
3 40.3 97
4 49.3 107
5 58.1 114
6 66.3 125
8 81.5 131 (smoke)
10 94.5 144

XHNBR latex (Example 7B) coated rubber block Time (minutes) Internal temperature (C) Surface temperature (C)
First 0 21 20
1 22.3 69
2 28.2 80
3 35.6 90
4 43.5 95
5 51.4 100
6 59.9 113
8 72.8 123 (smoke)
10 85.6 129

Polyethane (Example 7C) Coated rubber block Time (min) Internal temperature (° C) Surface temperature (° C)
First 0 22.2 20
1 24.4 53
2 32.4 63
3 40.7 79
4 49.2 83
5 57.2 87
6 64.73 125
8 81.5 92
10 90.2 106 (no smoke)

  The results of comparing the surface temperature of the uncoated control and coated sample based on Examples 7A, 7B and 7C are shown graphically in FIG.

Example 8
A room temperature curable reflective paint formulation was made as follows:
Example 8A Example 8B
Component Weight part
MIBK 90.0 90.0
DIBK 5.0 5.0
Therban KA-8889
(X-HNBR) 5.0 5.0
After dissolving the polymer, the following ingredients were added:
Aminopropyltriethoxysilane 5.0 5.0
Aluminum paste 586 2.5 2.5
KBM-7803 ---- 5.0

KBM-7803 is heptadecatrifluorodecyltrimethoxysilane CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and is commercially available from Shin-Etsu Silicone. Each of the paints was applied to a 15.2x15.2x1.9 cm natural rubber pad (65 durometer). After curing the paints, they were exposed to an infrared lamp suspended 15.2 cm above the paint. The surface temperature was monitored at the time intervals shown below using a Cole-Parmer Dual JTEK thermocouple thermometer model 91100-40.

Surface temperature measurement
Non-coated Coated 93-6 Coated 93-6
Time (min) Temperature (° C) Temperature (° C) Temperature (° C)
First 0 27.7 27.7 27.7
1 80 53.8 48.8
2 112 70 63
3 137 87.7 76
4 151 90 85
6 171 99.4 95
7 173.8 102 97
Discoloration at 175 ° C-aging: intense minimal

Radiant paints based on hydrolyzable mixtures of aminoalkyltrialkoxysilanes and fluoroalkyltrialkoxysilanes exhibit low discoloration after rapid curing and heat aging.
Although the best mode and preferred embodiments have been presented according to the patent law, the scope of the present invention is not limited thereto but is limited to the appended claims.

Figure 5 is an internal temperature versus time noplot for a coated versus uncoated rubber block exposed to an infrared heating source for 120 minutes. (Example 2) It is a graph which shows the influence of the 0.00040 cm heat conductive coating apply | coated to the natural rubber on the internal heat which generate | occur | produces under the radiant heat in 0, 10 and 20 phr of a heat conductive pigment. (Example 6A) It is a graph which shows the influence of the 0.00040 cm heat conductive coating apply | coated to the natural rubber on the internal heat which generate | occur | produces under the radiant heat in 0, 10 and 20 phr of a heat conductive pigment. (Example 6B) It is a graph which shows the influence of the 0.00040 cm heat conductive coating applied to natural rubber on the internal heat generated under radiant heat at 0, 20, and 50 phr of the heat conductive pigment. (Example 6C) It is a graph which shows the influence of the 0.00040 cm heat conductive coating applied to natural rubber on the internal heat generated under radiant heat at 0, 20, and 50 phr of the heat conductive pigment. (Example 6D) FIG. 6 is a graph showing the effect on internal temperature of a natural rubber block coated using three different thermally conductive paints versus an uncoated block after 10 minutes under radiant heat.

Claims (25)

A two-liquid coating composition comprising a first part and a second part, a reactive to 0 ℃ exhibited the following T _g of active hydrogen-containing curing agent in the first part, and an active hydrogen-containing group A flexible film-forming polymer having a functional group introduced therein and containing 10% or less of ethylenic unsaturation; an active hydrogen-containing group and a cross-linking group, or a group reactive with the active hydrogen and the cross-linking group in the second part; An ambient temperature curable, two-part liquid coating composition comprising: a curable component; and a carrier liquid. Further, (a) 10 to 100 parts by weight of thermally conductive metal particles having an average particle size of 2 to 10 μm per 100 parts by weight of the film-forming polymer, or (b) 10 to 150 parts by weight of 20 to 60 μm of average particle size The coating composition according to claim 1, comprising thermally conductive metal particles having The coating composition according to claim 1, wherein the film-forming polymer is a hydrogenated random or block diene copolymer having a molecular weight of 20,000 to 200,000. The coating composition according to claim 1, wherein the film-forming polymer is carboxylated HNBR. The coating composition according to claim 1, wherein the film-forming polymer is a functionalized acrylic rubber. The coating composition according to claim 1, wherein the film-forming polymer is derived from an ethylenically unsaturated monomer and an α, β-unsaturated carboxylic acid. The functional groups of the film-forming polymer are sulfonic acid, sulfonic acid derivative, chlorosulfonic acid, vinyl ether, vinyl ester, primary amine, secondary amine, tertiary amine, mono-carboxylic acid, dicarboxylic acid, 2. A partial or fully derivatized mono-carboxylic acid, selected from the group consisting of partially or fully derivatized dicarboxylic acids, dicarboxylic anhydrides, cyclic imides of dicarboxylic acids, ionomer derivatives thereof, and mixtures thereof. The coating composition as described. The coating composition according to claim 1, wherein the film-forming polymer is a hydrogenated diene elastomer comprising a methylol functional group. The coating composition according to claim 6, wherein the film-forming polymer is a hydrogenated diene elastomer comprising a phenol methylol functional group. The coating composition according to claim 1, wherein the film-forming polymer is a heat cracking reactive organism of diaryl carboxylate and amine-functionalized HNBR. The film-forming polymer, ethylene, C ₁ -C ₄ alkyl acetates and coating composition according to claim 5, comprising the terpolymer of carboxylic acid monomer units. 6. The coating composition according to claim 5, wherein the film-forming polymer comprises at least 30 mol% ethylene and 10 to 70 mol% monoethyl maleate. The film-forming polymer is a carboxylated block copolymer derived from an elastomer, and is selected from a hydrogenated styrene-butadiene-styrene block copolymer and a hydrogenated styrene-isoprene-styrene block copolymer. The coating composition according to claim 1, wherein The coating composition according to claim 1, wherein the film-forming polymer is a poly α-olefin-acrylic ester-acrylic carboxylate terpolymer. The coating composition according to claim 1, wherein the film-forming polymer is a hydrogenated nitrile butadiene polymer containing a hydroxyl group. The film-forming polymer is hydrogenated hydroxyl butadiene, carboxy modified chlorinated polyethylene, chlorinated polyethylene, polyepichlorohydrin, polyethylene-acrylic acid, SBR, SBS, NBR, SIBS, EPDM, EPM, polyacrylate, 2. A mixture of a halogenated polyisobutylene and a film forming agent selected from the group consisting of polypropylene oxide (the total proportion of unsaturation in the mixture is 10% or less). Paint composition. The film-forming polymer is introduced by treating the hydrocarbon polymer under ozonation conditions to produce an ozonated saturated hydrocarbon polymer and subsequently reducing the ozonated saturated hydrocarbon polymer. The coating composition according to claim 1, comprising a base. The film-forming polymer is a carboxyl introduced by treating a hydrocarbon polymer under ozonation conditions to produce an ozonated saturated hydrocarbon polymer and subsequently reducing the ozonated saturated hydrocarbon polymer. The coating composition according to claim 1, comprising a group. The film-forming polymer comprises two or more α-monoolefins and a non-conjugated diene comonomer, and includes carboxylic acid, anhydride, epoxy, phosphoric acid, sulfonic acid, sulfenate, sulfinate, hydroxy, epoxy, isocyanate. 2. A coating composition according to claim 1, wherein a functional group selected from the group consisting of a nate, an amine and an oxazoline group is introduced. The film-forming polymer is a hydroxy-terminated poly prepared by introducing a hydroxy group into a terminal position of a cationically polymerized isobutylene by dehydrochlorination, hydrobromination and oxidation of a chlorine-terminated polyisobutylene. The coating composition according to claim 1, comprising isobutylene. 2. A coating composition according to claim 1, wherein the curing agent comprises a pisocyanate containing 10-50% reactive NCO groups which are liquid at ambient temperature. 2. A coating composition according to claim 1, wherein the curing agent is in two parts and is a reduction-oxidation curing agent system comprising a polyfunctional ethylenically unsaturated compound, an oxidizing agent and a reducing agent. The coating composition according to claim 1, wherein the film-forming polymer comprises a chlorinated polyolefin modified with an acid or anhydride group. Optionally, the surface of the molded elastomer product to be bonded to the shaped metal product is filled with a solution type, a metal powder pigment, and a room temperature-curing elastomer film-forming paint is sprayed on the surface of the molded elastomer product to be dipped or brushed. Is present at least 10% by weight of thermally conductive particles and a T _{g of} 0 ° C. or less, is reactive to the active hydrogen-containing curing agent, or introduces a functional group that is an active hydrogen-containing group, and is less than 10%. A method for coating a molded elastomer product comprising a flexible film-forming polymer containing ethylenic unsaturation. The elastomer product is a group consisting of natural rubber, styrene butadiene rubber, polybutadiene rubber, ethylene propylene rubber, ethylene propylene diene rubber, polyisobutylene-isoprene rubber, polychloroprene, and nitrile-butadiene rubber having a low acrylonitrile content (<25%). The method of claim 24, comprising an elastomer selected from:

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