TW200404878A - Composite and process for producing the same - Google Patents

Abstract

A resin-rubber composite in which a vulcanized rubber member is bonded to a resin member through a vulcanized rubber layer is produced by heating and molding a rubber element selected from the group consisting of an unvulcanized rubber composition, a semi-vulcanized rubber member and a vulcanized rubber member, and a resin element selected from the group consisting of an unmolded resin composition, a semi-molded resin member and a molded resin member with contacting with each other under a pressure, through an unvulcanized rubber layer containing a vulcanizing agent (a radical-generating agent such as an organic peroxide). The resin member may comprise a thermoplastic resin or a crosslinkable group-containing resin, or a resin having an active atom (a hydrogen atom or a sulfur atom). At least one component among an unvulcanized rubber composition for forming the vulcanized rubber layer, and the resin member may contain a polyfunctional polymerizable compound having a plurality of polymerizable groups. The present invention provides a composite in which a resin member and a vulcanized rubber member are firmly bonded in a wide range of combination.

Description

200404878 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a composite (or composite member) and a method for manufacturing the same by combining a resin and a vulcanized rubber into one body and useful as mechanical components, automobile components, and the like. [Prior art] A method of integrating a resin-molded member and a rubber-molded member into an integrated unit. 'A method using an adhesive to bond the resin molded body and the rubber molded body is known. However, the method using the adhesive has a complicated manufacturing process and Project management is cumbersome, which will not only increase costs, but also reduce heat resistance and water resistance, and may not necessarily achieve sufficient adhesion. There is also a proposal for a composite in which resin and rubber are directly combined. For example, in Japanese Patent Laid-Open Publication No. 50-25682, it has been disclosed that a thermoplastic component such as polyoxymethylene or an olefin polymer is brought into frictional contact with a vulcanized rubber component that is compatible with the thermoplastic plastic component so that A method for manufacturing a composite body in which a plastic surface is melted so as to solidify the plastic component and the rubber component in a contact state. A method for manufacturing a composite by utilizing the compatibility between a thermoplastic resin and a rubber. In Japanese Patent Laid-Open No. 6 1-204260, a method of applying heat treatment to a polyphenylene ether resin and a synthetic rubber in the presence of a vulcanization system has been disclosed. Method. In Japanese Patent Laid-Open No. 9-1 24803, a method has been proposed in which a thermoplastic resin containing acrylonitrile 'and a rubber containing acrylonitrile are heat-sealed to produce a composite member. The method of making a composite by using a chemical reaction between a thermoplastic resin and rubber to produce a composite is disclosed in Japanese Patent Laid-Open No. 2-150439, Japanese Patent Laid-Open No. 3_133631, and Japanese Patent Laid-Open No. 3-138114. A method using a polyamide resin and a rubber component using a rubber component containing a carboxyl group or an acid base, a peroxide component, and a rubber component containing a vulcanization active agent. In Japanese Patent Application Laid-Open No. 8-1 5 6 1 8 8, it is proposed to produce a composite member by vulcanizing a resin member containing an epoxy group with a rubber member containing a carboxyl group or an acid base, and vulcanizing the resin member. method. In addition, by using a specific additive to produce a composite, Japanese Unexamined Patent Publication No. 7-1 10 13 discloses a method in which a polyamide molded article, a rubber containing H, a peroxide curing agent, A method of vulcanizing by contacting with a silane compound and a rubber compound containing a vulcanizing active agent as needed. In addition, there is also a hard component using thermoplastic polyester, and a soft component using rubber and peroxide curing agent and difunctional or polyfunctional cis

Method for hydrammine and rubber component of vulcanization activator contained if necessary (Japanese Patent Laid-Open No. 7-304880), using rubber and peroxide vulcanizing agent and silane compound, and vulcanization activator contained when necessary Method of rubber composition (Japanese Patent Application Laid-Open No. 7-1 66043). However, in these methods, if high adhesive strength is desired, the types of thermoplastic resins and rubbers must be limited. In particular, it is difficult to obtain a composite of a vulcanized rubber and a thermoplastic resin which lack reactivity. In Japanese Patent Laid-Open No. 10-5 8605, a substrate film (polyester film, etc.) and a polyfunctional methacrylate-containing rubber film (silicone rubber) as an adhesive improver have been disclosed. , Ethylene-propylene-based rubber, etc.), which are laminated and vulcanized to prepare a composite film by the 200404878 method. However, in order to obtain sufficient adhesion strength to the substrate film according to this method, a rubber containing a large amount of adhesion improver must be used, and the substrate film must be subjected to a corona discharge treatment or an easy adhesion treatment. In addition, in the examples of this document, it is described that it is necessary to use an electron beam of a high energy ray when performing the bonding, and therefore it is difficult to apply it to a combination of a thick and three-dimensional rubber molded body and a resin molded body. As described above, a highly versatile technique for combining a resin member and a rubber member with a high adhesive strength has not been known. In particular, there are cases where the bonding strength varies greatly depending on the type or formula of the rubber, resulting in a forced change of the rubber formula%, or even when the rubber formula is changed, high bonding strength may not be obtained. For example, from the viewpoint of the performance of rubber components, it is necessary to increase the rubber formulation of additives such as fillers, fillers, and plasticizers, or rubber formulations with restricted types of vulcanizing agents (such as rubber formulations that require sulfur-based vulcanizing agents). In the case of), the range of formulas required to increase the bonding strength will be greatly limited. Coupled with the measures to change the rubber formula itself, there are often many difficulties.

In view of this, an object of the present invention is to provide a composite body capable of firmly bonding a resin molded body and a vulcanized rubber molded body in a wide range of combinations, and a method for manufacturing the same. Another object of the present invention is to provide a composite body capable of firmly bonding a resin molded body and a vulcanized rubber molded body without applying an easy-adhesion treatment to the surface of the resin molded body, and a method for producing the same. Another object of the present invention is to provide a composite body capable of firmly bonding a resin molded body and a vulcanized rubber molded body without changing the rubber formula of the vulcanized rubber member, and a method for manufacturing the same. Still another object of the present invention is to provide a composite body in which a resin molded body and a vulcanized rubber molded body are firmly combined even in a three-dimensional structure, and a method for manufacturing the same. [Summary of the Invention] The inventors and others have conducted intensive review results in order to achieve the above problems, and found that if rubber and rubber are easily combined, an unvulcanized rubber layer containing a vulcanizing agent is interposed between the rubber member and the resin member, and is heated by By vulcanizing the unvulcanized rubber layer by other means, the rubber member and the resin member can be firmly integrated in a wide range of combinations, and a resin / rubber composite can be efficiently obtained to complete the present invention. That is, the composite system of the present invention combines a vulcanized rubber member and a resin member by a vulcanized rubber layer vulcanized by a vulcanizing agent to form a resin / rubber composite. In the present invention, since the bonding strength can be improved regardless of the type of the vulcanizing agent, the vulcanizing agent may be a sulfur-based vulcanizing agent (sulfur or a sulfur compound) or a peroxide-based vulcanizing agent (a radical generating agent such as an organic peroxide). . The resin member may be composed of at least one selected from a thermoplastic resin and a resin having a crosslinkable group, and the resin having a crosslinkable group may be a thermosetting resin and / or a thermoplastic resin having an unsaturated bond. In addition, the unvulcanized rubber composition and the resin member for forming the vulcanized rubber layer generally satisfy at least one of the following conditions (i) to (iii): (0) The resin member is composed of: at least 2 in one molecule. A thermoplastic resin that can be represented by the following formula U) with an orbital interaction energy coefficient S of 0.006 or more (selected from at least one active atom of hydrogen atom and sulfur atom 200404878): s = (CHOMO'n ) / | Ec-EH0M0, n | + (CLUMO, n) 2 / I Ec_

ElUM Ο, η I (1) [wherein ’Ec, CH0MO, n, ΕηΟΜΟ’π, ClUMO, !! , ELUMO’n

Both are calculated by the semi-empirical molecular orbital method MOPA CPM3. Ec represents the radical orbital energy (eV) of the radical generator as a vulcanizing agent, and CH0M0, n represents the nth element constituting the basic unit of the thermoplastic resin. The molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of the active atom, EHOMO, n represents the orbit energy (eV) of the above HOMO, and CLUM0, n represents the lowest empty molecular orbital (LUMO) of the nth hydrogen atom described above. Molecular orbital coefficient,

ELUMO, n represents the orbital energy (e V) of the above LUMO]; (ii) the component of at least one of the unvulcanized rubber composition and the resin member is a polyfunctional polymerizable compound having a plurality of polymerizable groups; (iii) ) Resin members are composed of thermosetting resins, or unsaturated bonds in the molecule

The unvulcanized rubber composition is composed of a polyfunctional polymer compound having a plurality of polymerizable groups. In the composite, at least one of the vulcanized rubber layer, the vulcanized rubber member, and the resin member may be formed by a composition containing a vulcanizing active agent. The vulcanizing activator may be composed of a polyfunctional polymerizable compound having a plurality of polymerizable groups. For example, the vulcanized rubber layer may be formed of an unvulcanized rubber composition containing a vulcanizing agent and a vulcanizing active agent, and a member including at least one of a vulcanized rubber member and a resin member (for example, a resin member) may be formed of a composition containing a vulcanizing active agent. . The amount of the vulcanization active agent may be 0.1 to 10 parts by weight for 100 parts by weight of the resin / -10-200404878 rubber, and may be 2 parts by weight or less for 100 parts by weight of the rubber, for example. The resin member may further contain a stabilizer for the vulcanization active agent (such as an antioxidant, a light stabilizer, a thermal polymerization inhibitor, etc.). The ratio of the vulcanization active agent to the stabilizer may also be the former / the latter (weight ratio) = 9 9 / 1 ~ 2 5/7 5 or so. The resin member system may be, for example, polyamine resin, polyester resin, polyacetal resin, polyphenylene ether resin, polysulfide resin, polyether ketone resin, polycarbonate resin, polyimide resin. Resin, polyboron resin, polyurethane resin, polyolefin resin, halogen-containing vinyl resin, styrene resin, (meth) acrylic resin, thermoplastic elastomer, phenolic resin, amine resin , Epoxy resin, thermosetting polyimide resin, thermosetting polyurethane resin, silicone resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, and thermosetting (Meth) acrylic resin. The vulcanized rubber layer may be vulcanized with a sulfur-based vulcanizing agent. For example, the vulcanized rubber layer may be composed of a diene rubber (a styrene-diene rubber vulcanized by a sulfur vulcanizing agent, etc.), and the resin member may be a polyphenylene ether resin. The method of the present invention uses a layer of unvulcanized rubber composition containing a vulcanizing agent to make a rubber element selected from an unvulcanized rubber composition, a semi-vulcanized rubber member, and a vulcanized rubber member, and a member selected from an unformed resin composition, a semi-formed resin member, and The resin member of the molded resin member contacts and vulcanizes the unvulcanized rubber or semi-vulcanized rubber to produce a resin in which the above-mentioned unvulcanized rubber layer combines the vulcanized rubber member of the rubber element and the resin member of the resin element through the vulcanized vulcanized rubber layer / Rubber compound. In this method, '-11-200404878 can also vulcanize unvulcanized rubber or semi-vulcanized rubber, and if necessary, mold rubber and resin components. In addition, a layer of an unvulcanized rubber composition containing a vulcanizing agent may be formed on a bonding surface of at least one of the bonding surfaces of the rubber element and the resin element, and the rubber may be heated under pressure by the unvulcanized rubber composition layer. Components and resin components. The unvulcanized rubber composition layer containing a vulcanizing agent may be formed of a film or a coating agent of the unvulcanized rubber composition. In this method, the unvulcanized rubber composition of the intermediate layer may also be formed between the molded resin member and a rubber element selected from the unvulcanized rubber composition and the semi-vulcanized rubber member, while molding uncured rubber φ rubber and / or semi-vulcanized rubber While cross-linking or curing. At least one of the unvulcanized rubber composition, the rubber element, and the resin element may contain a vulcanization active agent. If the resin element contains a vulcanization activator, the amount of the vulcanization activator may be about 0.1 to 5 parts by weight based on 100 parts by weight of the resin element. Furthermore, a layer of an unvulcanized rubber composition containing an organic peroxide and a polyfunctional polymerizable compound containing several polymerizable groups may be introduced between a rubber element and a resin element containing a vulcanizing agent, and the pressure may be applied under pressure. Heating and molding. Furthermore, at least one of the rubber element and the resin element may contain a polyfunctional polymerizable compound having H having a plurality of polymerizable groups. According to the meaning of "rubber" in this specification, it refers to rubber used to form a vulcanized rubber layer, or rubber used to form a vulcanized rubber member (the above-mentioned rubber element). In addition, the meaning of "resin" includes resin (the above-mentioned resin element) for forming a resin member. Detailed description of the present invention [resin member]

-12-200404878 In the composite of the present invention, the resin member is composed of at least one selected from the group consisting of a thermoplastic resin and a resin having a crosslinkable group (hereinafter also referred to as a resin for short). (Thermoplastic resin) Examples of the thermoplastic resin include polyamine resin, polyester resin, poly (thio) ether resin (polyacetal resin, polyphenylene ether resin, polysulfide resin, and polyetherketone resin). Resins, etc.), polycarbonate-based resins, polyimide-based resins, poly-maple-based resins, polyurethane-based condensation thermoplastic resins; polyolefin-based resins, halogen-containing vinyl-based resins, styrene-based resins, Ethylene polymer-based thermoplastic resins such as φ (meth) acrylic resins; thermoplastic elastomers and the like. These resins can be used alone or in combination of two or more. When two or more resins are used in combination, the resin composition may be formed into a composite resin composition such as a plastic alloy. (1) Polyamide-based resin Polyamine-based resins include: aliphatic polyamine-based resins, alicyclic polyamine-based resins, aromatic polyamine-based resins, and the like. Aliphatic polyamine resins include: aliphatic diamine components (C4_1G alkylene diamines such as tetramethylene diamine, hexamethylene diΦ amine) and aliphatic dicarboxylic acid components (adipic acid, Condensates of sebacic acid, dodecanedioic acid, and other alkylene dicarboxylic acids having about 4 to 20 carbon atoms (such as polyamide 46, polyamide 66, polyamide 610, and polyamide 610) 6 1 2 etc.), lactam [ε -caprolactam, ω-lauryl lactam and other carbon atoms having 4 to 20 carbon atoms, etc.] or amine carboxylic acid [ω -amine eleven Alkanoic acid] monomers or copolymers (such as amino acids having 4 to 20 carbon atoms, etc.) (such as polyamide 6, polyamide 11, 1, polyamide 12, etc.), etc.-13-200404878 Copolymerized fluorene (e.g. polyamine 6/1 1, polyamine 6/12, polyamine 66/1 1, polyamine 66/12, etc.) obtained by copolymerizing the fluorene components. The alicyclic polyamine resin includes a polymer using an alicyclic diamine and / or an alicyclic dicarboxylic acid as at least a part of the alicyclic diamine component and / or an alicyclic dicarboxylic acid component. Amidine and so on. The alicyclic polyamines include: · For example, the above alicyclic dicarboxylic acid components and alicyclic diamine components [C5-8 cycloalkyldiamines such as cyclohexanediamine; bis (aminocyclohexyl) methane, 2 , 2-bis (aminocyclohexyl) -propionate and other bis (amine C 5 -8 cyclohexyl) hydrocarbons (such as bis (aminocyclohexyl) alkanes) etc.] condensates. % Aromatic polyamine resins include: at least one of the above aliphatic diamine component and aliphatic dicarboxylic acid component is an aromatic polyamine, for example, a polyamine having a diamine component as an aromatic component Amines [condensates of aromatic diamines such as MXD-6 (m-xylylene diamine, etc.) and aliphatic dicarboxylic acids, etc.], polyamines whose dicarboxylic acid components are aromatic components [aliphatic diamines (Trimethylhexamethylene diamine, etc.) and aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.), etc.], diamine components and dicarboxylic acid components are aromatic components Total amine [poly (m-phenylene-m-xylylenediamine)], etc. All I aromatic polyfluorene (aromatic polyamine), etc.] and the like. Polyamine resins further include polyamines using dimer acids as dicarboxylic acid components, polyamines that use a small amount of polyfunctional polyamines and / or polycarboxylic acid components to introduce branched chain structures, and modifications. Polyamines (N-alkoxymethylpolyamines, etc.), high-impact polyamines obtained by mixing or graft-polymerizing modified polyolefins. In polyamide resins, the ratio of the terminal NH2 group to the terminal COOH group is -14-200404878. There is no particular limitation on the ratio. For example, a hydrogen atom with a terminal amino group and a hydrogen atom at the α-carbon atom position constitute an active hydrogen atom. In this case, it can be selected from the group consisting of terminal amine group / terminal carboxyl group = 10/90 to 100/0 (molar ratio), preferably about 20/8 to 95/5 (molar ratio), and more preferably 25/7 5 ~ 95/5 (Molar ratio) In addition, when the active hydrogen atom is constituted only by the hydrogen atom of the terminal amine group, the terminal amine group / terminal carboxyl group = about 50/50 to 100/0 (mole ratio), preferably 60/40 to 95/5 (mole (Ratio), more preferably 70/30 ~ 95/5 (Molar ratio). (2) Polyester resin Although the polyester resin may be an aliphatic polyester resin, an aromatic polyester resin is usually used, for example, a poly (alkylene) polyaryl resin or a saturated aromatic polymer is used. Ester-based resin. Aromatic polyester resins include poly (alkylene) polyaryl resins [such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and other polyterephthalates. C2_4 alkylene dicarboxylic acid dicarboxylic acid; C2_4 alkylene terephthalate corresponding to the polyalkylene terephthalate (such as polyethylene naphthalate); Poly (1,4-cyclohexyldimethylene terephthalate) (pct)]; polyphenols obtained by polycondensation with bisphenols (bisphenol A, etc.) and aromatic polydicarboxylic acids (terephthalic acid, etc.) Aromatic ester resins (such as polyarylate resins); fully aromatic or liquid crystal aromatic polyesters (such as liquid crystal polyesters using parahydroxybenzoic acid, etc.). The polyester resin may be a copolyester containing an alkylene aryl ester unit as a main component (for example, 50% by weight or more). Examples of the copolymerization component of the copolyester include ethylene glycol, propylene glycol, butylene glycol, adipic acid, and the like. C2_6 ethylene glycol, (poly) oxy C 2 · 4 ethylene glycol, phthalic acid , A-15-15 200404878 asymmetric aromatic dicarboxylic acid such as phthalic acid or its anhydride, adipic acid and other c6_12 aliphatic dicarboxylic acid. In addition, a small amount of a polyol and / or a polycarboxylic acid may be used to introduce a branched chain structure into the linear polyester. If the aromatic polyester-based resin does not have the above-mentioned active atom at a specific concentration, a modified polyester-based resin modified with a modifying compound having an active atom (for example, having a group selected from an amine group and an oxygen group) may also be used. An aromatic polyester resin of at least one of the alkylene groups). Active atoms, especially compounds having active hydrogen atoms, may be exemplified: polyamines [aliphatic diamines, such as ethylene diamine, trimethylene diamine, propylene diamine, tetramethylene diamine Φ Number of carbon atoms such as amine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane Linear or branched chain alkylene diamines of about 2 to 10; alicyclic diamines, such as: isophorone diamine, bis (4-amino-3-methylcyclohexyl) methane, Bis (aminomethyl) cyclohexane, etc .; aromatic diamines, such as: phenylenediamine, xylylenediamine, diaminodiphenylmethane, etc .; polyalcohols [eg, ethyl C2_6 alkylene glycols such as diols, propylene glycol, butanediol, and hexanediol; (poly) ethylene oxide glycol, (poly) oxytrimethylene glycol, (poly) oxypropylene glycol, (poly ) Oxidized tetramethylene glycol, etc. (Poly) oxidized c2_4 Diphenyl glycols, etc.]. The modification can be achieved, for example, by heating and mixing the polyester resin and the modified compound, and then using amidation, esterification, or ether exchange reaction. The degree of modification of the polyester-based resin may be a functional group (hydrocarbon group or carboxyl group) of the polyester-based resin depending on the amount of active nitrogen atoms in the compound, and may be, for example, a modified compound. Mol is preferably 0.2 to 15 moles, and more preferably 0.3 to 1 mole. When used for transesterification, the amount of poly-16-200404878 alcohol used may be about 1 to 50 parts by weight, preferably about 5 to 30 parts by weight, based on 100 parts by weight of the polyester resin. (3) Poly (thio) ether-based resin Poly (thio) ether-based resin includes polyoxyalkylene-based resin, polyphenylene-ether-based resin, polythio-based resin (polythioether-based resin), and polyetherketone-based resin. The polyoxyalkylene resin system includes: polyoxymethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxymethylene glycol-polyoxypropylene glycol block copolymer. In addition: Zhisiya Methyl monoalcohol polyoxy C2-4 is based on diols. Preferred polyether-based resins include polyacetal-based resins, polyphenylene-ether-based resins, polysulfide-based resins, and polyetherketone-based resins. (3a) Polyacetal resin Polyacetal resin may be a homopolymer (a separate monomer polymer of formaldehyde) or a copolymer (trioxane, ethylene oxide, and / or 1). , 3-monooxapentane copolymer, etc.). In addition, the ends of the polycondensation resin can be blocked to stabilize it. (3b) Polyphenylene ether resin Polyphenylene ether resin contains various resins containing 2,6-dimethylphenylene oxide as the main component #, such as 2,6-dimethylphenylene oxide and Copolymers of phenols, modified resins in which styrene resins are mixed or grafted. Other modified polyphenylene ether-based resins include, for example, polyphenylene ether / polyamine-based, polyphenylene ether / saturated polyester, polyphenylene ether / polyphenylene sulfide, and polyphenylene ether / polyolefin. It is possible that “modification using the present vinyl resin” may cause the heat resistance of the polyphenylene ether resin to decrease, which may cause deformation due to heating during the vulcanization process. In addition, the addition of this vinyl-based resin may adversely affect the adhesion between rubber and poly-17-200404878 benzoic acid-based resin, so it is not suitable to add an excessively heavy styrene-based resin. On the other hand, polyphenylene ether-based resins have low melt fluidity, and if they are not used in combination with styrene-based resins, their moldability will decrease. Based on these viewpoints, the ratio of the styrene-based resin should be 50 to 50 parts by weight, preferably 3 to 100 parts by weight, and more preferably 5 to 50 parts by weight based on 100 parts by weight of the polyphenylene ether resin. Servings. (3c) Polysulfide-based resin (polythioether-based resin) The polysulfide-based resin is not particularly limited as long as it is a resin having a sulfur group (_S-) in the polymer chain. Examples of such resins include polyphenylene sulfide resins, polydisulfide resins, polysulfide biphenylene resins, polysulfide ketone resins, polysulfide resins, and the like. In addition, the polysulfide-based resin may have a substituent such as an amine group like poly (aminosulfide propylene). A preferred polysulfide-based resin is a polyphenylene sulfide resin. (3d) Polyetherketone resin

Examples of the polyetherketone resin include polyetherketone resins obtained by polycondensation of dihalobenzophenone (dichlorobenzophenone, etc.) and dihydrobenzophenone, and dihalobenzophenone and hydroquinone. Polyetheretherketone resin and the like obtained by polycondensation. (4) Polycarbonate resin Polycarbonate resin can also be used as aliphatic polycarbonate resin, but aromatic polycarbonate resin is usually used. For example, it is made of aromatic hydroxy compounds (bisphenol A, bisphenol F, bisphenol compounds such as bisphenol AD, bisphenol S, etc.), aromatic polycarbonates and the like obtained by reaction with carbochlorine or carbonic acid diesters (dialkyl carbonates such as diphenyl carbonate and the like). (5) Polyimide resin-18-200404878 Polyimide resins include: thermosetting polyimide-based resins, such as aromatic tetracarboxylic acids or their wild (benzophenone tetracarboxylic acid, etc.), Polyimide resins, polyimide resins, polyesterimine resins, etc., obtained by the reaction of a group diamine (diaminodiphenylmethane, etc.). (6) Poly code resin

Examples of the polyfluorene resin include polymaple resins and polyether resins obtained by polycondensation of dihalodiphenyl maple (dichlorodiphenyl maple, etc.) 'and bisphenols (bisphenol A or a metal salt thereof). , Poly Allyl Maple Resin (Product Name: r ADAL

(7) Polyurethane-based resin Polyurethane-based resins can be prepared by reacting diisocyanates, polyalcohols (especially glycols), and chain extenders when necessary. Two different

Examples of the cyanate esters include aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; 1,4-cyclohexane diisocyanate and isophorone Cycloaliphatic diisocyanates such as diisocyanate; aromatic diisocyanates such as phenylene diisocyanate, methylphenylene diisocyanate, 4,4, -diphenylmethane diisocyanate; aromatics such as xylylene diisocyanate Aliphatic diisocyanates and the like. Diisocyanates may also be substituted with an alkyl group (e.g. methyl) in the main chain or ring. Diols are available: polyester diols [C4_! 2 aliphatic dicarboxylic acid components such as adipic acid, C2_4 aliphatic diol components such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, etc., from ε- Polyester diols obtained from C4_i 2 lactone components such as caprolactam], polyether diols [polyethylene glycol, polypropylene glycol, polyethylene oxide-polyoxypropylene block copolymer, polyoxysilane Methyl glycol, bisphenol A-epoxy-19-200404878 alkane adduct, etc.]; polyester ether glycol [part of the glycol component is a polyester glycol using the above polyether glycol] and the like. As for the chain elongating agent, in addition to 0-alkylene glycols such as ethylene glycol and propylene glycol, hexamethylene diamines can also be used. Diamines can be exemplified by aliphatic diamines, such as ethylene diamine, trimethylene diamine, pentamethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, 1,7-diaminoheptane, 1,8-diaminooctane and other straight or branched chain alkylene diamines having 2 to 10 carbon atoms; diethylene triamine, triethylene Linear or branched polyalkylene polyamines, such as ethyltetraamine, tetraethylene pentamine, and propylene triamine; alicyclic Φ diamines, such as isophorone diamine , Bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, etc .; aromatic diamines, such as: phenyldiamine, xylylenediamine, di Amino diphenylmethane and the like. (8) Polyolefin-based resins Polyolefin-based resins include, for example, polyethylene, polypropylene, and ethylene-propylene

Copolymers, olefins such as poly (methylpentene-1) alone or copolymers, copolymers of olefins and copolymerizable monomers (ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- ( (Meth) acrylate copolymers, etc.). These polyolefin-based resins can be used singly or in combination of multiple types of rain. Preferred polyolefin-based resins include polypropylene-based resins having a propylene content of 50% by weight or more (especially 75-1000% by weight), such as polypropylene, propylene-ethylene copolymers, and propylene-butene copolymers. Polymers, propylene-ethylene-butene copolymers, and the like. It is preferable that the 'poly-smoke-based resin is crystalline. (9) Halogen-containing vinyl resins Examples of halogen-containing vinyl resins include polyvinyl chloride, polyvinylidene chloride-200404878 vinyl chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymerization. Materials, such as vinyl chloride-based resins, such as polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, copolymers of tetrafluoroethylene and copolymerizable monomers, and the like. The preferred halogen-containing ethylene-based resin is a fluorine-containing ethylene-based resin (e.g., polyvinyl fluoride, polyvinylidene fluoride, etc.). (10) Styrene-based resins The ethylenic-based resins include: styrenic monomers alone or copolymers [waterborne ethylene, ethylbenzene-vinyltoluene copolymer, styrene-methylstyrene Copolymers, etc.]; copolymers of styrene-based monomers and copolymerizable monomers [styrene-acrylonitrile copolymer (AS resin), (meth) propionic acid ester-styrene copolymer (MS resin, etc.), Styrene-maleic anhydride copolymer, styrene-butadiene copolymer and other styrene copolymers]; impact-resistant polystyrene (HIPS), acrylonitrile-butadiene-styrene-flammable copolymer (ABS resin ), Acrylonitrile-acrylic rubber-styrene copolymer (acrylonitrile-acrylate_styrene copolymer) (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS), acrylic -Ethylene Acrylic Storage Rubber-Styrene;) ¾ Copolymer (AES), Acrylonitrile- (styrene-Ethyl Acetate Copolymer) -Styrene Ethylene Copolymer (Acrylonitrile_vinyl acetate-styrene copolymer) (AXS resin) and other styrene-based graft copolymers. (1 1) (Meth) acrylic resin (meth) acrylic resin includes: (meth) acrylic monomer alone or copolymer, (meth) acrylic monomer and copolymerizable monomer Copolymers, etc. (Meth) acrylic single systems include: (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (methyl 200404878) isopropyl acrylate, and butyl (meth) acrylate Ci Q alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, C5_] 0 cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, (meth) C6_1 () aryl (meth) acrylates such as phenyl acrylate, hydroxy C2-10 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, Glycidyl (meth) acrylate and the like. Copolymerizable monomer systems include vinyl monomers such as vinyl acetate and vinyl chloride, styrene monomers such as styrene and α-methylstyrene, and the like.

(12) Thermoplastic elastomer

The thermoplastic elastomer system includes: polyamide elastomer [copolymer with polyamide as hard phase and aliphatic polyester as soft phase], polyester elastomer [with polyalkylene acrylate as hard phase, Copolymer with aliphatic polyether or aliphatic polyester as soft phase], polyurethane elastomer [Polyurethane with short chain ethylene glycol as hard phase, aliphatic polyether or fatty Group polyesters are copolymers with a soft phase, for example: polyester polyurethane elastomers, polyether polyurethane elastomers, etc.], polystyrene elastomers [with polystyrene blocks as Hard phase, block copolymer with diene polymer block or hydrogenated block as soft phase], polyolefin elastomer [with polyethylene or polypropylene as hard phase, ethylene-propylene rubber or ethylene- The propylene diene rubber is an elastomer with a soft phase, an olefin-based elastomer composed of a hard phase and a soft phase with different degrees of crystallinity, etc.], a polyvinyl chloride-based elastomer, and a fluorine-based thermoplastic elastomer. Aliphatic polyethers can be used: (poly) oxy C2.4 alkylene glycols [for example: (poly) oxyethylene glycol, (poly) oxytrimethylene glycol, (poly) propylene oxide glycol, ( Poly) tetramethylene glycol, especially (-22-200404878 poly) ethylene oxide glycol], etc., aliphatic polyesters can be used for polyester diols, etc. described in the polyurethane resin section . These thermoplastic elastomers can be used alone or in combination of two or more. When the thermoplastic elastomer is a block copolymer, the block structure is not particularly limited, and may be a triblock structure, a multiblock structure, a star block structure, or the like. The better thermoplastic elastomer systems include polyamide elastomers, polyester elastomers, polyurethane elastomers, polystyrene elastomers, and polyolefin elastomers.

[Resin having a crosslinkable group] A resin having a crosslinkable group can be roughly classified into a thermoplastic resin having an unsaturated bond (polymerizable or crosslinkable unsaturated bond) and a thermosetting resin having a crosslinkable functional group. Among them, the crosslinkable resin may have the aforementioned unsaturated bond and a crosslinkable functional group. [Thermoplastic resin with unsaturated bond]

The present invention can also be applied to the combination of various thermoplastic resins and rubbers containing unsaturated bonds active to radicals at specific concentrations. Therefore, if the thermoplastic resin is a resin having no unsaturated bond or a resin having a concentration of unsaturated bonds that does not reach a specific concentration, it can also be used as a modified resin or a modified resin in which unsaturated bonds are introduced. The above unsaturated bond is not particularly limited as long as it can be activated by a vulcanizing agent (such as a radical generator), and may be various bonds that exhibit crosslinkability or polymerizability by imparting heat or light (for example, Polymerizable unsaturated bonds). Such an unsaturated bond or a unit having an unsaturated bond can also be obtained through a linking group (ether bond (-〇-), ester bond [(-OC (= 0)-, -c (= 〇) 〇-),醯 Amine bond [-NHCO-; -CONH-], imine bond (-NH-), -23-200404878 carbamate bond NHC (= 0) 0-], urea bond, diuretic bond, etc. ) And bonded to a thermoplastic resin. In addition, the unsaturated bond or its unit may be located at the end of the resin (the end of the main chain) and / or the side chain. It may also be located at the main chain of the resin. Further, it may be located at a different part of the combination. Examples of the group having an unsaturated bond include vinyl, 1-propenyl, isopropenyl, 1-butenyl, allyl, 2-methyl-2-propenyl, 2-butenyl, etc. C2_6 chain flammable group; C2-6 chain such as 4-ethenylphenyl, 4-isopropenylphenyl

Alkenyl-C6_2Garyl; C6_2Garyl-c2_6 alkenyl such as styryl; ethynyl, 1-propynyl, 1-butynyl, propargyl, 2-butynyl, 1-methyl- 2-Propynyl and other C2_6 alkynyl groups; vinylidene, methyl vinylidene, ethyl vinylidene, 1,2-dimethyl vinylidene and other mono- or bis Cl_6 alkyl vinylidene, chloroethynyl, etc. Vinylidene which may have substituents such as halogenated vinylidene; vinylidene; ethenylidene.

Examples of the thermoplastic resin having an unsaturated bond include: (1) a compound having a reactive group (A) and an unsaturated bond and a reactive group (B) having a reaction with the reactive group (A); Resin produced resin; (2) thermoplastic resin that introduces unsaturated bonds by copolymerization or copolycondensation; (3) polymer blends formed from resins with unsaturated bonds and resins; (4) by Various organic reactions (for example, introduction of vinyl by Reppe reaction using acetylene, introduction of unsaturated bonds by organometallic reagents such as vinyl lithium, introduction of unsaturated bonds by coupling reaction, etc.) Saturated bond thermoplastic resin, etc. Preferred resins are the above (1), (2), or (3). In the above resin (1), a polymerizable compound having at least one reactive group (A) and at least one unsaturated bond, and a reactive group (A) having the above polymerizable -24-200404878 compound have By reacting a resin having a reactive reactive group (B), an unsaturated bond can be introduced into the resin. The representative reactive group (A) of the polymerizable compound may be exemplified by (A 1) a hydroxyl group, (A2) a carboxyl group or an anhydride group thereof, (A3) an amine group, (A4) an epoxy group, and (A5) isocyanate Acid group and so on. Examples of the combination of the polymerizable compound reactive group (A) and the resin-reactive group (B) include the following combinations. The parentheses indicate the bond form between the reactive group (A) and the reactive group (B). (A1) hydroxyl group: (B) carboxyl group or its anhydride group (ester bond), isocyanate group (ester bond) φ (A2) carboxyl group or its anhydride group: (B) hydroxyl group (ester bond), amine group (amidoamine) Bond), epoxy group (ester bond), isocyanate group (amido bond) (A3) amino group: (B) carboxyl or its anhydride group (amido bond), epoxy (imine bond), iso Cyanate group (amido bond) > (A4) epoxy group:

(B) carboxyl group or its anhydride group (ester bond), amine group (imine bond) (A5) isocyanate group: (B) hydroxy group (ester bond), carboxyl group or its anhydride group (amido bond), amine group (Ammonium amine bond) As for the reactive group (B), in the polyamido resin, for example, the remaining carboxyl group or amine group may be used as the reactive group (B). In the polyester resin, for example, the remaining group may be used. A carboxyl group or a cationic group is used as a reactive group. In the poly (thio) ether-based resin, the remaining hydroxyl group, hydrogenthio group, and the like can also be used as the reactive group (B). • 25-200404878 In polyacetal, the remaining hydroxyl group can be used as a reactive group (B). In polycarbonate resins, the remaining hydroxyl groups can be used as reactive groups (B), and in polyfluorene imine resins, the remaining carboxyl groups or acid anhydride groups, amine groups, and imine groups can be used as reactive groups. Base (B). In the polyurethane resin, for example, the remaining hydroxyl group, amine group, and isocyanate group can be used as the reactive group (B). In the (meth) acrylic resin, the reactive group is used. The monomer (B) is used as a copolymerization component, whereby the above-mentioned reactive group (B) can be introduced.

Examples of the polymerizable compound include compounds containing a hydroxyl group [for example, C3_6 alkynol such as allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, C3_e alkynol such as propargyl alcohol, ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, butanediol (meth) acrylate, etc. C2_6 alkylene glycol mono (meth) acrylate, mono (meth) Polyoxymono (meth) acrylic acid C2-6 alkylene glycols such as diethylene glycol acrylate, C2-6 alkenyl phenols such as 4-hydroxystyrene, 4-hydroxy-α-methylstyrene, dihydroxystyrene, B

Alkenyl naphthol, etc.]; carboxyl groups or compounds containing acid anhydride groups [eg C3-6 alkenyl carboxylic acids such as (meth) acrylic acid, crotonic acid, 3-butenoic acid, itaconic acid, maleic acid, maleic anhydride, etc C4_8 alkenyl dicarboxylic acid or its anhydride, unsaturated aromatic carboxylic acids such as vinyl benzoic acid, cinnamic acid, etc.]; compounds containing amine groups (for example, C3_6 alkenylamines such as allylamine, 4-amine groups Styrene, diaminostyrene, etc.); compounds containing epoxy groups (eg, allyl glycidyl ether, glycidyl (meth) acrylate, etc.); isocyanate compounds (eg, isocyanate Vinyl ester, etc.). In addition, in the above resin (1), if a resin having no reactive group (B) or a resin having a low concentration of the reactive group (B) is used, it is also possible to introduce anti-26-26200404878

Responsive group (B) to modify or modify the resin. The method of introducing a reactive group (B) into a resin can be used: (i) when manufacturing a resin, a monomer having a reactive group (B) (such as the polymerizable compound exemplified above), and a resin material (or A method of copolymerizing a monomer or oligomer of a resin raw material, (ii) introducing various organic reactions such as a carboxyl group by an oxidation reaction, a halogenation method, and a grafting method of a polymerizable monomer. In addition, in the ethylene polymerization resin, a monomer having the above-mentioned reactive group (B) is usually used as a copolymerization component. In many cases, the above-mentioned reactive group (B) is introduced. Any of the resins can easily introduce the reactive group (B) by a graft reaction of a polymerizable compound having the reactive group.

In the above resin (2), the method for introducing unsaturated bonds can be exemplified as follows: When preparing a condensation resin (such as a polyamide resin, a polyester resin, etc.), 'as a part of the reaction component (common monomer) Compounds that have polyfunctional unsaturated bonds [for example: aliphatic unsaturated dicarboxylic acids (maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citric anhydride, C4_1G aliphatic unsaturated dicarboxylic acids such as Zhongkang acid, etc.) and unsaturated polycarboxylic acids; aliphatic unsaturated diols (C4_10 aliphatic unsaturated diols such as 2-butene-1,4-diol, etc.), etc. Unsaturated polyhydric alcohols, etc.] A method of copolycondensation (or copolymerization). In addition, in addition polymerization resins (such as olefin resins), monomers having a conjugated unsaturated bond (for example, 1,3 -Butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, chloroprene and other conjugated Cm chain dienes) Copolymerization method and so on. In the above resin (3), a thermoplastic resin (A) is mixed with a tree -27-200404878 lipid (B) having an unsaturated bond to form a polymer blend (or resin composition). The unsaturated bond is introduced into the thermoplastic resin. The thermoplastic resin (A) is not particularly limited, and examples thereof include various thermoplastic resins [for example, thermoplastic resins (polyamine-based resins, polyester-based resins, etc.) to be described later]. The thermoplastic resin (A) may be a saturated resin having no unsaturated bond or a resin having an unsaturated bond. Examples of the resin (B) having an unsaturated bond include the above-mentioned resins (1), (2), or (4), such as thermoplastic resins having unsaturated bonds introduced therein, and rubbers containing unsaturated bonds (for example, polybutadiene, Polyisoprene, polypentene, polyheptene, polyoctene, poly (3-methyloctene), polydecene, poly3-decene, polydodecene, etc. Base; copolymers of C4-15 alkenes such as butadiene-isoprene copolymers; rubber-modified polyolefins such as butadiene-modified polyethylene; etc.). The polyC4_15 alkenylene group may also be a cycloolefin type (for example, a C5_2 () cycloolefin system having substituents such as cyclopentene, cycloheptene, cyclooctene, cyclodecene, and dodecylcycloene). Etc.) It is produced by metathesis polymerization, hydrogenation of a part of polyalkenylene, etc. In the resin (4), the ratio of the resin (B) is within a range where unsaturated bonds can be introduced at a specific concentration for the polymer blend, and is, for example, resin (A) / resin (B) (weight ratio). = 5/9 5 to 95/5, preferably 30/7 0 to 95/5, and more preferably about 50/50 to 95/5. In addition, when the resin (B) uses a rubber containing unsaturated bonds (such as polyoctene, etc.), the ratio of the resin (B) can be freely selected within a range that does not impair the properties of the resin (A). For example, the resin ( A) / resin (B) (weight ratio) 50/50 to 95/5, preferably 60/40 to 95/5, and more preferably about 70/30 to 95/5. 200404878 In addition, in the resin composition of the above resin (A), the resin (A) and the resin (B) can also be formed into a polymer alloy (a polymer alloy with a sea-island structure, etc.). Examples of thermoplastic resins include: Amine resin, polyester resin, polythioether resin (polyacetal resin, polyphenylene ether resin, polysulfide resin, polyetherketone resin, etc.), polycarbonate resin, polyimide Polycondensation-based thermoplastic resins such as resins, polyfluorene-based resins, and polyurethane-based resins; ethylene-based thermoplastics such as polyolefin resins, halogen-containing vinyl resins, styrene resins, and (meth) acrylic resins Resin; thermoplastic 9-elastomer, etc. These resins may be used alone or in combination of two or more. When two or more kinds are used in combination, the resin composition may form a composite resin composition such as a polymer alloy.

Although the ratio of unsaturated bonds varies depending on the type of resin and the degree of activation of the unsaturated bonds, for example, the resin has, for example, an average of 0.1 or more (for example, 0.1 to 1,000) per molecule, preferably 1 on average Or more (for example, 1 to 100 or more), more preferably 2 or more (for example, about 2 to 50) on average. The concentration of unsaturated bonds is, for example, 0.001 to 6.6 moles for 1 kg of resin, preferably 0.01 to 4 moles (for example, 0.001 to 1 mole), and more preferably 0.02 to 2 moles (for example, 0.05 ~ 0.5 Mor)). In addition, when unsaturated bonds are introduced according to the polymer blend, although the number of unsaturated bonds can be calculated according to the weight fraction of each resin, making the unsaturated bonds an average 値, but it is more convenient to make the resin composition The number of unsaturated bonds in the substance is calculated as the concentration of ears / kg. (Thermosetting resin having a crosslinkable functional group) -29-200404878 The thermosetting resin is a functional group (for example, methylol, Alkoxymethyl, epoxy, isocyanate, etc.). Examples of such thermosetting resins include polycondensation or addition polycondensation resins (phenol resins, amine-based resins, epoxy resins, thermosetting polyimide resins, thermosetting polyurethane resins, silicone resins, etc. ), Addition polymerization resin (unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, thermosetting (meth) acrylic resin, etc.). The thermoplastic resins can be used alone or in combination of two or more. Φ (13) Phenolic resin

Although the phenol resin includes a phenol resin, a phenol resin (1. ^ 〇1), and the like, a phenol resin is usually used. Phenolic resins can be prepared by reacting phenols with aldehydes in the presence of an acid catalyst. Examples of phenols are: phenol, o-, m-, or p-cresol, 2,5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, ethylphenol , Cl_4 alkyl benzene, such as propylphenol, dihydroxybenzene, resorcinol, naphthol, etc. These phenols can be used alone or in combination of two or more. Examples of the aldehydes include: formaldehyde, polymethylamine, aliphatic aldehydes such as acetaldehyde and propionaldehyde; aromatic aldehydes such as benzaldehyde and salicylaldehyde; and the like. These aldehydes can be used individually or in combination of 2 or more types. U4) Amine-based resins Amine-based resins are usually prepared by reacting compounds containing amine groups with aldehydes (for example, aliphatic aldehydes such as formaldehyde, acetone, and propionaldehyde, and aromatics such as phenylacetaldehyde). Amine resins include: urea resin (urea resin obtained from the reaction between urea and aldehydes), aniline resin (from aniline, naphthylamine, toluene-30-200404878 amine, dimethylaniline, N, N_dimethylamine Anilines such as aniline and benzidine, aniline resins obtained by reaction with stilbene, etc.), melamine resins (melamine resins obtained by reaction of melamines with aldehydes, etc.), guanamine resins (by benzoguanidine Guanamines such as amines, acetoguanamine, and metformin, and guanamine resins obtained by reaction with aldehydes, etc.). (15) Epoxy resins Epoxy resins include bisphenol epoxy resins, phenolic epoxy resins, and amine epoxy resins.

Examples of the bisphenol epoxy resin include glycidyl ethers such as 4,4-bisphenol, 2,2-bisphenol, bis | fractional ρ, bisphenol AD, and bisphenol A. Examples of the phenolic lacquer resin that constitutes the phenolic lacquer type epoxy resin include the phenolic lacquer resin obtained by the reaction of benzene and phenols described in the section on the lacquer resin. Examples of the amine component constituting the amine-based epoxy resin include aromatic amines such as aniline and toluidine, aromatic diamines such as diaminobenzene, xylylenediamine, aminohydroxybenzene, and diaminodiphenyl Methane, etc.

(16) Thermosetting polyesterimine-based resins Thermosetting polyesterimine-based resins include the resins described in the above-mentioned polyesterimine-based resins section (for example, curable resins having a number of ring-closeable imine groups) Composition). (1 7) Thermosetting polyurethane-based resin The thermosetting polyurethane-based resin includes the resin described in the above-mentioned polyurethane-based resin section (for example, a resin having a plurality of free isocyanates). Based prepolymer, and hardening resin (31-200404878 composition) composed of polyester components such as polyester polyol. (18) Silicone-based resin Shixian-based resin contains: a unit represented by the formula: RaSi〇 (4a) / 2 (where the coefficient a is about 1.9 to 2.1); and a unit represented by the formula: (where The coefficient b is about 0.9 to 1.1). In the formula, R system includes, for example, Cm such as methyl, ethyl, propyl, and butyl. Halogenated Cl_1G alkyl such as alkyl, 3-chloropropyl, 3,3,3-trifluoropropyl, C2_1 () alkenyl such as vinyl, allyl, butenyl, phenyl, tolyl, naphthalene Cm aryl groups such as alkyl, c3_1 () cycloalkyl groups such as cyclopentyl and cyclohexyl, Cmaryl-Ci4 alkyl groups such as phenylφmethyl and phenethyl. (19) Unsaturated polyester-based resin Unsaturated polyester-based resin includes: using an unsaturated dicarboxylic acid or an anhydride thereof (for example, maleic acid, maleic anhydride, fumaric acid, etc.) in the polyester resin; Unsaturated polyester with dicarboxylic acid. (20) Vinyl ester resin

Vinyl ester resins include polymers obtained by reacting the above-mentioned epoxy resin with (meth) acrylic acid, and polymers obtained by reacting polyhydric phenols with glycidyl (meth) acrylate. (21) diallyl phthalate resin diallyl phthalate resins include phthalates such as diallyl phthalate and diallyl isophthalate Resins and the like obtained from diallyl formate resin monomers. (22) Thermosetting (meth) acrylic resins Thermosetting (meth) acrylic resins are resins described in the (meth) acrylic acid-32-200404878 dilute acid resins section (reactive groups with hydroxyl groups and other reactive groups). (Meth) acrylic resin and hardener resin composition, etc.) Also, if the resin is a thermoplastic resin and a resin having a crosslinkable group (especially a crosslinkable resin other than a thermosetting resin), It may have several hydrogen atoms (active hydrogen atoms) or sulfur atoms (active sulfur atoms) that exhibit high activity with respect to radicals (hereinafter, these hydrogen atoms and sulfur atoms may be referred to as active atoms). The resin system may have an active atom selected from at least one of the above-mentioned active hydrogen atom and active sulfur atom, and may also have active atoms of both φ active hydrogen atom and active sulfur atom. If a resin having the above-mentioned active atoms is used, the vulcanized rubber layer can be made stronger, and the bond with the vulcanized rubber member can be made stronger. That is, the resin having an active atom 'may have an active atom having a certain 値 (e.g. 0.006, preferably 0.000) or more in the orbital interaction energy coefficient s represented by the following formula. The orbital interaction energy coefficient S of the better active atom is 0.006 to 0.06, preferably 0.007 to 0.05 (especially 0.001 to 0.045). The active proto

The number of sons depends on the bonding portion (terminal, branched chain, or main chain, etc.) of the functional group with active atoms. For example, there can be an average of two or more (about 2 to 10,000) in a molecule of resin. The average number is preferably 2.5 or more (about 2.5 to 5,000), and more preferably the average is 3 or more (about 3,000 to 10,000): S = (CHOMO, n) / | Ε (: -Εη〇ΜΟ, π | + (CLUMO, n) ** / | Ec-ELUMO, n I (1) [where EC, CH0M0, n 'EHOM0, n, CLUM0, n, and ELUMOji are -33-200404878 by Calculated by the semi-empirical molecular orbital method MOPACPM3, Ec represents the radical orbital energy (eV) of the radical generator as a vulcanizing agent, C Η Ο Μ Ο, and η represents the η that constitutes the basic unit of the thermoplastic resin. The molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of each active atom, EH0M0, nS represents the orbital energy (eV) of the above HOMO, CLUM0, n represents the lowest empty molecular orbital (LUMO) of the nth hydrogen atom above The molecular orbital coefficient, ELUM0, n represents the orbital energy (eV) of the above LUMO].

The basic unit in formula (1) means a model molecular structure formed by a polymer terminal and about 1 to 3 repeating units. In other words, when MOPACPM3 is used to calculate related polymer compounds, since the number of molecules that make up the molecule is too large, it is difficult to calculate the molecule itself. Therefore, a branch structure model (basic unit) formed by about 2 to 3 repeating units can also be used for calculation. For example, the branching structure (repeated units) of polybutylene terephthalate (PBT) can generally have the chemical formula-(CH2-CH2-CH2-CH2-0-C (= 0) -C6H4-C (= 0) -0) n-, but in the above formula (1), for convenience, the basic unit may also be taken as 11〇-0: 112-ch2-ch2-ch2-oc (= o) -c6h4-c (= o) oh. In addition, the orbital energy Ec (eV) of the radical of the radical generator is preferably calculated as MOPACP.M3 according to the branching structure of the radical, but it is also convenient to use a specific one according to the type of the radical generator. value. For example, if the radical generator is an organic peroxide, then Ee = -8 eV, if it is an azo compound, then Ee = -5 eV, if it is an organic compound containing sulfur other than sulfur, then Ec = -6 eV. The orbital interaction energy coefficient S is -34-200404878 hydrogen atom of a specific tritium (eg 0.006) or more. When the radical generator is an organic peroxide, it includes: amine group (-NH2) (such as terminal amine group), Amine group (-NH-) (for example, main chain or terminal imine group, -NH- group of amidine bond, etc.), hydrogen thio group (-SH), methyl group (_CH3), methylene group (-CH2- ) (Methylene adjacent to the electron-attracting group, that is, active methylene), hydrogen atom such as methine (-CH = 0 (main chain or terminal methine)).

In addition, the orbital interaction energy coefficient S is a sulfur atom (active sulfur atom) with a specific thorium (e.g. 0.006) or more. When the radical generator is an organic peroxide, it includes a sulfur group (-S-) and a hydrogen sulfur group. (-SH), alkylthio (methylthio, ethylthio% Ci_4 垸 thio, etc.), sub-mine (-SO-) and other sulfur atoms.

Examples of the methyl group include a methyl group bonded to an alkylene chain, a cycloalkylene chain, or an aromatic ring, and a methyl group (methoxymethyl group) bonded to an oxygen atom. Examples of the methylene group include, for example, a methylene group adjacent to an oxygen atom of a polyoxyalkylene unit such as a polyoxymethylene unit and a (poly) oxyethylene unit, and also an amine group or an imine group. And so on. Examples of the methine group include, for example, an methine group adjacent to the α-position of an amine group or an imine group, and an methine group to the α-position of the amine cycloalkyl group. The number of active atoms is not a single molecule, but a mixture of many different molecules such as structure or chain length. Therefore, the main basic units that can be expected can be calculated. For example, active hydrogen contained in a polymer (Polyamide 66) with repeating units-[NH- (CH2) 6-NH-C (= 0)-(CH2) 4- (C = 0)] n- The number of atoms can be calculated according to the basic unit of the model NH2- (CH2) 6-NH_C (= 0)-(CH2) 4-C (= 〇) -〇H, and when the radical generator is an organic peroxide, The two hydrogen atoms of the terminal NH2 group are -35-200404878 active hydrogen atoms (ie, S g 0.006). At this time, regarding the average number N of active hydrogen atoms in one molecule of polyamide 66, the ratio of the terminal NH2 group to the terminal COOH group of the polymer (polyamine 66) as an aggregate can be calculated according to the following formula (2 ) To calculate: N = 2xA (2) [where A represents the number of average terminal NH2 groups in a molecule]. For example, in the case of a terminal N Η 2 group / terminal / C Ο Ο Η group == 1/1 (molar ratio), the number of terminal NΗ2 groups in a molecule A = 1, the number of active hydrogen atoms in a molecule N = 2. In addition, when the terminal NH2 group / terminal / COOH group = 1/2 (9 mole ratio), the number of terminal NH2 groups in one molecule A = 2/3, and the number of active hydrogen atoms in one molecule N = 4 / 3.

In addition, when the resin is a mixed resin composed of a plurality of resins having mutually different numbers of active atoms, the number of active atoms of the mixed resin may be expressed as an average number of active atoms of each resin. In other words, the number of active atoms is calculated individually from each resin basic unit constituting the mixed resin, and the average number of active atoms is calculated based on the weight ratio of each resin, thereby calculating the apparent active atom number of the mixed resin. For example, the mixed resin is composed of the N = 2 polyamide 66 (A) and the N = 4/3 polyamide 66 (B), and (A) / (B) = 1/1 ( Moore ratio), the number of active atoms in one molecule of the mixed resin can be regarded as N = 5/3. In addition, if the mixed resin is composed of the above-mentioned N = 2 polyamide 66 (A) and polyamine 66 (C) having carboxyl groups at all terminals (that is, n = 0), and (A) / (C When) = 3/1 (Molar ratio), the number of active atoms in one molecule of the mixed resin can be regarded as N = 3/2. Among the resins exemplified above, resins having such an active atom are package-36-200404878 a. For example, polysaline resin, polyester resin, polyacetal resin, polyphenylene fluorene resin, polysulfide resin, Polyurethane resin, thermoplastic elastomer, amine resin, epoxy resin, etc. In the fe: line tree S, for example, a chlorine atom of a terminal limb group, or a hydrogen atom of a terminal carbon atom bonded to an α-position, a hydrogen atom bonded to an -NΗ- group adjacent to an amine bond Carbon atom hydrogen atom (methylene hydrogen atom or methine hydrogen atom, etc.), especially the terminal amine group hydrogen atom will constitute an active hydrogen atom

In polyester resins 'the methylene hydrogen atom which is usually adjacent to the oxygen atom of the (poly) oxygen radical unit will constitute an active atom. In modified polyester resins' the terminal hydrogen atom of the amine group, or A hydrogen atom of a terminal amine group bonded to a carbon atom at the α-position, a hydrogen atom bonded to a carbon atom adjacent to a -NΗ- group of a fluorenyl bond (methylene hydrogen or methine hydrogen atom) Etc.), especially the hydrogen atom of the terminal amine group will constitute an active hydrogen atom.

In polyacetal resins, for example, the hydrogen atom of a formaldehyde unit, the hydrogen atom of an alkoxy group (particularly a methoxy group) terminated at the end, and especially the hydrogen atom of a formaldehyde unit will constitute an active hydrogen atom. In the resin, for example, a hydrogen atom of a methyl group bonded to a benzene ring will constitute an active hydrogen atom, and in a polyfluorene resin, for example, a sulfur group in the main chain will constitute an active hydrogen atom, respectively. In polyurethane resins, for example, a hydrogen atom (especially a benzyl hydrogen atom) bonded to a main chain or a ring alkyl group of a diisocyanate, a polyol or a polyoxyalkylene glycol A hydrogen atom of an alkylene group, a hydrogen atom of an amino group of a chain elongator, etc. will constitute an active hydrogen atom. In the polyolefin-based resin, the polyolefin-based resin includes, for example, a hydrogen atom of a methylene group of the main chain of -37-200404878, a hydrogen atom of a methyl group branched from the main chain, and the like, which constitute an active hydrogen atom. In a thermoplastic elastomer, for example, a hydrogen atom of an oxyalkylene unit constituting a soft phase may constitute an active hydrogen atom. In an amine resin, for example, an amine group (for example, an amine group constituting melamine, guanamine, etc.) will constitute an active hydrogen atom. In the epoxy resin, for example, a hydrogen atom bonded to a carbon atom constituting an epoxy group will constitute an active hydrogen atom.

The resin composition (especially a resin having a crosslinkable group) required for forming a resin member may contain a crosslinking accelerator to promote crosslinking. The cross-linking accelerator can be selected according to the type of resin. For example, when the resin has a cross-linkable functional group, if an acid, a salt, or a hardener (organic hardener, inorganic hardener, etc.) is used, it can be significant. Promote cross-linking (or hardening

Such crosslinking agents include: radical generators (free radical generators to be described later); acids [fatty acids such as acetic acid, sulfonic acids such as p-toluenesulfonic acid, organic acids such as aromatic fatty acids such as benzoic acid, and inorganic acids such as hydrochloric acid Acids, etc.]; bases [aliphatic amines such as triethylamine, aromatic amines such as aniline, heterocyclic amines such as pyridine, etc.]; organic hardeners [polycarboxylic acids or their anhydrides (such as glyoxal, Malonaldehyde, glutaraldehyde, terephthalaldehyde, etc.); compounds with several aldehyde groups, epoxy compounds (such as alkylene glycol diglycidyl ether, polyoxyalkylene glycol diglycidyl ether , Glycerol triglycidyl ether, trimethylolpropane triglycidyl ether and other compounds with several epoxy groups, etc.); nitrogen-containing compounds [such as urea resin, guanamine resin, amine resins such as melamine resin, the above (7) Diamines and the like described in the polyurethane resin section]; compounds with methylol or alkoxymethyl [Examples -38-200404878 If N-hydroxymethyl (methyl ) Polymers of acrylamide], polyisocyanate Acid esters, etc.]; inorganic hardeners [boric acid or borates (borax, etc.), zirconium compounds, titanium compounds, aluminum compounds, phosphorus compounds, silane coupling agents, etc.]; hardening catalysts (organic tin compounds, organic aluminum compounds, etc.). These crosslinking accelerators can be used alone or in combination of two or more.

In addition, the resin composition used to form the resin member may also contain various additives such as additives or reinforcing agents, stabilizers (ultraviolet absorbers, antioxidants, heat stabilizers), colorants, plasticizers, and lubricants , Flame retardants, antistatic agents, etc. [Rubber member (vulcanized rubber member)] (Rubber)

The rubber member (vulcanized rubber member) can be obtained by molding (vulcanizing) a rubber composition containing a vulcanizing agent and rubber. In the present invention, since various rubbers can be firmly combined, the types of the rubbers are not particularly limited. Examples of the rubber include diene rubber, olefin rubber, acrylic rubber, fluorine-containing rubber, silicon rubber, urethane rubber, epichlorohydrin rubber (epichlorohydrin alone polymer CO, epichlorohydrin and ethylene oxide). Copolymers ECO, copolymers obtained by further copolymerizing allyl glycidyl ether, etc.), chlorosulfonated polyethylene, polyoxypropylene rubber (GPO), ethylene-vinyl acetate copolymer (EAM), Polynorbornene rubber, and such modified rubber (acid-modified rubber, etc.). These rubbers can be used alone or in combination of two or more. From the standpoint of practicality, diene rubber, olefin rubber, acrylic rubber, fluorine-containing rubber, silicon rubber, urethane rubber, and the like are widely used among these rubbers. -39-200404878 Diene-based rubber systems include, for example, natural rubber (NR), isoprene rubber (IR), isobutylene ... isoprene rubber (butyl rubber) (IIR), butadiene rubber (BR), Polymers of diene monomers such as chloroprene rubber (CR); acrylonitrile-butadiene rubber (NBR), nitrile chloroprene rubber

(NCR), nitrile-isoprene rubber (NIR) and other acrylonitrile-diene copolymer rubber; styrene-butadiene rubber (SBR, such as random copolymers of styrene and butadiene, embedded by styrene SB block copolymers composed of segments and butadiene blocks), styrene-chloroprene rubber (SCR), styrene-isoprene rubber (SIR), styrene-diene copolymer rubber, etc. . Diene rubbers also include hydrogenated rubbers such as hydrogenated nitrile rubber (HNBR). The styrene-diene copolymer rubber may be a random copolymer or a block copolymer. The ratio of the styrene component in the styrene-diene copolymer rubber is, for example, 10 to 80% by weight, preferably 20 to 70% by weight, and more preferably 30 to 60% by weight (for example, 40 to 50% by weight). Examples of the olefin-based rubber include ethylene-propylene rubber, etc.

Propylene-diene rubber (EPDM, etc.), polyoctene rubber, etc. Examples of acrylic rubber include rubbers containing alkyl acrylate as a main component. For example, copolymers of alkyl acrylate and chlorine-containing crosslinkable monomer (ACM), copolymers of alkyl acrylate and acrylonitrile (ANM ), Copolymers of alkyl acrylates with carboxyl and / or epoxy-containing monomers, ethylene-acrylic rubber, and the like. Fluorinated rubber can be exemplified ····················································· Copolymer of ethylene and perfluoromethyl vinyl ether -40-200404878 polymer (FFKM), etc. The silicone rubber (Q) is a polyorganosiloxane composed of a unit represented by the formula: RaSiO ^ a ^ 2. In the formula, R system includes, for example, alkyl groups such as methyl, ethyl, propyl, and butyl, 3-chloropropyl, and halogenated Cl · 10 alkyl such as 3,3,3 · trifluoropropyl, vinyl, and olefin. C2_1G alkenyl such as propyl, butenyl, phenyl, methylbenzyl, naphthyl, etc. C6_i2 chain alkyl, cyclopentyl, cyclohexyl, etc. c3_1 cycloalkyl, benzyl, phenethyl, etc. Cm aromatic -Cl_4 alkyl and the like. The coefficient a in the formula is about 1.9 to 2.1. Preferred R is methyl, alkenyl (vinyl, etc.), or fluoroCualkyl. The molecular structure of φ silicone rubber is usually linear, but it may have a branched structure or molecular chain. The main chain of the silicone rubber can be composed of, for example, a polydimethylsiloxane chain, a polymethylvinylsiloxane chain, a polymethylphenylsiloxane chain, and a copolymer of the siloxane units. Chain [Dimethylsiloxane-methylvinylsiloxane copolymer chain, dimethylsiloxane-methylbenzyl radical copolymer bond, dimethylsiloxane-methyl (3 , 3,3 · trifluoropropyl) siloxane copolymer chain, dimethylsilane-methylvinylsilicone compound-methylbenzyloxy compound copolymer chain, etc.]. Both ends of the silicone rubber may be, for example, trimethylsilyl group, dimethylvinylsilyl group, silanol group, tri (^ · 2alkoxysilyl group, etc.) The silicone rubber (Q) series contains : For example, methyl silicone rubber (Mq), vinyl silicone rubber (VMQ), phenyl silicone rubber (pMQ), phenyl vinyl silicone rubber (PVMQ), fluorinated vinyl silicone (VVmq), etc. And silicon rubber is not limited to the above-mentioned high temperature vulcanization (HTV) solid rubber 'also includes: room temperature vulcanization (RTV) or low temperature vulcanization (LTV) silicone rubber -41-200404878 Glue, such as liquid or paste rubber. Polyurethane rubber (u) series includes, for example, polyester-type polyurethane elastomers, polyether-type polyurethane elastomers, etc. Modified rubber series contains : Acid-modified rubbers, such as residual styrene-butadiene rubber (X-SBR), carboxylated nitrile rubber (X_NBR), carboxylated ethylene-propylene (-diene) rubber [X-EP (D) M ] And other rubbers with carboxyl or acid anhydride groups. (Vulcanizing agent)

The above rubber can be vulcanized with various vulcanizing agents, and the type of the vulcanizing agent is not particularly limited. For example, any of sulfur-based vulcanizing agents such as sulfur and sulfur-containing compounds, and non-sulfur-based vulcanizing agents (such as radical generating agents such as organic peroxides) may be used as the vulcanizing agent. Examples of the sulfur system include powder sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Sulfur-containing compounds in sulfur-based vulcanizing agents include: for example, sulfur chloride (

Sulfur monochloride, sulfur dioxide, etc.), disulfide heterocyclic compounds (4,4, -dithiomorpholine-containing compounds containing disulfide groups), trisulfide containing hydrogenthio groups (2-di-n-butane Aminosulfanyl-4,6-dihydrothio-S-triazine, 2,4,6-trihydrothio-S-triazine, and other compounds containing hydrogen thio groups, etc.), thiurams (monosulfide Tetramethylthiuram (TMTM), Tetramethylthiuram disulfide (TMTD), Tetraethylthiuram disulfide (TETD), Tetrabutylthiuram disulfide (TBTD), Diarylene tetrasulfide Amyl thiuram (DPTT), etc., amine salt (Di-Ci-4 alkylamine salt such as dimethylamine salt, diethylamine salt, etc.), and alkali metals (sodium, potassium, etc.) , Transition metals (iron, copper, zinc, etc.), salts with metals of Group 6B of the periodic table (selenium, tellurium, etc.), thiazoles (2-hydrothiobenzobenzothiazole, 2- (4'- Morpholine dithio) benzothiazole, etc.). -42-200404878 The preferred vulcanizing agent is a free radical generator-type vulcanizing agent that can be combined with resin members in a wide range. The vulcanizing agent acts as a free radical generator and can activate rubber to form a strong bond. As the radical generator of the vulcanizing agent, various radical generators can be used. For example, the radical generator can be selected from organic peroxides, azo compounds, and sulfur-containing organic compounds other than sulfur. In addition, sulfur not only causes ionic reactions, but also has low generation efficiency of free radicals, but also traps free radicals that are generated, so it is not included in the free radical generator. These radical generators can be used alone or in combination of two or more. φ Organic peroxides include: diallyl peroxides [lauryl peroxide, benzene peroxide, 4-chlorophenylhydrazine, 2,4-dichlorophenylhydrazine, etc.]; Alkyls [Di-tertiary butyl peroxide, 2,5-bis (tertiary butyl peroxy) -2,5-dimethylhexane, 1,1-bis (tertiary butyl peroxy Radical) -3,3,5-trimethylcyclohexane, 2,5-bis (tertiary butylperoxy) -2,5-dimethylhexane-3,1,3-bis (tri Butylperoxyisopropyl) benzene, dicumyl peroxide, etc.]; alkyl hydroperoxides [tertiary butyl hydroperoxide, cumene hydrogen peroxide, 2,5-dimethyl Hexane-2,5-dihydrogen peroxide, di-isopropylbenzene hydroperoxide, etc.]; peroxyalkylenes [ethyl methyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (Tertiary butyl peroxy) 3,3,5-trimethylcyclohexane, etc.]; peresters [tertiary butyl peracetate, tertiary butyl pervalerate, etc.]. The azo compound system includes azobisisobutyronitrile and the like. In addition, the above-mentioned sulfur-containing organic compounds, mid-autumn, amine salt, and thiazole, can also function as a radical generator. -43-200404878 If light irradiation can be applied, the photopolymerization initiator can also be used as a radical generator. The photopolymerization initiator system includes, for example, benzophenone or its derivative [3,3'-dimethylmethoxybenzophenone, 4,4-dimethoxybenzophenone, etc.]: alkyl Phenyl ketone or its derivative [Acetophenone, Dimethoxyacetophenone, 2-hydroxymethyl-1-phenylpropane-one, benzyldimethylketal, 1-hydroxycyclohexylphenyl Ketone, 2-benzyl-2-dimethylamino-1- (morpholinyl) -butanone, etc.); allicone or its derivative [2-methylallylquinone, etc.]; thioxanthone or Its derivatives [2-methylchlorothioxanthone, alkylthioxanthone, etc.]; benzoin ether or its derivative (benzoin, benzoin alkyl ether, etc.): phosphine oxide or its φ derivative Wait. The radical generator also contains persulfate (ammonium persulfate, potassium persulfate, etc.). Among these compounds, a preferred radical generator is an organic peroxide. The ratio of the vulcanizing agent is, for example, 100 parts by weight of the unvulcanized rubber, and can be selected from a range of about 0.5 to 15 parts by weight, usually about 1 to 10 parts by weight, and preferably about parts by weight (for example, 2 to 7 parts by weight). It is about 3 to 5 parts by weight.

The ratio of the radical generator is 100 parts by weight of the unvulcanized rubber. For example, it can be selected from about 0.5 to 15 parts by weight, usually about 1 to 10 parts by weight, preferably 1 to 8 parts by weight (for example, 2 to 7 parts by weight). Servings) around. In addition, vulcanizing agents (such as sulfur-based vulcanizing agents) can also be used with various compounds, such as: metal oxides [polyvalent metal oxides such as zinc oxide, magnesium oxide, lead oxide]; benzoquinone dioxime [p-benzoquinone dioxime] , P, p'-benzylidene benzoquinone dioxime, etc.]; poly-p-dinitrobenzene, modified phenolic resin [alkyl novolac resin, brominated alkyl novolac resin, etc.] are used in combination. -44-200404878 [Vulcanized rubber layer (or intermediate layer)] The present invention is a combination of a vulcanized rubber member and a resin member with a vulcanized rubber layer vulcanized by a vulcanizing agent. With such a structure, the phenomenon that rubber and rubber are easy to adhere can be used. Even if the rubber types or formulations of the above-mentioned vulcanized rubber members are different, they can be reliably and firmly combined with a wide range of resins. This point means that for a rubber member that has already been put into practical use, it is possible to easily and reliably produce a composite body in which a vulcanized rubber member and a resin member are firmly bonded without changing the formulation. The rubber of the vulcanized rubber layer can be selected and used from a wide range of φ like the above-mentioned vulcanized rubber members, for example, selected from the group consisting of diene rubber, olefin rubber, acrylic rubber, fluorine-containing rubber, silicone rubber, and polyurethane. Ester-based rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, propylene oxide rubber (GPO), ethylene-vinyl acetate copolymer (EAM), polynorbornene rubber, modified rubber (acid-modified) Rubber, etc.) etc. These rubbers can be used alone or in combination of two or more. Rubber of vulcanized rubber layer, if used with vulcanized rubber structure

The rubber of the same system (preferably of the same type) can reliably increase the bonding strength. For example, even if the rubber member is a sulfur-containing vulcanized diene rubber (IIR, NBR, SBR, etc.), the rubber of the vulcanized rubber layer can use the rubber of the same system (rubber with similar molecular structure, such as olefin rubber such as EPDM). It is not the same rubber, if you use the same type (diene rubber), you can get higher bonding strength. Although the vulcanizing agent may be any of a sulfur-based vulcanizing agent (sulfur or a sulfur-containing compound) and a radical generator-based vulcanizing agent (such as a peroxide-based vulcanizing agent such as an organic peroxide), it is preferably selected and supplied. Sulfur-45-200404878 vulcanizing agent used for vulcanizing rubber components. Vulcanizing agent of the same system (especially the same kind). Examples of the sulfur-based vulcanizing agent and the radical generating agent-based vulcanizing agent include the same compounds as described above. Preferred vulcanizing agents are free-radical generator-based vulcanizing agents (especially organic peroxides) that can be combined with a wide range of resins. The ratio of the vulcanizing agent of the radical generator is, for 100 parts by weight of the unvulcanized rubber, for example, selected from a range of about 0.5 to 15 parts by weight, usually about 1 to 10 parts by weight, preferably 1 to 8 parts by weight (for example, 2 to 7 parts by weight)

[Vulcanization active agent]

In order to surely combine at least one layer or member of the vulcanized rubber member and the resin member, the vulcanized rubber layer, the vulcanized rubber member, and the resin member should be formed of a composition containing a vulcanizing active agent, which is advantageous. In other words, at least one of the unvulcanized rubber composition, the vulcanized rubber member, and the resin member used to form the vulcanized rubber layer may contain a vulcanization active agent. The vulcanizing active agent may be contained in at least either an unvulcanized rubber composition (composition for an intermediate layer) or a resin member. In particular, when at least a vulcanizing active agent and a radical generator-based vulcanizing agent are contained in an unvulcanized rubber composition (composition for an intermediate layer), the vulcanizing active agent not only promotes rubber vulcanization, but also promotes rubber molecules and resin members in the intermediate layer. The cross-linking of the resin molecules can make the bonding of the vulcanized rubber member and the resin member easier. For example, when the resin is a polyamide resin, if a free radical generator and a vulcanization active agent are used in combination, a cross-linking reaction can be performed between the resin member and the vulcanized rubber member through an intermediate layer, so that the two are firmly and firmly bonded. . In addition, as long as the vulcanization active agent is present in an amount necessary to promote vulcanization of rubber and form a bond between rubber and resin -46-200404878, if it is added in excess of the required amount, the physical properties of rubber or resin may be reduced. , So you should choose the appropriate amount of addition. The above-mentioned vulcanization active agent includes an organic compound having a carbon-carbon double bond (polymerizable unsaturated bond) [for example, a vinyl-based monomer (divinylbenzene, etc.), an allyl-based monomer (diene phthalate) Propyl ester, trispropyl phosphate, triallyl (iso) cyanate, etc.), (meth) propionic acid monomers, etc.]; maleimide compounds, etc. These vulcanizing active agents can be used alone or in combination of two or more. As the vulcanizing active agent, a polyfunctional polymerizable compound having a plurality of polymerizable groups (polymerizable unsaturated bonds) is generally used. (Meth) acrylic monomers can be exemplified: for example, difunctional (meth) acrylates [Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, i, 4-butanediol di (meth) acrylate, hexylene glycol di (meth) acrylate, di (methyl) Base) di (meth) acrylic acid such as neopentyl glycol acrylate C2_1 () dialkylene glycol ester; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polybis (methyl) Base) ethylene glycol acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polybutylene di (meth) acrylate, etc. Poly c (2_4) alkanediol di (meth) acrylate; glyceryl di (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentaerythritol di (meth) acrylate, bisphenol C2_4 oxyalkylene adduct bis (meth) propylene of A Esters, etc.]; trifunctional or polyfunctional (meth) acrylates [tris (meth) acrylic acid-47-200404878 glyceride, tris (methyl) acrylate trimethylolethane, tris (methyl) acrylate ) ^ Trimethylolpropane acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, propane tetra (meth) acrylate, Dinepentaerythritol hexa (meth) acrylate, etc.] and the like. A maleimide compound having several maleimide groups can be prepared by reacting a polyamine with maleic anhydride. Examples of maleimide compounds are: aromatic maleimide [1 ^, '-1,3-phenylene dimaleimide, N, N'-1,4-phenylene Dimaleimide, N, N'-3-methyl-1,4-phenylene φ dimaleimide, 4,4'-bis (N, N'-maleimide) Diphenylmethane, 4,4'-bis (N, N'_maleimide) diphenylmaple, 4,4'-bis (N, N, -maleimide) diphenyl ether Etc.]; Aliphatic bismaleimide [N, N'-1,2-ethylidenebismaleimide, N, N'-1,3-propylidenebismaleimide, Ν, Ν'-1,4-tetramethylenebismaleimide, etc.] and the like. A preferred vulcanizing active agent is a compound having several (for example, 2 to 6, especially about 3 to 6) carbon-carbon double bonds (polymerizable unsaturated bonds) in one molecule, such as (iso) cyanuric acid three Allyl esters; difunctional to polyfunctional (f meth) acrylates (especially trifunctional or polyfunctional (meth) acrylates); aromatic maleimide compounds, etc. It is not necessary to add a vulcanizing active agent in the present invention. For example, depending on the type of rubber material used, two components can be combined without the presence of a vulcanizing activator. However, in order to reliably combine the rubber member and the resin member, it is often advantageous to add a vulcanizing active agent. The vulcanizing active agent is usually composed of at least one of unvulcanized rubber (or unvulcanized rubber composition -48-200404878) and resin (or resin composition) added to the intermediate layer (rubber layer), but it may be Added to both ingredients. Further, a vulcanization active agent may be added to the rubber (unvulcanized rubber) used to form the vulcanized rubber member. If the resin is a resin having a crosslinkable unsaturated bond group, a vulcanization active agent is added to the resin component, thereby activating the resin-rubber cross-linking, so that the resin member and the intermediate layer are more firmly bonded. There are many situations. The amount of vulcanizing activator used varies depending on the type of vulcanizing activator used or the type of ingredients added, but it is usually used in an amount that promotes the adhesion of the resin to the rubber. For example, for a rubber selected from [the rubber used to form a vulcanized rubber layer or 100 parts by weight of at least one component of rubber (rubber element)] and resin [resin (resin element) for forming resin member] for vulcanized rubber members, and the vulcanization active agent may be about 0.1 to 10 parts by weight, preferably About 0.1 to 5 parts by weight, more preferably selected from the range of about 0.1 to 3 parts by weight. For example, when the vulcanization active agent is an acrylate of a polyhydric alcohol, the addition amount of the vulcanization active agent is about 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, for 100 parts by weight of at least one component selected from rubber and resin. It is more preferably 0.1 to 3 parts by weight, and practically 0.1 to 1.9 parts by weight (for example, 0.5 parts by weight or 1.0 parts by weight). In addition, if it is added to both rubber and resin, a small amount of resin may be added, and about 100 parts by weight of the resin may be about 0.1 to 7 parts by weight of the vulcanization active agent, preferably about 0.1 to 5 parts by weight, more It is preferably about 0.1 to 3 parts by weight. In addition, even if it is added to the rubber component or the resin component, it is best not to exceed 100 parts by weight for 100 parts by weight of the vulcanizing active agent, and care should be taken when the amount exceeds 5 parts by weight. And -49-200404878 should be reviewed beforehand the impact on the material to be added. If you want to obtain sufficient bonding strength of rubber members and resin members without extra concern about the effect on the material to be added, the amount of vulcanization activator is added. When the material to be added is rubber, it should be 1,000 parts by weight for rubber. It is 2 parts by weight or less, for example, about 0.1 to 1.9 parts by weight (for example, 0.5 to 1.9 parts by weight), and when the material to be added is a resin, 1,000 parts by weight of the resin should be 5 parts by weight or less, for example 〇. About 1 to 5 parts by weight (for example, 3 to 5 parts by weight).

In addition, when a vulcanizing activator is added to rubber, the ratio of the vulcanizing agent (especially a radical generating agent-based vulcanizing agent) to the vulcanizing activator is, for example, the former / the latter = 0.3 · 1/1 to 2 0/1 (for example, 0.5 / 1 ~ 2 0/1) (weight ratio), preferably 0.4 / 1 ~ 15/1 (e.g. 1/1 ~ 15/1) (weight ratio), and more preferably 0.5 / 1 ~ 10/1 (for example, 2/1 to 10/1) (weight ratio). [Vulcanization aid]

In the present invention, in order to improve the bonding efficiency, a vulcanization aid may be further used. Depending on the type of rubber and resin, the combination of rubber member and resin member can be made stronger by adding a vulcanization aid. The vulcanization aid is at least one of unvulcanized rubber (or unvulcanized rubber composition) added to the intermediate layer, unvulcanized rubber (or unvulcanized rubber composition) and resin (or resin composition) of the vulcanized rubber member, and may be added. To all the ingredients, or both the unvulcanized rubber (or unvulcanized rubber composition) and the resin (or resin composition) of the intermediate layer. Generally, the vulcanization aid is usually composed of at least one of an unvulcanized rubber (or an unvulcanized rubber composition) and a resin (or a resin composition) added to the intermediate layer (especially a resin or a resin composition). In this case, if necessary, vulcanization aid -50-200404878 can be added to the unvulcanized rubber of the vulcanized rubber member. The vulcanization aid can be selected according to the type of the resin or rubber, and examples thereof include, for example, the number of oligomers of the condensation-type thermoplastic resin (for example, the oligomers of the polyamide resins and the oligomers of the polyester resins). An oligomer having an average molecular weight of about 100 to 1,000. However, when used as a vulcanization aid, the oligomer does not necessarily need to have a crosslinkable group as described above.), Polyamines (such as described in (2) Polyols in the polyester resin section, etc.), polycarboxylic acids or their anhydrides, compounds having several aldehyde groups, epoxy compounds, nitrogen-containing resins (amino resins, etc.), and methylol groups Or alkoxymethylated Φ compounds, polyisocyanates, etc. These vulcanization assistants can be used alone or in combination of two or more.

Preferred vulcanization aids are compounds having two or more active hydrogen atoms in one molecule of the active atoms represented by the above formula (1), such as condensation-type thermoplastic resins (such as polyamide resins, polyester resins, etc.). ), Urethanes, etc. The ratio of the vulcanizing agent is, for example, from 0.1 to 30 parts by weight, preferably from 0.5 to 20 parts by weight, and more preferably from about 1 to 15 parts by weight with respect to 100 parts by weight of the rubber and / or the resin. [Other additives] For the rubber composition required to form the above-mentioned vulcanized rubber member or intermediate layer, various additives may be mixed as necessary, such as additives, plasticizers or softeners, and co-vulcanizing agents (metal oxides such as zinc oxide) Vulcanization accelerators (reaction products of aldehydes and ammonia such as cyclohexamethylenetetramine or acetaldehyde-ammonia, condensation products of aldehydes and amines, guanidines, thioquinones, thiazoles, sulfenimidines, Thiurams, ammonium salts, xanthates, etc.), anti-aging agents (heat-51-200404878 anti-aging agents, ozone degradation inhibitors, antioxidants, ultraviolet absorbers, etc.), adhesion-imparting agents , Processing aids, lubricants (stearic acid, stearic acid metal salts, rhenium, etc.), colorants, foaming agents, dispersants, flame retardants, antistatic agents, etc.

The aforementioned concrete (or reinforcing agent) includes, for example, granular concrete or reinforcing agent (mica, clay 'talc silicic acid, silica, calcium carbonate, magnesium carbonate, carbon black, ferrite, etc.), fibrous concrete Or reinforcing agents (organic fibers such as rhenium, nylon, vinylon, aromatic polyamide fibers, carbon fibers, glass fibers, etc.).

When the rubber is a silicone rubber, the most common material added as a reinforcing agent is sandstone powder. Stone cutting powder generally used for cutting oxygen-based rubber can be divided into two types: wet silica manufactured by wet method, and dry silica manufactured by dry method. The silica powder suitable for siloxane rubber is dry silica. When dry silica is used, a high bonding strength between a resin member and a rubber member can be easily obtained. When wet silica is used, the moisture contained in the silica powder will hinder the cross-linking between the resin member and the rubber member. However, even if it is a wet silica, it is not a combination of lethal obstruction of the rubber member and the resin member, but there are also some types of resins or siloxane rubbers used, types of vulcanizing activators or their usage amounts, and molding conditions. It can be used even if it is wet silica. It is also advisable to mix dry silica with wet silica. The plasticizer is not limited as long as it can impart plasticity to the rubber composition. Conventional softeners (linoleic acid, oleic acid, castor oil, palm oil and other vegetable oils; paraffin, process oils, synergists Mineral oil, etc.), plasticizers (phthalic acid esters, aliphatic dicarboxylic acid esters, sulfur-containing plasticizer-52-200404878, polyester polymer plasticizers, etc.). The content of the material is, for example, about 0 to 300 parts by weight based on 100 parts by weight of the rubber, preferably about 0 to 200 parts by weight, and more preferably about 0 to 100 parts by weight. The content of the plasticizer or softener is, for example, about 0 to 200 parts by weight, preferably about 0 to 150 parts by weight, and more preferably about 0 to 120 parts by weight based on 1,000 parts by weight of the rubber. In addition, the content of the co-vulcanizing agent, anti-aging agent, processing agent, lubricant, colorant, etc. may be an effective amount. For example, the content of the co-vulcanizing agent is about 0 to 20 parts by weight for 100 parts by weight of rubber. It may be about 0.5 to 15 parts by weight, and more preferably about 1 to 10 parts by weight. In addition, for systems containing active ingredients such as vulcanizing activators (unvulcanized rubber composition for intermediate layers, unvulcanized rubber composition for vulcanized rubber members, composition for resin members, especially compositions for resin members), a stabilizer is used. Combined, it can suppress or prevent gels (or one by one) in the heat mixing process (such as the kneading process of resin and vulcanization activator, etc.) even if a vulcanization activator with a polymerizable unsaturated bond is used. Granules). Therefore, without impairing the strength or appearance of the above-mentioned composite, the vulcanizing active agent can effectively exert its function, and the resin and the rubber can be firmly and firmly combined or adhered. From such a viewpoint, although the above-mentioned stabilizer may also stabilize the resin or rubber, it is preferred that at least the vulcanization active agent is stabilized. The stabilizer may be an antioxidant (including a heat-resistant processing stabilizer), a light stabilizer, or a hydroquinone such as a thermal polymerization inhibitor (hydroquinone, methylhydroquinone, etc.). The antioxidant system includes, for example, phenol-based antioxidants, amine-based antioxidants -53-200404878 oxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydroquinone-based antioxidants-, gadolinium-based antioxidants, ketoamine resins, and the like. · Benzene antioxidants include hindered phenol antioxidants, such as: monoacids, bisphenols, polyphenols, etc. Monophenols may be exemplified by mono- or di-tertiary butylphenols which may have a substituent [for example: 2,6-dibutyl-p-methoxycresol, 2,6_tertiary butyl- 4_ Ethylbenzidine and other C〗 4 Ci-Di-tertiary-butylbenzene hydrazone; 2-tertiary-butyl_4-methoxyphenol, 3_tertiary-butyl_4-methoxyphenol, etc. Ci4 Alkoxy mono- or di-tertiary butyl phenol; stearyl propionate -yg-(3,5_ di-tertiary butyl via φ basic group) esters, etc. -(Di-tertiary butyl-basic radical) vinegar, 2-ethylhexyl acetate- (2,6-di-tertiary butyl-4-teranyl benzylthio) ester and other C2_6 carboxylic acid Cnoalkane -(Di-tertiary-butyl-hydroxybenzylthio) ester; distearyl phosphonate- (3,5-di-tertiary-butyl-4_hydroxybenzyl) ester, etc. C10 ^ ( ) Alkyl- (di-branched C2_6alkyl-benzyl) phosphonic acid], benzene having a C4_iothiol group [2,4_bis (octylthio) methyl-6-methyl Benzyl hydrazone (Irganox 1520, manufactured by Ciba-Geigy, etc.)]; Monoesters of bisphenols and (meth) acrylic acid [eg: acrylic acid 2- (2-hydroxy-3 · tertiary butyl) Methyl-5-methylbenzyl) -4-methyl -6-Tri-butylphenyl ester (SUM1RAIZER-GM, manufactured by Sumitomo Chemical Industries), 2- [1- (2-hydroxy-3-tertiary-butyl-5-methylphenyl) acrylic acid Ethyl] -4-methyl-6-tertiary butylphenyl ester (SUM1RAIZER-GS, manufactured by Sumitomo Chemical Industries, Ltd.), etc. (^ _4 alkylene bis (mono- or di-tertiary butyl Phenol), (monoesters of (meth) acrylic acid, etc.] etc. Bisphenols can be exemplified by 2,2'-methylenebis (4-methyl-6-tert-butylbenzene-54-200404878

Phenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-ethylenebis (4,6-di-tert-butylphenol), 4,4, -Butylene bis (3-methyl-6-di-tert-butylphenol), 4,4'-Butylene bis (3-methyl-6-tert-butylphenol), 4, 4'-methylenebis (2,6-di-tert-butylphenol) and other Cm alkylenebis (mono- or di-tert-butylphenol); 4,4'-thiobis (3- Methyl-6-tertiary-butylphenol) and other thiobis (mono- or di-tertiary-butylphenol); bis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) Propionic acid] -1,6-hexanediol ester, bis [3- (3-tertiarybutyl-5-methyl-4-hydroxyphenyl) propionic acid] -triethylene glycol ester (Irganox 245, Ciba- (Made by Geigy) and other (mono- or di-tertiary butyl-hydroxyphenol) C2_6 carboxylic acid-mono- to tetra-C2.4 alkylene glycol ester; bis (3,5-di -Tertiary butyl-4-hydroxy-hydrogenated cinnamyl (Irganox MD-1024, manufactured by Ciba-Geigy), N, N'-trimethylenebis (3,5-di-tertiary butyl) -4-hydroxy-hydrogenated cinnamon tincture)

, N, N'-hexamethylenebis (3,5-di-tertiarybutyl-4-hydroxy-hydrocinnamonamidine), etc. (mono- or di-tertiary butyl-hydroxyphenyl) C3_6 carboxylic acid Diamines with CG_8 alkylene diamines; 3,9-bis {1,1-dimethyl-2- [/ 3-(3-tert-butyl-hydroxy-5-methylphenyl) Propyloxy] ethylbuthyl 2,4,8-10 · tetraoxo [5,5] undecane (SUM1RAIZER-GA80, manufactured by Sumitomo Chemical Industries, Ltd.), etc. (single- or second-third grade Butyl-hydroxyphenyl) C3.6 carboxylic acid and dihydroxy heterocyclic spiro compounds diesters. Polyphenols, including: phenols {for example: 1,3,5-trimethyl-2,4,6-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (ADEKASTUB A0-3 30, manufactured by Asahi Chemical Industry Co., Ltd.) etc. (mono- or di-tertiary butyl-hydroxybenzyl) C6-10 aromatic hydrocarbons; 1,1,3-ginseng (2-methyl) 4-hydroxy-5-tri-55-200404878 grade butylphenyl) butane and other ginseng (mono- or di-tertiary butyl-hydroxyphenyl) Cl-6 alkane; see [3_ (3,5- Di-tertiary butylhydroxyphenyl) propionic acid] glyceride, etc. (mono- or di-tertiary butyl-hydroxyphenyl) Triesters of C2 6 carboxylic acid and C3 6 alkanetriol; 1, 3, 5-ginseng (3,5, -di-tertiarybutyl-4, -hydroxyphenyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione (ADEKASTAB) A0-20, manufactured by Asahi Denka Kogyo Co., Ltd.), 13,5-ginseng (2 ,, 6, dimethyl-3, -hydroxy-4'-tertiary butylbenzyl) -S_triazine-2, Tetraphenols such as 4,6- (lH, 3H, 5H) triketones (mono- or di-tertiary butyl · hydroxybenzyl) -S_triazine-trione {e.g. Methyl-3- (3,5, -di-tert-butyl-4, -hydroxyΘphenyl) propionate] methane (Irg anox 1010, manufactured by Ciba Specialty Chemicals Corporation) and other (mono- or di-tertiary butyl-hydroxyphenyl) tetraesters of C36 carboxylic acid and C3_6 alkyltetraol; bis (3,3'_bis (4 ' -Hydroxy-3'-tertiary butylphenyl) butanoic acid) glycol esters and other bis (mono- or di-tertiary butyl-hydroxyphenyl) C3_6 carboxylic acids-mono to tetra C2_4 alkylene glycol esters} Wait.

Amine-based antioxidants include aromatic amines, such as: phenyl-;!-Naphthylamine, phenyl-2-naphthylamine, N, N'-diphenyl-i, 4-phenylene di Amine, N-phenyl-N'-cyclohexyl-1,4-phenylene diamine and the like. Phosphorus antioxidants include, for example, tri-isodecyl phosphite, phenyl diisodecyl ortho acid, diphenyl isodecyl phosphite, triphenyl phosphite, and phosphite ( 2,4-di-tertiary butylphenyl) ester (ADEK AS TAB 2112, manufactured by Asahi Denka Kogyo Co., Ltd.), ginseng (nonylphenyl) phosphite, dinonylphenyl bis (phosphite) Nonylphenyl) Ester, Octyl Phosphite 2,2-Methylene Bis (4,6-Di-Tri-Butylphenyl) Ester (-56-200404878 ADEKA STAB) (Manufactured by Kogyo Kogyo Co., Ltd.), dodeca-triyl phosphite 4,4'-butylene bis (3-methyl-6-tertiary butylphenyl) ester, and phosphite (2,4-di-tertiary butyl) Phenyl) ester, phosphite (2-tert-butyl-4-methylphenyl) ester, phosphite (2,4-di-tert-pentylphenyl) ester, phosphite (2 -Tertiary butylphenyl) ester, phenyl bis (2-tertiary butylphenyl) phosphite, ginseng [2- (1,1-dimethylpropyl) phenyl] ester, [2,4- (1,4-dimethylpropyl) phenyl] phosphate, ginseng (2-cyclohexylphenyl) phosphite, Phosphite (2-tert-butyl-4-phenylphenyl) phosphite, diisodecyl neopentaerythritol diphosphite, cyclic neoφ pentane tetrail bis (octadecyl) ester ( ADEKASTAB PEP-8, manufactured by Asahi Denka Kogyo Co., Ltd.), cyclic neopentane phosphite tetrail bis (2,4-di-tert-butylphenyl) ester (ADEkaSTAB PEP-24G, Asahi Denka) (Manufactured by Industrial Co., Ltd.), cyclic neopentane phosphite tetrail bis (2,6_di-tertiary butyl-4-methylphenyl) ester (ADEKASTAB PEP-36, manufactured by Asahi Chemical Industry Co., Ltd.), etc. Phosphite compounds; triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylvinylphosphine, allyldiphenylphosphine, triphenylphosphine, methylphenyl- P-anisylphosphine, p-anisyldiphenylphosphine, p-tolyldiphenylphosphine, di-p-anisylphenylphosphine, mono-p-phenylphenylphosphine, tris-m-aminophenylphosphine , Tri-2,4-dimethylphenylphosphine, tri-2,4,6-trimethylphenylphosphine, tri-o-tolylphosphine, tri-m-methylbenylphosphine, di-p-toluene Phosphine, tri-o-anisylphosphine, tri-p-anisylphosphine, I, 4- (Diphenylphosphino) butane and the like containing a phosphine compound. Sulfur-based antioxidants, including, for example, dilauryl 3,3- thiodipropionate, di (tridecyl) thiodipropionate, and 2,2-dithiopropionate Myrtle 57-200404878 Phenyl ester, 3,3 -thio-monopropionate monocrotyl ester, 3,3 -thiodipropionate lauryl stearate, 3,3 -thio monopropionate Aliphatic esters, such as thioc 2 * residual acid di Ci0_2i-membered vinegar '3,9-mono (laurylthioethyl) -2,4,8,10 -tetraoxospira [5, 5] Undecane and the like. Hydroquinone-based antioxidants include, for example, 2,5-di-tertiary butyl hydrogen, 2,5-primary-secondary pentylhydrogen, and the like; g-series antioxidants include, for example, 6-ethyl Oxy_2,2,4-trimethyl-I, 2-dihydrogallium and the like. The light stabilizer 'system includes a hindered amine light stabilizer (HALS), a quencher, and the like. The hindered amine light stabilizer (Hals) contains, for example, tetramethylpiperidine (for example, Ci_4 alkane such as 4-methoxy_2,2,6,6-tetramethylpiperidine) which may have a substituent. Oxy-tetramethylpiperidine; 4-phenoxy-2,2,6,6-tetramethylpiperidine and other Cnoaryloxy-tetramethylpiperidine; 4-benzyloxy-2 , 2,6,6 · Tetramethyl-pyridine and other Cmaryloxy-tetramethylqididine; 4-Methacrylfluorenyloxy-2,2,6,6-tetramethylpiperidine ( ADEKASTAB (produced by LA-87 'manufactured by Asahi Denka Kogyo Co., Ltd.), 4-methacrylfluorenyloxy-N_methyl- 2,2,6,6-tetramethylpiperidine (ADEKASTAB) 82, manufactured by Asahi Denka Kogyo Co., Ltd., etc. (meth) acrylfluorenyloxy-tetramethylpiperidine, etc.) • Dipiperidine alkane dicarboxylate [eg, bis (2,2,6 , 6-tetramethyl-4-piperidinyl) oxalate, bis (2,2,6,6-tetramethylpiperidinyl) malonate, bis (2,2,6,6_tetra Methyl-4_piperidinyl) adipate, bis (2,2,6,6-tetramethyl-4_piperidinyl) sebacate (ADEKASTAB LA-7 7, Asahi Denka Manufactured by Industrial Co., Ltd.), bis (1,2,2,6,6-pentamethyl_4-pulsalyl) sebacate, (Meth -2,2,6,6_ of N_ -4_ tetramethyl piperidyl) sebacate (S AN 0L (transliteration) LS-765, Sankyo Co., Ltd.) 200 404 878

Cl! 〇 Aromatic diacid bis (tetramethyl-4-piperidinyl) ester, etc.]; Aromatic piperidinyl dicarboxylic acid esters which may also have a substituent [eg, bis (2,2,6,6 -Tetramethyl-4-piperidinyl) terephthalate, etc. C6_1Q aromatic dicarboxylic acid bis (tetramethylpiperidinyl) ester etc.]; bis (piperidinyloxy) which may have a substituent ) Alkanes [for example: 1,2-bis (2,2,6,6-tetramethyl-4-piperidinyloxy) et al. Bis (tetramethylpiperidinyloxy) (^ -4 Hydrocarbons, etc.]; bis (2piperidinyloxycarbonyl) hydroxyphenylalkanes {eg: 丨 _ (3,5_di-tertiary-butyl-4-hydroxyphenyl) -i, i-bis (2, 2,6,6-tetramethyl-4-piperidinyloxycarbonyl) pentylene (Tinuvin 144, manufactured by Ciba-Geigy) and other bis (tetramethylpiperidinyloxycarbonyl) -hydroxybenzene Alkanes, etc. ;; di- to tetra-piperidinyl esters of tetracarboxylic acid [eg, 1,2,3,4-butanetetracarboxylic acid (2,2,6,6-tetramethyl-4-piperidine) Pyridyl) esters (ADEKASTAB LA-57, manufactured by Asahi Denka Kogyo Co.) and other tetracarboxylic acid (tetramethylpiperidinyl) esters; 12,3,4 _ butane tetracarboxylic acid bis (2,2 , 6,6-tetramethyl-4-piperidinyl - bis (tridecyl) ester (ADEKASTAB (transliteration) LA-67, manufactured by ADEKA Corporation)

1,2,3,4-butanetetracarboxylic acid bis (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) -bis (tridecyl) ester (ADEKASTAB (Translated) LA-62 manufactured by Asahi Denka Chemical Industry Co., Ltd.) and other tetracarboxylic acid bis (tetramethylpiperidinyl) -bis (triC8_20 alkyl) esters, C! _4 alkylidene bis (tetraalkylpiperazine) Ketone), for example: [1,1,3,3,3 ', 3', 5,5,5,5, -octamethylpiperazine-2,2, -dione (GoodriteUV -3034, Cy extended alkyl bis (tetraalkylpiperazinone) made by Goodrich, etc.]; polymer HALS [such as Chimassorb 944LD (made by Ciba Specialty Chemicals), Tinuvin 144 622LD (made by Ciba Specialty Chemicals) ), ADEKASTAB (translated) LA-63 (-59-200404878 manufactured by Asahi Denka Chemical Industry Co., Ltd.), ADEKASTAB (translated) LA-68 (made by Asahi Denka Chemical Industry Co., Ltd., etc.). Pentane) nickel, {[2,2'-thiobis (4-tertiary octylphenolate)]-n-butylamine nickel complex-3,5-di-tertiary butyl-4 -Hydroxybenzyl-monoethyl phosphate}, nickel dibutylamine oxalate, nickel 1-phenyl-3-methyl-4-decylpyrazole, etc. Nickel complexes Machine; cobalt dicyclohexyl dithiophosphoric acid and the like organic cobalt complexes and the like.

These stabilizers may be used alone or in combination of two or more. Preferred stabilizers include stabilizers having a free radical trapping ability such as a phenol-based antioxidant and HALS. In addition, such stabilizers having a free-radical trapping ability may be used in combination with other stabilizers. Such a combination includes, for example, a combination of a phenol-based antioxidant and a sulfur-based antioxidant and a combination of a phenol-based antioxidant and a phosphorus-based antioxidant Oxidants, etc. In addition, such stabilizers having free-radical trapping ability can be used in combination with other stabilizers. Such a combination includes, for example, a combination of a phenol-based antioxidant and a sulfur-based antioxidant, a phenol-based antioxidant and a phosphorus-based antioxidant. Combination, etc.

The use amount of the stabilizer is, for example, 0.01 to 15 parts by weight (for example, 0.00 to 10 parts by weight), preferably 0.054 to 0 parts by weight (for example, 0.05 to 8 parts by weight) for 100 parts by weight of the resin or rubber. More preferably, it may be about 0.1 to 7 parts by weight (for example, 0.1 to 5 parts by weight). In addition, when using stabilizers (phenol-based antioxidants, HALS, etc.) with free-radical trapping ability in combination with other stabilizers (phosphorus-based antioxidants, sulfur-based antioxidants, etc.), the ratio of these stabilizers is also It can be the former / the latter (weight ratio) = 99/1 ~ 20/80 (for example, 95/5 ~ 40/60) about -60-200404878 In addition, the ratio of the vulcanization active agent to the stabilizer can be determined by the vulcanization active agent or Stabilizer, mixing temperature, etc. can be selected. It can be the former / the latter (weight ratio) = 99/1 ~ 25/75, preferably 98/2 ~ 3 5/65, and more preferably 97/3 ~ 45/65 (for example, 97/3 to 60/40). [Combination of Resin Member and Vulcanized Rubber Member] In the present invention, since the above-mentioned vulcanized rubber layer is interposed between the resin member and the vulcanized rubber member, even if the resin member and the vulcanized rubber member are combined in a wide range, it can be reliably combined. Rugged to produce a highly integrated body. In addition, even if the vulcanization system uses a sulfur-containing vulcanization system or a non-sulfur vulcanization system, the bonding strength between the resin member and the vulcanized rubber member can be improved. Therefore, the combination of the resin member and the vulcanized rubber member is not particularly limited, and the above resin and rubber can be appropriately combined.

When the resin member and the vulcanized rubber member are combined, if it is desired to increase the bonding strength, it is preferable to form at least one of the vulcanized rubber layer, the vulcanized rubber member, and the resin member with a composition containing a vulcanizing active agent. For example, if a vulcanized rubber layer is formed from an unvulcanized rubber composition containing a vulcanizing agent and a vulcanizing active agent, and at least one of a vulcanized rubber member and a resin member (particularly at least a resin member) is formed from a vulcanizing active agent-containing composition. That is, the resin member and the vulcanized rubber member can be combined under extremely high bonding strength. In addition, if the thermoplastic resin of the resin member or its composition is made of polyphenylene ether, and the unvulcanized rubber of the vulcanized rubber layer or its composition is made of styrene-diene copolymer rubber, the vulcanized rubber layer is made of a radical generator. -61-200404878 (organic peroxide, etc.) can be combined with a vulcanized rubber layer with high bonding strength when vulcanized or vulcanized with a sulfur-based vulcanizing agent. In this case, the polyphenylene ether resin can be modified or modified with a styrene resin. In addition, when the styrene-diene copolymer rubber is vulcanized with a sulfur-based vulcanizing agent, the amount of the sulfur-based vulcanizing agent is 1 to 10 parts by weight, preferably 2 to 7 parts by weight, and more preferably 3 to 100 parts by weight of the rubber. ~ 5 parts by weight. [Manufacturing method of composite body]

The present invention relates to a rubber element and a resin element through contact with an unvulcanized rubber layer containing a vulcanizing agent, vulcanizes the unvulcanized rubber or the semi-vulcanized rubber, and shapes the rubber element and the resin element to manufacture the above-mentioned composite body (that is, to make The unvulcanized rubber layer is a resin / rubber composite in which the vulcanized rubber member of the rubber member and the resin member of the resin member are combined by the vulcanized rubber layer. More typically, the vulcanized rubber member and the resin element are brought into contact with each other through an unvulcanized rubber layer containing a vulcanizing agent, and the above unvulcanized rubber layer is vulcanized by means such as heating, whereby the vulcanized rubber member and the resin member can be obtained. Combined complex.

The rubber element (rubber material) constituting the above-mentioned vulcanized rubber member may be a vulcanized rubber material, an unvulcanized rubber material (unvulcanized rubber composition), or a semi-vulcanized rubber material (semi-vulcanized rubber member). If the rubber component (rubber material) is an unvulcanized rubber composition or a semi-vulcanized rubber component, it will be vulcanized together in the vulcanization process of the unvulcanized rubber layer. The resin element (resin material) used to constitute the resin member may be an unmolded resin composition, a semi-molded resin member, or a molded resin member. In addition, "vulcanized rubber member", "rubber member" and "resin member" are -62-200404878, which means a member having a specific shape formed into a final product member, and "unvulcanized rubber composition" and "unmolded resin composition" mean Composition with a specific shape. As for "semi-vulcanized rubber material", "semi-vulcanized rubber member", and "semi-molded resin member", it means that the component does not have the shape and / or composition of the processed person and / or the component does not have the shape of the final product component, and may also include components Preforms of vulcanized rubber, active vulcanizing agent, vulcanizing activator or uncrosslinked resin.

As described above, the rubber element (especially the unvulcanized composition and the semi-vulcanized rubber member) contains at least a vulcanizing agent (especially a radical generator systemizing agent). Furthermore, in order to improve the bonding strength with the intermediate layer, the rubber element (especially the unvulcanized composition and the semi-vulcanized rubber member) may contain a vulcanization activator (a polyfunctional polymerizable compound having several polymerizable unsaturated bonds). The ratio of each component is as described above.

The resin element may contain a crosslinking accelerator as described above. The resin element (thermoplastic resin or resin having a crosslinkable group) may further contain a vulcanization activator (a polymerizable compound having several polymerizable unsaturated bonds) as described above. In addition, in order to improve the bonding strength between the vulcanized rubber member and the resin member, the polyfunctional polymerizable compound having a plurality of polymerizable groups is preferably contained in at least one of the rubber element and the resin element. In both ways. The ratio of these components is also as described above. The unvulcanized rubber composition for forming the unvulcanized rubber layer may include at least a vulcanizing agent (especially a radical generating agent-based vulcanizing agent such as an organic peroxide), but preferably further contains a vulcanizing active agent (having several Polyfunctional polymerizable compound). As for the unvulcanized rubber composition, the content of sulfur -63-200404878 chemical agent and vulcanizing active agent is as described above. A preferred aspect is (i) the resin constituting the resin member is composed of a resin having the above-mentioned specific active atom (active hydrogen atom and / or active sulfur atom). (Ii) At least one of the unvulcanized rubber composition and the resin member contains a polyfunctional polymerizable compound having a plurality of polymerizable groups. (Iii) The resin member is composed of a thermosetting resin or a resin having an unsaturated bond in the molecule, and the unvulcanized rubber composition contains a polyfunctional polymerizable compound having a plurality of polymerizable groups. The unvulcanized rubber layer may be formed on the bonding surface of at least one of the bonding surfaces of the rubber element and the resin element. In addition, although the unvulcanized rubber layer is generally a substantially uniform layer, as long as the combination of the vulcanized rubber member and the resin member is not impaired, for example, the unvulcanized rubber layer may be a layer having a non-uniform thickness (for example, an uneven surface). Layer or interspersed layers, etc.). The vulcanization molding is generally performed by exposing the resin element and the resin element to pressure with the unvulcanized rubber layer described above, and irradiating the resin element with heat, particularly by heating. In this process, the rubber composition or the semi-vulcanized rubber member for the vulcanized rubber member is also vulcanized together with the vulcanization of the unvulcanized rubber composition. In addition, with heating, an unmolded resin composition or a semi-molded resin member is also molded, so that a resin having a crosslinkable group is crosslinked and hardened. The aforementioned unvulcanized rubber layer is not limited to a film (sheet) of an unvulcanized rubber composition interposed on a bonding surface of a rubber element and / or a resin element, and may be a coating layer formed by using a coating agent. For example, a liquid unvulcanized rubber composition (such as a solution or dispersion of an unvulcanized rubber composition (emulsion, -64-200404878 suspension), etc.) as a coating agent is applied to a combination of rubber elements and / or resin elements An unvulcanized rubber layer can be formed on the surface and dried if necessary. In addition, the film or sheet of the unvulcanized rubber composition may be formed in advance in accordance with the molding method as described above, and formed by a two-component extrusion method at the same time as the composition for the vulcanized rubber member or the resin member.

More specifically, the method of the present invention includes the following three methods and the like. That is, while the resin composition and the unvulcanized rubber composition of the intermediate layer and the unvulcanized rubber composition of the vulcanized rubber member are separately molded, the resin composition and the intermediate layer and the unvulcanized rubber composition are brought into contact or merged during the molding process to make the resin member A method of combining or bonding with a vulcanized rubber member through an intermediate layer (single-stage method), molding one of a resin element and a rubber element (for example, preforming or molding one of the resin member and the vulcanized rubber member in advance to a final shape) Product component form), and then contact the molded component of one side with the unvulcanized rubber composition of the middle layer and the unformed component (unshaped resin composition or unvulcanized rubber composition) of the other side while molding the unvulcanized rubber A method of cross-linking or vulcanizing a composition so that a resin member and a vulcanized rubber member are combined or followed by an intermediate layer (two-stage method), and molding the resin in a state in which an unvulcanized rubber composition is used as the intermediate layer. Components (pre-formed or formed into final products A molded rubber member in the shape of a piece), and contact with a molded rubber element (a molded resin member that is pre-formed or molded into the final product member shape) to 'crosslink or vulcanize the resin member and the vulcanized rubber member through an intermediate layer The combination or continuation method (three-stage method), etc. More specifically, in the single-stage method, for example, using a conventional multi-color molding machine -65-200404878 (multi-color injection molding machine, multi-layer extruder, etc.), the resin composition and the unvulcanized rubber composition of the intermediate layer and The unvulcanized rubber composition of the vulcanized rubber member is melted and kneaded separately and then injected or extruded into a specific shape, and the resin composition and the unvulcanized rubber can be crosslinked or vulcanized during the molding process or after molding. A composite molded body was prepared. In addition, in the contact interface area between the resin composition and the unvulcanized rubber composition, the resin composition and the unvulcanized rubber composition may be mixed and present together.

In the two-stage method, conventional molding machines (injection molding machines, extrusion molding machines, hot press molding machines, etc.) can be used for the molding of molded resin components. For the molding of molded rubber components, conventional molding machines (injection molding machines, compression molding machines, transfer molding machines, extrusion molding machines, etc.) can be used. For example, the molded resin element may be housed in a mold (or cavity) corresponding to the shape of the composite body, and the unvulcanized rubber composition for the intermediate layer and the unvulcanized rubber composition for the vulcanized rubber member may be injected or extruded from the resin element so that The vulcanized rubber composition is crosslinked or vulcanized, so that the vulcanized rubber member and the resin member are bonded via an intermediate layer. In addition, when the composite is a plate-like or sheet-like member having a two-dimensional expansion, the film or sheet of the unvulcanized rubber composition for the laminated intermediate layer of the molded resin element can be used without using the mold (or cavity) described above. 'A composite is produced by cross-linking or vulcanizing a plate-like or sheet-like unvulcanized rubber composition for forming a vulcanized rubber member. In addition, 'When the molded resin element is brought into contact with the unvulcanized rubber composition (adhesion, etc.)', in order to remove volatile components or gaseous components from the unvulcanized rubber composition, it may be added by a hot press molding method or an injection molding method. Pressing can also be performed under reduced pressure. -66-200404878 In the three-stage method, it is also possible to obtain a composite by contacting a molded resin element and a molded rubber element with a thin film (sheet) of an unvulcanized rubber composition, and then crosslinking or vulcanizing the composite. The coating liquid of the unvulcanized rubber composition is coated on the bonding surface of at least one of the molded resin element and the molded rubber element to form an unvulcanized rubber layer, and the molded resin element and the molded rubber element are added through the unvulcanized rubber layer. Press and press-mold to produce a composite. The thickness of the film (sheet) of the unvulcanized rubber composition is not particularly limited, and may be, for example, 0.1 to 10 mm, preferably 0.5 to 5 mm, and more preferably 0.5 to 3 mm. In addition, the coating amount (converted to solid content) of the contact surface or the bonding surface may be, for example, about 0.1 to 500 g / m2, preferably about 10 to 300 g / m2, and particularly preferably 50 to About 100 g / m2. The cross-linking (or vulcanization) temperature (or the bonding temperature of the rubber member and the resin member) of the molded resin material and the molded rubber material can be selected from, for example, 70 to 250 ° C, preferably 100 to 23 0 ° C, more It is preferably in the range of about 150 to 200 ° C. The pressure acting on the rubber / resin can be selected from, for example, 0.1 to 350 MPa ', preferably 1 to 150 MPa, and more preferably about 2 to 100 MPa. When the solvent of the coating agent is a low-molecular-weight rubber (for example, liquid rubber), the solvent may be appropriately selected from hydrocarbons (aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons), although not necessarily required, Alcohols, esters, ketones, ethers, fluorenes, amidoamines or mixed solvents of these. In the present invention, since a vulcanized layer of an unvulcanized rubber composition containing a vulcanizing agent is interposed between the resin member and the vulcanized rubber member, a wide range of combinations can be obtained -67 · 200404878 Complex. In addition, the resin molded body and the vulcanized rubber molded body can be firmly combined without the need to apply easy adhesion treatment to the surface of the resin molded body. In addition, without changing the rubber formula, even sulfur-containing vulcanized rubber members can be firmly combined with resin members. In addition, since the vulcanized layer of the above-mentioned unvulcanized rubber composition is interposed between the resin member and the vulcanized rubber member, the resin member and the vulcanized rubber member can be firmly bonded even with a three-dimensional structure. Industrial applicability

The composite obtained as described above is bonded to the rubber element and the resin element at a significantly high strength by vulcanization. Therefore, the characteristics of resin and rubber can be effectively used, and can be advantageously used in various applications, such as automotive parts (vibration absorbing sleeves, spring plates, door lock members, water tank brackets, etc.), vibration-proof rubber, valves , Electrical plugs and other components. [Embodiment] The present invention will be described in more detail based on the embodiments, but the present invention is not limited to these embodiments.

[Composition of Resin Member] PA612 (Aik Polyamine 612 (NH2 end / COOH end = 1/1 (Mole ratio) alone PA612 (A1) modulation: hexamethylene diamine and dodecanedioic acid An 80% by weight aqueous solution of salt was heated (220 ° C) under pressure (17.5 kg / cm2) in an autoclave replaced with nitrogen, so that the water in the system took 4 hours to be discharged out of the system together with nitrogen. It took 1 hour to slowly raise the temperature (275 ° C) to drain the water outside the system -68-200404878. After that, the internal pressure of the autoclave was returned to normal pressure, and polyamide 6 12 was obtained after cooling. The polymer has a number average molecular weight (Mn) of 20,000 to 25,000, and the ratio of amine terminal to carboxyl terminal = 1/1 (molar ratio). This polymer is used as a resin composition PA6 12 (A1) alone. When the vulcanizing agent is an organic peroxide, the number of active hydrogens of PA6 12 (A1) is 4 per molecule. PA612 (A2): Polyamide 612 (NH2 end / COOH end = 3/7 (Mo

Ear ratio) Preparation of PA612 (A2) alone: The above resin composition PA6 12 (A1) and the following resin composition (A3) are mixed with a biaxial extruder at a weight ratio of 1/1. This was used as a resin composition PA6 12 (A2) and used alone. PA612 (A2) has 2.4 active hydrogens per molecule. PA612 (A3): Polyamide 612 (NH2 end / COOH end = 1/9 (molar ratio) modulation of PA612 (A3) alone:

A specific amount of dodecanedioic acid was added to an 80% by weight aqueous solution of a salt of hexamethylenediamine and dodecanedioic acid, and the autoclave was replaced with nitrogen under pressure (17.5 kg / cm2) Heating (220 ° C), it takes 4 hours for the water in the system to be discharged out of the system together with nitrogen. Then, it took 1 hour to slowly raise the temperature (275 ° C) to drain the water out of the system. Then, the internal pressure of the autoclave was returned to normal pressure, and polyamide 6 1 2 was obtained after cooling. The obtained polymer had a number-average molecular weight (Mn) of about 20,000, and a ratio of amine-terminus to carboxy-terminus of 2/1 (molar ratio). This polymer was used alone as a resin composition -69-200404878 PA6 12 (A3). The number of active hydrogens of PA6 12 (A 3) is 0.8 PPE per molecule (Bn: Polyphenylene ether resin is Vestoran 1900 manufactured by Degussa. The number of active hydrogens per molecule is 6 or more. PPS (C1 ): Polyphenylsulfur resin

The system uses Polylon's Fortlon 0220A9. The number of active sulfur per molecule is 6 or more. m-PBT (ΡΠ: Modified PBT resin m-PBT (D1) modulation:

1.82 g of calcium acetate and 3.64 g of antimony oxide were added to 883 g of dimethyl terephthalate, 747 g of butanediol, and 70.4 g of butylene glycol, and then fed to a tube equipped with a stirrer and a nitrogen introduction tube. 2. The side tube for distillation, and the polymerization tube connected to the vacuum system. The polymerization tube was heated to 1 80 ° C in an oil bath, while nitrogen was slowly passed through, and the amount of methanol distilled off reached the theoretical level, it began to disturb the companion, and the temperature of the system was gradually raised. To 25 0 ~ 2 60 ° C, and slowly increase the vacuum to below 100 Pa. While distilling off the produced butanediol dropwise, it took 2 to 3 hours to perform the condensation reaction, and the relative viscosity in a mixed solvent of tetrachloroethane / phenol = 40/60 was appropriately measured, and the number When the average molecular weight reaches 10,000, the reaction is completed. The concentration of unsaturated bonds in the obtained polymer was an average of 4 molecules per molecule of the polymer, 0.4 mol / kg. This polymer was used alone as a modified PBT resin composition (D1). King saturated PPE (E1): unsaturated polyester resin -70-200404878 The system of unsaturated PPE (El) in the week · The presence of 0.22 g of hydroquinone monomethyl ether and 0.6 g of dibutyl zinc oxide as an esterification catalyst Next, 604 g of maleic anhydride and 507 g of propylene glycol were dehydrated and condensed at a pressure of 180 to 190 ° C in a nitrogen stream at normal pressure to obtain an unsaturated polyester having a weight average molecular weight of 5,800. To this unsaturated polyester was added 3.4 g of cobalt naphthenate, and it was dissolved and diluted with 600 g of ethyl methacrylate and 100 g of styrene. 100 parts by weight of the diluted solution was added with 3 parts by weight of an organic peroxide (Perbutylau (translated by Ben Fat Corporation)) and stirred, and then hardened at 80 ° C to obtain a flat plate having a thickness of 3 mm. . This was used as a sample of the unsaturated polyester resin composition (E 1). Melamine (F1): The melamine resin is made of Sumitomo Baklite's "SUM1CON (Translated) MMC-50" (black color), and is made into a 4 mm thick flat plate as a sample for the melamine resin composition (F1) use. TRIM: Trimethylolpropane trimethacrylate [composition of vulcanized rubber layer] SBR: "JSR0 202" (46% by styrene) made by JSR EPDM: "Keltan 509x 1 00" made by DSM NR: # 3 NBR made in Thailand: "Nipol 1042" made by ZENON, Inc. VMQ-1 uses a molar ratio of 99.98: 0.02 (A) dimethylchlorosilane (CH3) 2SiCl2 and (B) methyl vinyl Chlorosilane (CH3) CH2 = CH-SiCl2 to obtain (C1) cyclic dimethylsiloxane-methylvinylsiloxane tetramer. For the (c 丨) tetramer -71-200404878, 100 mol of potassium hydroxide was added at 0.0011 mol, and at 155.聚合 Polymerization under nitrogen atmosphere. The limiting viscosity [7?] (25 ° C), cSt) of the polymer (siloxane A) obtained is log 7? = 7.7, and the average molecular weight is 290,000 and the polymerization degree is 4, based on the limit viscosity. 〇〇〇 around poly sand oxygen hospital. In addition, regarding the amount of ethylene in the prepared polymer, quantitative results were obtained by 1H-NMR, and it was found that there were an average of 0.02 vinyl groups in 100 repeating units, that is, each molecule had an average of 0.8 bis. key.

In addition, the ratio of (A) dimethylsiloxane to (B) methylvinylsiloxane (B) was 50:50, and (C2) was prepared. -Methylethoxysilane tetramer. To this (C2) tetramer, 100 mol was added 0.45 mol potassium hydroxide to perform polymerization. The obtained polymer (siloxane B) was subjected to gas chromatography (capillary column · DURABOND DB-1701 manufactured by J & W)

, Injection temperature: cool on-column 50 ° C / 30 seconds to 270 ° C, carrier gas: helium 30 ml / min, detector: FID) analysis results, the degree of polymerization is about 10, and according to the analysis according to 1H-NMR, it is found that there are an average of 50 vinyl groups in 100 repeating units, that is, an average of 5 double bonds per molecule. These siloxanes A and siloxane B were mixed at a molar ratio of 47:53, and used as VMQ-1 with an average of three double bonds per molecule. FKM ·· Daikin (Daikin) Industrial Co., Ltd. DaiELG902 DCP: Dicumyl peroxide, manufactured by Japan Oil Corporation “Perkmyl D” S: Sulfur powder, “# 325” manufactured by Tsurumi Chemical Industry Corporation “Rubber Component Composition "-72-200404878 EPDM: 100 parts by weight of the above EPDM, 3 parts by weight of Vestenamer 8012 (manufactured by Degussa), 3 parts by weight of carbon black" N582 "(manufactured by Asahi CARBON), and magnesium silicate" MISTRON PAPER (Transliteration ) "(Manufactured by MISTRON, Japan), 25 parts by weight, naphthalene-based oil" Daiana Process Oil! J NS 100 "(manufactured by Idemitsu Kosan Co., Ltd.), 5 parts by weight, paraffin oil" Daiana Process Oil PW380 "(Idemitsu Kosan 14 parts by weight, 1 part by weight of polyethylene glycol (4000), 0.5 parts by weight of stearic acid, 3 parts by weight of zinc oxide, SBR60 / NBR40: 60 parts by weight of SBR, 40 parts by weight of NBR, 50 parts by weight of carbon black "N582" (manufactured by Asahi Carbon Corporation), 10 parts by weight of naphthalene-based oil "Daiana Process Oil NS 100" (manufactured by Idemitsu Kosan Co., Ltd.), 1 part by weight of stearic acid, and 5 parts by weight of zinc oxide And stabilizer "n〇NFLEX (transliteration) RD" (Seiko Chemical 1 part by weight, stabilizer "SUNT1GHT Z" (manufactured by Seiko Chemical Co., Ltd.) 1 part by weight, stabilizer "SUNGUARD PVI" (manufactured by FLEXYS) 0.2 parts by weight, vulcanization accelerator " NOCSELLER_CZ "(parts by weight of Onai Shinko Chemical Co., Ltd., vulcanization accelerator" NOCSELLER-TS "(manufactured by Onai Shinko Chemical Co., Ltd.) 0.3 parts by weight. SBR60 / NR40: SBR60 parts by weight, NR4 above. Parts by weight, 45 parts by weight of carbon black "Asahi # 7〇" (manufactured by Asahi Carbon Company), parts by weight of naphthalene-based oil "Daiana Process Oil NS 100" (manufactured by Idemitsu Kosan Co., Ltd.), stabilizer "200404878 NOCLAC ODA" ( 1.5 parts by weight of Ina Shinko Chemical Co., Ltd., stabilizer NOCLAC 224 (manufactured by Ina Shinko Chemical Co., Ltd.) 1.5 parts by weight, vulcanization accelerator "NOCSELLER-DM" (manufactured by Ina Shinko Chemical Co., Ltd.) 0.6 Parts by weight, 0.3 parts by weight of a vulcanization accelerator "NOCSELLER-CZ" (manufactured by Ochiu Shinko Chemical Co., Ltd.), 0.3 parts by weight of a vulcanization accelerator "NOCSELLER-TS" (manufactured by Ouchi Shinko Chemical Co., Ltd.), 1.5 parts by weight of stearic acid, Zinc oxide 5 weight VMO-2: Toray-Dow Corning's "silicone rubber SH851" FKM: Fluorine-containing rubber "DaiELG902" (manufactured by Daikin Industries) 100 parts by weight, carbon black "ThermaxN990 '' 10 parts by weight of BR made by Cancarb Corporation:

100 parts by weight of a butadiene-based rubber "BUNACB100" (manufactured by Bayer), 10 parts by weight of a naphthalene-based oil "Daiana Process Oil NS 24" (manufactured by Idemitsu Kosan Co., Ltd.), and carbon black "SHOW (BLACKN330T)" (Manufactured by Showa Kyabott) 50 parts by weight, 15 parts by weight of a stabilizer "Vulkanox 40 10NA" (manufactured by Bayer), 1 part by weight of a vulcanization accelerator "NOCSELLER-CZ" (manufactured by Onai Shinko Chemical Co., Ltd.) 2 parts by weight of fatty acid and 5 parts by weight of zinc oxide. DCP:

"Perkmyl" made by Nippon Oil Corporation "Perkmyl D -74-200404878 js ^ _ Sulfur powder," # 3 25 "manufactured by Tsurumi Chemical Industry Co., Ltd. TAIC: triallyl isocyanate [test Method] Each of the above resin compositions is molded by injection molding or compression molding to obtain a flat plate having a thickness of 4 mm. On one side of the flat plate, a rubber solution prepared by the following method was applied by a bar coater to a thickness of 1000 m. After the rubber solution is applied, it is left for 1 hour to allow the solvent to air dry to form an unvulcanized rubber layer. Put the resin flat plate with an unvulcanized rubber layer so that the unvulcanized rubber layer is on top, put it in a mold that has been temperature-adjusted to 170 ° C, and then place a specific amount of the above-mentioned rubber member on the unvulcanized rubber layer. The unvulcanized resin composition is vulcanized and bonded to the unvulcanized rubber layer and the unvulcanized rubber member while being compression-molded so that the thickness of the rubber member becomes 3 mm. Heating time is approximately 15 minutes

In addition, Table 1 shows the combination of the resin flat plate, the vulcanized rubber layer, and the vulcanized rubber member. In the table, "*" marks in Examples 2, 3 and Examples 10 and 11 indicate that after the unvulcanized rubber layer is formed on the resin flat plate, the unvulcanized rubber composition for a rubber member is placed on the vulcanized rubber layer and the 170 ° C Vulcanizer. [Preparation of rubber solution] 100 parts by weight of the rubber layer for the rubber layer with the composition ratio (parts by weight) shown in the table • 75-200404878 parts, dissolved in ethyl acetate, MEK, and toluene at a ratio of 1: 1 400 parts by weight of the solvent was mixed, and a vulcanizing agent and trimethylolpropane trimethacrylate (TRIM) were added to the solution at the ratios shown in the table to prepare a rubber solution. [Evaluation of Adhesiveness] The flat plate-shaped composite of the resin / rubber layer / rubber member obtained by the above method was cut to a width of 30 mm, and the obtained test piece was used for a 180 ° peel test. This peeling test is based on the following adhesive evaluation: "A": The peeling interface occurs in the rubber layer or rubber member (that is, cohesive failure occurs), and the damage is 100% cohesive failure; "B" : More than 50% is cohesive failure; "C": sufficient adhesion, more than 50% of peeling occurs at the resin / rubber layer interface, or occurs at the rubber layer / rubber member interface;

"D": It is easy to peel off at the resin / rubber layer, or at the rubber member interface of the rubber layer. The results are shown in Table 1. The ratios of the components in the table are parts by weight. As is clear from Table 1, the composite systems obtained in the examples showed high bonding strength. -76-200404878 at # < PO PQ < < < PQ ο u < 〇QQ < < < < < < < < PQ 鹚 inchy 1 1 1 1 1 1 1 1 1 1 I 1 1 1 TAIC4 I Η < Η un Η (N (Ν (Ν in (Ν (Ν tn < N CN ^ T) CN (N CN in (N (N (N (N til p3 CN C / D (N 00 Ph U Oh 〇 Cu υ Ρη U Ph U PLh ua, u CU U u Ph U (N cn (N cn (N cn (N 00 (Ν 00 (Ν00 Ph U CU 〇Ph u Ph u Xin QQQQQQQQQQQQQQQQ Salt 鹚 EPDM 2 PQ 5 § 2 < N σ § SS Ρη s S 〇hs Ph s Oh s Ph O 2 m 1 5 Ρη CQ (N σ s ρμ § (N ά § S > ρη Q ω Q ω QWQ ω Q ω Q ω Q ω Q ω Q ω 5 O ο νο Q ω > QWS > PQ 00 PQ 00 s PQ C / D ω C / 0 m ΓΟ m υη mm TRIM 0.5 VA oooo SHSS Η SS Η ο ο OOO ss 〇ο ο ο 〇s H s 2 H s 2 H (N & * (N CN DCP2 (N DCP2 CN (N < N * (N (N (N & l t; N 燧 沃 Ph U o VwP u Q o Q u G υ Q Oh uo PU u Q 〇Q δ Ω UQ CN 00 (Ν 00 (Ν 00 u Q u 0 PU u Q u QS Rubber EPDM SBR SBR VMQ- 1 EPDM EPDM EPDM EPDM EPDM EPDM EPDM SBR SBR Q Pη § CQ 00 SBR VMQ-1 EPDM FKM VMQ-1 < ^ T) mss / ^ s un s wn sso S sr ^ \ > 2 H 2 H 2 H Vw ^ 2 H 2 H s H 2 H Position π | Active Atomic Inch Inch Inch Inch Inch To Inch (N Inch (N to CN oo o 00 d VD 'O' Ο 'Ο' O Double bond U-Ui Μ r—H r—4 r— (/ ~ N r? cn rn / ^ N / —N / ^-N / ^ s / ^ S u / —s Ξ s / —smn = q < (N < (N < (N < (N < < N < (N < (SJ < < N < CN < (N < (N < (N < mr- (DQ rH β r-M 0Q β 5 H r · 1 S m S s 3 sss ω Ph ω Ph ω Pη ω Pη C / D PQ Ph i Jg Warp < n. ≪ pt < pt < pt < ρ (< ρη cp , < π, cp (< Ph < Ph < pt < Oh Ph PU Ρη thin MH cr—H (N cn m inch ν〇m b t H 00 a \ m (N rn inch 〇t—1, r— ^ rH (N ΐ—Η r—I r—1 v〇00 t—H, edit, hold, edit, edit) IK 1¾ UU | ι; | 1; U u ± Λ Xi㈣ Compilation Dance m grip IK Ιϋ ι <# ϋ IK i < IK in

Claims (1)

200404878 Patent application scope 1 · A resin / rubber composite, characterized in that the vulcanized rubber member and the resin member are combined by a vulcanized rubber layer vulcanized by a vulcanizing agent. 2. The composite according to item 1 of the application, wherein the vulcanizing agent is a sulfur-based sulfurizing agent or a peroxide-based vulcanizing agent. / 3 • The composite according to item 1 of the patent application scope, wherein the vulcanizing agent is an organic peroxide. 4. The composite according to item 1 of the patent application, wherein the resin member is composed of at least one selected from a thermoplastic resin and a resin having a crosslinkable group. 5. The composite according to item 4 of the patent application, which has The resin of the crosslinkable group is at least one selected from a thermosetting resin and a thermoplastic resin having an unsaturated bond. 6. The composite according to item 1 of the scope of patent application, wherein the unvulcanized rubber composition and resin member used to form the vulcanized rubber layer can satisfy at least one of the following conditions (i) to (iii): (0 resin member The reason is that the orbital interaction energy coefficient S represented by the following formula (1) is 0.006 or more, and is composed of a thermoplastic resin having at least two active atoms (at least one selected from hydrogen and sulfur atoms) in one molecule. Composition: S = (C Η Ο Μ Ο, η) 2 / | Ec-EηΟΜΟ, π | + (CLU Μ Ο, η) 2 / | E c · E l U Μ Ο, η I (1) [Formula The 'Ec, CHOMO'n, Εη〇ΜΟ, π, CLUMO'n, and ELUM〇, n are all calculated by the semi-empirical molecular orbital method ΜΡΑCPM3, Ec -78-200404878 represents the radical as a vulcanizing agent The radical orbital energy (eV) of the generator 'CH0M0, n represents the molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of the ^ th active atom constituting the basic unit of the thermoplastic resin, and EH0M0, n represents the above-mentioned HOMO Orbital energy (ev), CLUMO, n represents the first The molecular orbital coefficient of the lowest empty molecular orbital (LUMO) of η active atoms, ELuM0, n represents the orbital energy (eV) of the above LUMO]; (Π) at least one of the unvulcanized rubber composition and the resin member 'It contains a polyfunctional polymerizable compound with several polymerizable groups; (iii) The resin member is composed of a thermosetting resin or a resin having an unsaturated bond in the molecule, and the unvulcanized rubber composition contains several polymerizable polymers. A multifunctional polymerizable compound based on a base 7. The composite according to item 1 of the patent application scope, wherein at least one of the vulcanized rubber layer, the vulcanized rubber member, and the resin member is formed of a composition containing a vulcanizing active agent. 8. The composite according to item 7 of the application, wherein the vulcanizing active agent is composed of a polyfunctional polymerizable compound having a plurality of polymerizable groups. 9. The composite according to item 1 of the application, wherein the vulcanized rubber layer is formed of an unvulcanized rubber composition containing a vulcanizing agent and a vulcanizing active agent, and at least one of the vulcanized rubber member and the resin member is a vulcanizing active member Agent composition. 10. The composite according to claim 7 in which the resin member is formed of a composition containing a vulcanizing active agent. 1 1 · The composite according to item 7 of the scope of patent application, wherein the amount of the vulcanizing active agent is -79-200404878 12. 13. 14. 15. 16 is 0.1 parts by weight based on 100 parts by weight of at least one component selected from resin and rubber ~ 10 parts by weight. For example, the composite according to item 7 of the application, wherein the amount of the vulcanizing active agent is 2 parts by weight or less based on 1,000 parts by weight of the rubber. For example, the composite of item 10 in the scope of patent application, wherein the resin member further contains a stabilizer for a vulcanization active agent, and the stabilizer is composed of at least one selected from an antioxidant, a light stabilizer, and a thermal polymerization inhibitor. For example, for the composite of item 13 in the scope of patent application, the ratio of the vulcanization active agent to the swell stabilizer is the former / the latter (weight ratio) == 99/1 ~ 25/75. For example, the composite of item 1 of the patent scope, wherein the resin member is selected from the group consisting of polyamide resin, polyester resin, polyacetal resin, polyphenylene ether resin, polysulfide resin, and polyetherketone system. Resin, polycarbonate resin, polyimide resin, polyfluorinated resin, polyurethane resin, polyolefin resin, halogen-containing vinyl resin, styrene resin, (meth) acrylic acid Resins, thermoplastic elastomers, phenolic resins, amine resins, epoxy resins, thermosetting polyimide resins, thermosetting poly% urethane resins, silicone resins, unsaturated polyester resins, vinyl ester resins And at least one of a diallyl phthalate resin and a thermosetting (meth) acrylic resin. • The composite body according to item i of the patent application, wherein the vulcanized rubber layer is vulcanized by a sulfur-based vulcanizing agent. • The composite body according to item 丨 of the patent application scope, wherein the vulcanized rubber layer is composed of a diene rubber. -80-17 200404878 1 8 · The composite according to item 1 of the patent application, wherein the vulcanized rubber layer is composed of a styrene-diene rubber vulcanized with a sulfur vulcanizing agent, and the resin member is made of polyphenylene ether. Made of resin. 19. A method of manufacturing a resin / rubber composite, wherein a rubber element selected from an unvulcanized rubber composition, a semi-vulcanized rubber member, and a vulcanized rubber member is selected from an uncured resin through a layer of an unvulcanized rubber composition containing a vulcanizing agent, and a resin selected from unformed resin. The composition, the semi-molded resin member, and the resin elements of the molded resin member are in contact with each other to vulcanize the unvulcanized rubber or the semi-vulcanized rubber, and the vulcanized rubber member and the resin member are combined by a vulcanized rubber layer. 20. The method according to item 19 of the scope of patent application, wherein an unvulcanized rubber composition layer containing a vulcanizing agent is formed on a bonding surface of at least one of the bonding surfaces of the rubber element and the resin element, and the unvulcanized rubber is used. The composition layer heats the rubber element and the resin element under pressure. 2 1. The method according to item 20 of the patent application, wherein the unvulcanized rubber composition layer containing the vulcanizing agent is formed from a film or coating agent of the unvulcanized rubber composition. 22. The method according to item 19 of the scope of patent application, wherein the unvulcanized rubber composition of the intermediate layer is interposed between the molded resin member and a rubber element selected from the unvulcanized rubber composition and the semi-vulcanized rubber member, while molding the unvulcanized rubber. And / or semi-vulcanized rubber while being cross-linked or vulcanized. 23. The method according to item 19 of the scope of patent application, wherein at least one of the unvulcanized rubber composition layer, the rubber member and the resin member contains a vulcanization active agent. 24. The method according to item 19 of the scope of patent application, wherein the method is between a rubber element, -81- 200404878 and a resin element, and the non-functional polymerizable compound containing an organic peroxide and several polymerizable groups is used. The layers of the vulcanized rubber composition are interposed and heat-molded under pressure. 25. The composite according to item 24 of the patent application, wherein at least one of the rubber element and the resin element contains a polyfunctional polymerizable compound having a plurality of polymerizable groups. 26. The composite body according to item 19 of the scope of patent application, wherein the resin element contains a vulcanizing active agent, and the amount of the vulcanizing active agent is 0.1 to 5 parts by weight based on 100 parts by weight of the resin element. -82-200404878 vulcanizing agent (a radical-generating agent such as an organic peroxide). The resin member may include a thermoplastic resin or a crosslinkable group-containing resin, or a resin having an active atom (a hydrogen atom or a sulfur atom ) · At least one component among an unvulcanized rubber composition for forming the vulcanized rubber layer, and the resin member may contain a polyfunctional polymerizable compound having a plurality of polymerizable groups. The present invention provides a composite in which a resin member and a vulcanized rubber member are firmly bonded in a wide range of combination. (2) Brief description of the element representative symbols of this representative figure