TWI294894B - Resin compound, the complex using it and the method of using it - Google Patents

Description

1294894 发明Invention Description: [Technical Field] The present invention relates to a resin composition excellent in adhesion to rubber, a resin composition integrally bonded to rubber, and a useful composite for mechanical parts, automobile parts, and the like. Body (or composite parts) and its method of manufacture. [Prior Art] A method of bonding a resin molded portion to a rubber molded portion is known in which a binder is bonded to a rubber molded body. However, the method of using the adhesive is complicated in engineering and complicated in engineering management, and it is not only costly, but also cannot produce a sufficient adhesive. In addition, a composite in which a resin and a rubber are directly bonded is proposed. For example, a thermoplastic plastic component such as polyoxymethylene or an olefin polymer or a vulcanized rubber component (polybutadiene, nitrile, etc.) which is compatible with the thermoplastic plastic component is disclosed in Japanese Laid-Open Patent Publication No. H05-25682. A method for preparing a rubber-plastic composite in which a plastic surface is melted and a plastic component is brought into contact with a rubber component to be solidified. However, this method is limited in the shape of the bonding portion of the composite, and it is not possible to obtain a composite of a thermoplastic resin molded body having a complicated shape and a rubber molded body, and the productivity of the composite cannot be improved. A polyphenylene ether-based resin which can contain a styrene-based polymer or an additive, and SBR, BR, IR, I IR are disclosed in JP-A-61-204260. A method of producing a composite by heat-treating in the presence of a sulfur-added synthetic rubber. The ABS resin-rubber composite system is described in Japanese Laid-Open Patent Publication No. Hei. 5-3, No. 1,973, which is a non-sulfurized rubber which is a molded part containing an ABS resin and a rubber component having a critical surface tension of "~39 mN/m 1294894". After the film is laminated, the composite system is heated and bonded. In JP-A-9-124803, a thermoplastic resin containing acrylonitrile (AS, ABS resin, etc.) and a rubber containing acrylonitrile are heated and bonded. Composite parts. However, in order to improve the adhesion between thermoplastic resin and rubber, these methods can be compounded by the compatibility of the two components. The types of resins and rubbers are greatly limited and the utility is narrow. _ About Polyamide-Rubber In the Japanese Patent Publication No. Hei 2-150439, Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei. In the method of adding sulfur to a complex in the presence of sulfur, a rubber containing a carboxyl group-containing or anhydride group and a peroxide and a vulcanization activating agent (ethylene glycol dimethacrylate, triallyl isocyanate) are used. Wait And alkoxy decane compound as a rubber component. It is proposed in the patent publication No. 8-156188 to obtain a composite part by adhering an epoxy group-containing resin component to a rubber component containing a mercapto group or an acid anhydride group, and vulcanizing it. In the methods described in these documents, the resin is utilized in order to bond the resin to the rubber.

The reaction (the bonding reaction of an amine group with a carboxyl group or an acid anhydride group, and the bonding reaction of an epoxy group with a carboxyl group) limits the types of resins and rubbers, and the resin/rubber composite cannot be obtained to a large extent. For the polyester-rubber composite, in the manufacture of a thermoplastic component of a hard component and a vulcanized rubber composite of a soft component, a rubber and a peroxygen, a chemical vulcanizing agent and a difunctional or polyfunctional malaquinium are used. The rubber component of the imide and the period of the required sulfurization _ active agent (JP-A No. 7-304880), and the rubber component containing the rubber and the peroxide sulphurizing agent and the decane compound and the required sulphurizing active agent ( Japanese Patent Laid-Open No. Hei 7 - 1 66043). In addition, the composite film of the film 1294894 film and the rubber film is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The rubber film of vinegar is laminated and vulcanized as a rubber film (polyoxyalkylene rubber or ethylene propylene rubber) as a binder improver to obtain a composite sheet. When these methods are proposed to increase the adhesion, a sulfur-adding active agent is added to the rubber component, but the combination of the resin and the rubber does not allow the rubber and the resin which are widely limited to be bonded and integrated with high adhesive strength. Therefore, the object of the present invention is to provide a resin composition which can reliably and firmly bond a resin to a wide range of rubber without using a binder, and a process for producing the same. Another object of the present invention is to provide a resin composition of a resin and a rubber composite which can be stably and industrially produced by which a resin is strongly bonded to a rubber and a process for producing the same. Another object of the present invention is to provide a composite in which a resin and a rubber can be directly and reliably bonded, and a process for producing the same. SUMMARY OF THE INVENTION In order to achieve the above problems, the inventors of the present invention have further intensively studied and found that by combining a sulfur-adding active agent and a stabilizer to achieve a resin composition, the adhesion of the resin to a wide range of rubbers can be remarkably improved or improved. The present invention has been completed. In other words, the resin composition of the present invention is a resin, a sulfur-adding active agent (for example, a compound having several kinds of polymerizable unsaturated bonds), a stabilizer (for example, an antioxidant, in order to improve the adhesion of the resin to the rubber). Light stabilizer). As the resin composition, a resin material which is a composite in which a vulcanized rubber formed by vulcanization of unsulfurized rubber -8 to 1294894 is directly bonded can be used. The above composite may be directly bonded to a resin member composed of the above resin composition and a vulcanized rubber member composed of a vulcanized rubber. The resin constituting the above resin composition is at least one selected from the group consisting of the following formula (1) and is selected from an average of two orbital interaction energy coefficients s in one molecule of 0.006 or more hydrogen atoms and/or sulfur atoms, and has no A crosslinkable resin of a thermoplastic resin having a saturated bond and a thermosetting resin having a crosslinkable functional group. S = (CH0M0,n)2/ 丨Ec-EHOM〇,n | +(CLlJM(),n)2/ I Ec_ELUM0,n 丨(1) (where ' E c, CH.M.. n, EH.M 〇 η, CL υ M.n, EL.M 〇. n are all obtained by the semi-empirical molecular orbital method MOPACPM3, E. It represents the radical orbital energy (eV) of the radical generator, CH〇M ( n) indicates the molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of the n-th hydrogen atom or sulfur atom constituting the basic unit of the resin, and EHQM().n indicates the orbital energy (eV) of the above HOMO, (^ ϋΜ〇.η represents the molecular orbital coefficient of the lowest empty molecular orbital (LUM0) of the above-mentioned n-th hydrogen atom or sulfur atom, and E_Q.n represents the orbital energy (eV) of LUM0) The above-mentioned sulfur-adding active agent may also be a number a compound having an α,β-ethylenically unsaturated bond (for example, a plurality of compounds having a (meth) acrylonitrile group). The stabilizer may be a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, or sulfur. An antioxidant, a hydroquinone antioxidant, a porphyrin antioxidant, a hindered amine light stabilizer, a quenching agent, etc., or The base capturing function: the ratio of the above-mentioned sulfurizing active agent and stabilizer is 0.1 to 10 parts by weight, and the stabilizer is 0 _ 〇 1 to 5 parts by weight for 100 parts by weight of the resin. The ratio (weight ratio) of the sulfurizing active agent to the stabilizer is the former / 9 - 1294894 and the latter = 99 / 1 ~ 25 / 7.5. Further, the above resin composition may further contain one molecule represented by the above formula (1). The medium average has two or more orbital interaction energy coefficients S of 006 or more and a hydrogen atom and a molecular weight of 1 000 or less. The unsulphurized rubber in the above composite may be at least one selected from the group consisting of free radicals. The composition of the agent (organic peroxide, azo compound, sulfur-containing organic compound, etc.) and sulfur sulfurizing agent is formed, and the proportion of the sulfurizing agent is 1 to 10 by weight for 100 parts by weight of the unsulfurized rubber. The present invention comprises a method of kneading a resin with a sulfurizing active agent and a stabilizer to produce the above resin composition. Further, the present invention comprises (1) contacting the unsulfurized rubber composition containing the above resin composition and a sulfurizing agent. Forming with resin zero In the composite system method of bonding a rubber member made of a vulcanized rubber, the molding resin material of one of the resin composition and the resin component and the vulcanizing agent on the contact surface with the molding resin material are active, so that at least a composite system method in which a rubber composition of a sulfur rubber is formed in contact with one of the formed rubber materials of the preliminary molded body, and the formed rubber material is vulcanized or crosslinked to bond the resin component and the rubber component, and (2) The resin composition is kneaded and molded with an unvulcanized rubber containing a sulfurizing agent to produce a composite method comprising a vulcanized rubber phase and a resin phase. [Description of the Invention] The resin composition of the present invention is composed of a resin, a sulfurizing active agent and a stabilizer. When the resin composition is a resin which can highly improve or improve the adhesion to the rubber, it can be used as a resin material which is a resin/rubber composite which is directly bonded to a vulcanized vulcanized rubber of a non-sulfurized rubber. [Resin composition] - 1 0 - 1294894 [Resin] The resin used in the resin composition of the present invention is not particularly limited, and a wide range of resins (thermoplastic resin, thermosetting resin) can be used. The thermoplastic resin is, for example, a polyamine resin, a polyester resin, a polyurethane resin, a poly(thio)ether resin (polyacetal resin), a polyphenylene ether resin, a polysulfide resin, a polyether ketone resin, etc., a condensation-based thermoplastic resin such as a polycarbonate resin, a polyimide resin, a polyfluorene resin, or a polyurethane resin; a polyolefin resin; (meth)acrylic acid An Ethylene-based polymerizable thermoplastic resin such as a resin, a styrene resin, a halogen-containing resin, or a vinyl resin (for example, polyvinyl acetate or polyvinyl alcohol); a thermoplastic elastomer or the like. a thermosetting resin such as a phenol resin, an amine resin, an epoxy resin, a polyoxyalkylene resin, a thermosetting polyimine resin, a thermosetting polyurethane resin, or the like, a polycondensation or addition condensation resin; a thermosetting acrylic resin; An addition polymerization resin such as an ethyl ester-based resin, an unsaturated polyester resin, or a diisopropyl acrylate resin. These resins (thermoplastic resin, thermosetting resin) may be used singly or in combination of two or more. Further, the above resin may be a resin having high activity for a vulcanizing agent (e.g., a radical generator or the like) which is used for vulcanization of rubber. When the resin is used, it is compatible with the sulfurizing active agent, and the resin adhesion to the rubber can be further improved. The active resin of the vulcanizing agent is, for example, (i) a resin having an active atom, (i i) a resin having a crosslinkable group (hereinafter collectively referred to as such a resin as a resin or an active resin). -11- 1294894 (Resin having an active atom) The active atom system means an atom (i.e., an active hydrogen atom or an active sulfur atom) which is reactive with a radical generator. Specifically, the type of the resin-based radical generating agent is selected, and for example, the orbital interaction energy coefficient s is constant as shown by the following formula (1) (for example, 0·006, preferably 0. 008) The above active atoms. Preferably, the orbital interaction energy coefficient S of the active atoms is 0.006 to 0.06, preferably 0.007 to 0.05 (more preferably 0. 0 1 to 0. 0 4 5 ). The number of active atoms is related to a functional group bonding site (end, branch or main chain, etc.) having an active atom, for example, an average of 2 or more (about 2 to 10,000) in one molecule of the resin, preferably an average of 2.5. More than one (2.5 to 5000), and more preferably three or more (3 to 1000). The number of active atoms in one molecule of the resin is usually from 2 to 100 (preferably from 2.5 to 50, more preferably from 3 to 25, and most preferably from 3 to 20). S = (CH_,n)V 丨Ec-EH_,n I + (CL_,n)2/ | Ec-ELUM0,n | (1) (where ' Ec , CHOM〇.n , E HOMO.n , CLUM〇.n E LOMQ.n is the enthalpy obtained by the semi-empirical molecular orbital method M0PACPM3, E is the free radical orbital energy UV of the radical generator, and CHQMQ, n is the hydrogen of the nth constituting the basic unit of the resin. The molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of an atom or a sulfur atom, EHQM().n indicates the orbital energy (eV) of the above HOMO, and CluMO.η indicates the lowest of the above-mentioned nth hydrogen atom or sulfur atom. The molecular orbital coefficient of the empty molecular orbital (LUM0), and the EtUMQ.n system indicates the orbital energy (eV) of LUM0. The M0PACPM3 system of the formula (1) is one of the molecular orbital methods (M0). The molecular orbital method is one of the approximation methods for theorizing the electronic state of a molecule. It can be divided into - 1 2 - 1294894 as an empirical method such as the Huckel method, a semi-empirical method to improve the approximate Huckel method, and a molecular orbital calculation only by rigorous calculation. Three methods, such as non-experience methods of coefficients. In recent years, with the development of computers, the main methods are semi-empirical methods and non-experience methods. The molecular orbital method is one of the most powerful methods related to molecular structure and its chemical reactivity. For example, regarding the number of registrations of the molecular orbital method of the Japanese scientific and technical literature information base (]〇IS), when the keyword is detected as the "Molecular Orbital Method", there are about 5,300 pieces (period · · 1980) ~ 2 years in May). M0PACPM 3 is the core method of the NDDO (Neglect of Diatomic Differential Overlap) method which is one of the above semi-empirical methods. M0PACPM3 mainly uses the reaction of organic compounds for the purpose of investigation, many literatures or books ["Molecular Orbital Method M0PAC Handbook" (Hirano Hirano, Tanabe Kazuo, Haeeda, 199 1st), "Three Orders" (Mizawa Yujiro, he, Chemistry, 1 983), "Handbook of Computational Chemistry" (Da Zeying, translated by Tim Clark, Jiu Shan, 1985)]. The basic unit of the formula (1) means a molecular structure of a polymer terminal and 1 to 3 repeating units. In other words, when the polymer compound is calculated by M0PACPM3, since the number of atoms constituting the molecule is too large, it is difficult to calculate the molecule as an object. Therefore, it is also possible to calculate the molecular structure type (basic unit) formed by the polymer terminal and 1 to 3 repeating units. For example, 'Molecular structure of polybutylene terephthalate (PBT) (repeating unit) It is represented by the chemical formula (CH2-CH2-CH2-CH2-0-C(=0)-C6H4-C(=0)-〇))••, but H0-CH2-CH2 can also be simply used in the above formula (1). -CH2-CH2-0-C(=0) -C6H4-C(=0)-0H is calculated as the basic unit. 1294894 When the orbital interaction energy coefficient S of the formula (1) is called the reactivity index, there are definitions and explanations for the entire book, and the chemical reactivity is generally used. For example, in the "Introduction Boundary Orbital Theory" (72 pages, Yamagata Shinichi, Inaba, and Kodansha Natural Science and Technology, 1989), the orbital interaction energy coefficient S is "in the case of two orbital interactions. (a) The smaller the energy difference is, the smaller the (b) the larger the overlap, the larger the interaction, and the stronger the interaction. Formula (1) is based on the superdelocal ozability (Sr) proposition published in 1954 by Dr. Fukui, a Nobel laureate (see "Using the Molecular Orbital Method", page 71, Imoto, and the same person, 1 986), which is the same as the formula (1) advocated by Sr, and is derived from various books or documents. The focus here is on the molecular orbital method, which is widely known based on molecular structure and chemical reactivity. Therefore, the orbital interaction energy coefficient S[1/eV] defined by the formula (1) is not a simple number of enthalpy, and has the same meaning as the parameter or physical property 分子量 (molecular weight, functional group, etc.) for a specific material. Counting. Moreover, the radical orbital energy Ee(eV) of the radical generator is based on the molecular structure of the radical, and is preferably calculated by MOP ACPM3, but it can be used simply based on the type of the radical generator. And set it. For example, Ee=-8 eV when the radical generator is an organic peroxide and E when it is an azo compound can be calculated. = - 5 e V, when it is a sulfur-containing organic compound other than sulfur, E c = _ 6 e V 〇 Orbital interaction energy coefficient S is a hydrogen atom (active hydrogen atom) of a certain enthalpy (for example, 〇· 〇〇6 ) When the radical generator is an organic peroxide, for example, an amine (-NH2) group (for example, a terminal amine group) or an imido group (-NH _ ) (for example, a main chain or a 1294894 terminal imine group, a guanamine bond) NH-based, etc., methyl (-CH3) group, methyl (-CH2) group (main chain or terminal methyl group), methine group (-CH=) group (backbone or terminal methine group) ) such as a hydrogen atom. Further, the orbital interaction energy coefficient S is a sulfur atom (active sulfur atom) of a certain enthalpy (for example, 〇. 〇〇6) or more, and a thiol (-) group, such as thiol (-SH), when the radical generator is an organic peroxide. A sulfur atom such as a thiol group (such as a C! _ 4 alkylthio group such as a methylthio group or an ethylthio group) or a sulfonyl group (_SO-). The methyl group is, for example, an alkyl chain, a cycloalkyl chain or a methyl group bonded to an aromatic ring, a methyl group bonded to an oxygen atom (methyl group of a methoxy group), or the like. a methyl group, for example, a methyl group, a (poly)oxymethane unit, a (poly)ethylene oxide unit, or the like, which forms a linear or branched alkyl group of a main chain or a side chain, or a (poly)alkylene oxide group. The unit is a methyl group, an amine group or an imine group or the like which is adjacent to a nitrogen atom. The methine group is, for example, an a-methyl group adjacent to an amino group or an imido group, for example, an α-position methine group for an amine group of an aminocycloalkyl group. The resin may have several (e.g., an average of two or more) active atoms in one molecule. In other words, in general, the resin may be a single molecule or a mixture of a plurality of molecules having several different configurations or chain lengths. Therefore, the whole part does not need to have several active atoms, and when calculating the main basic units of the preset, the number of the average active hydrogen atoms in one molecule may be 2 or more. For example, a polymer having a weight of C(=0))η (polyamide 66) may have a basic unit of NH2-(CH2)6-NH-C(=0)-(CH2)4- C(=0)-0H is the benchmark calculation. When the free radical generator is an organic peroxide, the terminal NH2-(CH2)6-NH-c(=o)-(ch2)4-c(=o)-oh is In the reference, when the radical generator is an organic peroxide, two hydrogen atoms in the terminal NH2 group are active hydrogen atoms (ie, S ^ -15 - 1294894 〇·006 ). In this case, the average number of active hydrogen atoms in one molecule of polyamine 66 can be determined by the ratio of the terminal Ν 基 2 group of the polymer of the aggregate (polyamine 66) to the terminal COOH group. (2) Find the benchmark.

N = 2x A (wherein A represents the number of average terminal NH2 groups in one molecule). For example, when the terminal NH2 group/terminal COOH group = 1 / 1 (mole ratio), the number of terminal NH2 groups in one molecule A = One, the number of atoms of active hydrogen atoms in one molecule is N = 2. Further, when the terminal 2 base/terminal COOH group = 1/2 (mole ratio), the number of terminal thiol groups in one molecule, A = 2/3, and the number of active hydrogen atoms in one molecule N = 4/3 One. Further, when the resin is a mixed resin composed of a plurality of resins having different numbers of active atoms, the number of active atoms of the mixed resin can be expressed by the average 値 of the number of active atoms of each resin. In short, the number of active atoms formed by the basic unit of each resin constituting the mixed resin is determined individually, and the ratio of the weight of each resin is averaged to obtain the average number of active atoms, and the number of active atoms of the mixed resin can be determined. For example, the mixed resin is composed of the above N = 2 polyamine 6 6 (A) and the above N = 4/3 polyamine 66 (B), (8) / (8) = 1 / 1 (Mo In the case of the ear ratio, the number of active atoms in one molecule of the mixed resin is N = 5 / 3. Further, the mixed resin is composed of the above N = 2 polyamide 66 (A) and polyamine 66 (C) having a carboxyl group at the entire end (total of N = 0), and A/C = 3/1 (Mo In the case of the ear ratio, the number of active atoms in one molecule of the mixed resin is N = 3 / 2. The resin having an active atom is, for example, a polyamido resin, a polyester resin, a polyacetal resin, a polyphenylene ether resin, a thermoplastic elastomer or an amine resin exemplified above. Further, a resin which does not have the above-mentioned several kinds of active atoms or a modified resin in which an active atom (amine group, epoxy base, or the like) is introduced using -16-294494 sa 2/8 modified κ can be used. The thermoplastic resin is, for example, an ethylene polymerizable resin [(meth)acrylic resin (polymethyl methacrylate, methyl methacrylate-styrene copolymer (MS resin), polyacrylonitrile, etc.), styrene resin ( Polystyrene; styrene copolymer of AS resin, styrene-methyl methacrylate copolymer, styrene-bonded copolymer of HIPS, ABS resin, etc.), alone or copolymer of halogen-containing monomer ( Polyvinyl chloride, vinylidene chloride copolymer, etc.), ethylene resin (polyvinyl acetate, polyvinyl alcohol, etc.), etc., condensed resin [polycarbonate (bisphenol A type polycarbonate resin, etc.), poly A quinone imine resin, a polyfluorene-based resin, a polyether-based resin, a polyetheretherketone-based resin, a polyacrylate-based resin, or the like]. The ethylene polymerization-based resin, for example, a vinyl monomer and a monomeric copolymer having a carboxyl group or an acid anhydride group such as (meth)acrylic acid or maleic anhydride, and a carboxyl group or an acid anhydride group is introduced into the ethylene polymerization resin, and chlorine is required depending on the desired content. The sulfinyl group is reacted to form an acid chloride group, and ammonium, a monosubstituted amine (monoalkylamine, monoarylamine, etc.) or the above-exemplified diamine is reacted to form a modified resin by introducing an amine group. Further, (poly)alkylene glycol mono(meth)acrylate or (poly)alkylene oxide monoalkyl ether (meth)acrylic acid is copolymerized with the above ethylene monomer by grafting in an ethylene polymerization resin The polymerization is carried out by introducing an active hydrogen atom. Further, the ethylene polymerization resin or the condensation resin is a graft polymerization of a monomer having a carboxyl group or an acid anhydride group in the resin, and a carboxyl group or an acid anhydride group is introduced into the resin, and the desired reaction with the thionyl chloride group is carried out in the same manner as described above. The acid chloride group is formed to react ammonium, a monosubstituted amine or the above-exemplified diamine, and is introduced into an amine group to be modified. Further, the resin constituting the resin composition of the present invention may be composed of a resin (or a modified resin) containing the above-mentioned active atom in a predetermined concentration of -17 to 1294894 and another resin. The other thermoplastic resin contains an unmodified thermoplastic resin corresponding to the above-mentioned modified resin, for example, a styrene resin, a (meth)acrylic resin, a halogen-containing monomer alone or a copolymer (such as a fluorine-based resin), or a vinyl resin. A polycarbonate resin, a polyimide resin, a polyfluorene resin, a polyether oxime resin, a polyether ether ketone resin, a polyacrylate resin, a liquid crystalline polyester resin, or the like. Further, a thermosetting resin (for example, an amine resin such as urea resin, aniline resin, melamine resin or guanamine resin, or a condensed resin such as a phenol resin or an epoxy resin) can be used by using a hardener having an active atom. Join or harden to introduce active atoms. The curing agent may be selected depending on the type of the resin, for example, an amine-based curing agent (for example, an aliphatic polyamine such as tri-ethyltetramine, an aromatic polyamine such as phenyldiamine or diaminodiphenylmethane) ) a guanamine-based curing agent (for example, polyamine or the like). An addition polymerization resin (for example, an unsaturated polyester, a vinyl ester resin, a diallyl phthalate resin, etc.) such as a radical polymerization having a small active atom concentration can be copolymerized with a monomer having an active atom. Introduce active atoms. Monomer having an active atom such as a monomer having an epoxy c2.4 alkyl unit ((poly)oxiranol mono(meth)acrylate or the like (poly)alkylene oxide mono(meth)acrylate (poly)alkylene oxide mono (meth) acrylate, (poly) oxiranol monomethyl ether (meth) acrylate (poly) alkylene oxide single hospital ether (methyl) a polyacrylic acid ester, a polyfunctional monomer, a (poly) epoxy oxime di(meth) acrylate such as (poly) oxiranol di(meth)propionate, a bismuth A ring One of the oxygen-based adducts (meth)propionate, etc., a monomer having a guanamine bond (profenamine, methylene bis(methyl) acrylamide, hydrazine, bispropene Indoleamine - 1294894 Acrylamide such as ethane, etc. Further, the thermosetting acrylic resin may be crosslinked by an amine resin (for example, melamine resin or guanamine resin) as a crosslinking agent, and may be introduced into an active atom. The constituent monomer of the thermosetting acrylic resin is copolymerized with a polyfunctional polymerizable monomer having an active atom, and introduced into an active atom. The proportion of the resin of the active atom is from 3 〇 to 100% by weight, preferably from 50 to 100% by weight, more preferably from 80 to 100% by weight, based on the total amount of the resin component. 〇 (Resin having a crosslinkable group) The resin of the linking group (for example, when it is called a crosslinkable resin) is divided into a thermoplastic resin having an unsaturated bond (polymerizable or crosslinkable unsaturated bond) and a thermosetting resin having a crosslinkable functional group. Crosslinkability The resin may have the above-mentioned unsaturated bond and crosslinkable functional group. Among the thermoplastic resins having an unsaturated bond, the unsaturated bond may be activated by a sulfurizing agent (a radical generating agent or the like), and is not particularly limited. For example, by applying heat or light, various bonds (specifically, polymerizable unsaturated bonds) having crosslinkability or polymerizability. The unsaturated bond or a unit having an unsaturated bond can be via a bond group (ester bond (- 0C (=0) -, -C (=0) 0 -), guanamine bond (-NHCO-, -CONH -), imine bond (-NH -), urethane bond (- NHC (=0 ) 0 -), a urea bond, a biuret bond, etc. are bonded to the thermoplastic resin. Further, the above unsaturated bond or its unit may be At the end of the resin (end of the main chain) and/or the side chain, it may also be located on the resin primary bond 'may be on both. The group having an unsaturated bond such as a vinyl group, a 1-propenyl group, an isopropenyl group, or a C2.6 -19 - 1294894 alkenyl group of butenyl group, allyl group, 2-methyl-2-propenyl group, 2-butenyl group, etc.; C2 of 4-vinylphenyl group, 4-isopropenylphenyl group, etc. .6 alkenyl-C6.2Q aryl; C6_2G aryl-C2.6 alkenyl such as styryl; ethynyl, 1-propynyl, 1-butynyl, propargyl, 2-butynyl a C2_6 alkynyl group such as 1-methyl-2-propenyl; a mono- or di-1.6-alkyl group such as a vinylidene group, a methylvinylidene group, an ethylvinylidene group or a 1,2-dimethylvinylidene group; a vinylidene group which may have a substituent such as a vinylidene group such as a vinylidene group or a vinylidene chloride; a vinylidene group; an ethynylene group or the like. Specific examples of the thermoplastic resin having an unsaturated bond are, for example, the following forms (i) to (i v ). (i) a polymerizable compound having a reactive group (A) and an unsaturated bond, and a resin (i 1 ) formed by reacting a thermoplastic resin having a reactive group reactive with the reactive group (A) a thermoplastic resin (iii) which is copolymerized or co-condensed to introduce an unsaturated bond, and a polymer mixture (iv) composed of a resin having an unsaturated bond and a resin is introduced into a vinyl group by various organic reactions (for example, a Leber reaction using acetylene) A thermoplastic resin obtained by introducing an unsaturated bond by introducing an unsaturated bond by an organometallic reagent such as ethylene lithium or introducing an unsaturated bond by a coupling agent reaction. The resin containing a preferred unsaturated bond in the resin is resin (i), (i i ) or (i i i ). In the above resin (i), at least one reactive group (A) and a polymerizable compound having at least one unsaturated bond and a reactive group (A) for the above polymerizable-20-1294894 can be used. In the case of a resin having a reactive reactive group (B), an unsaturated bond is introduced into the resin. Typical reactive group (A) of a polymerizable compound such as (A 1 ) hydroxyl group, (A 2 ) residue or its anhydride, (A3) amine group, (A4) epoxy group, (A5) isocyanate group, etc. The reactive group (A) of the compound and the reactive group (B) of the resin are exemplified by the following combinations. Further, the brackets indicate the bonding form of the reactive group (A) and the reactive group (B). (A 1 ) Hydroxy group: (B) a carboxyl group or an anhydride group thereof (ester bond), an isocyanate group (ester bond) (A 2 ) a carboxyl group or an acid anhydride group thereof: (B) a hydroxyl group (ester bond), an amine group (melamine bond) , epoxy group (ester bond), isocyanate group (melamine bond) (A3) amine group: (B) carboxyl group or its anhydride group (melamine bond), epoxy group (imine bond), isocyanate group (醯) Amine bond) (A4) epoxy group: (B) carboxyl group or its anhydride group (ester bond), amine group (imine bond) (A5) isocyanate group: (B) hydroxyl group (ester bond), carboxyl group or its anhydride group (melamine bond), amine group (melamine bond) polymerizable compound such as a hydroxyl group-containing compound [such as allyl alcohol, 2-butene-1-alcohol, 3-buten-2-ol, etc. C6 6 alkane such as c3 6 alkynyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or butane diol mono (meth) acrylate such as alcohol or propynyl alcohol Polyalkylene oxide c2_6 alcohol mono(meth)acrylate, 4-hydroxystyrene, 4-hydroxy-α, such as diol mono(meth)acrylic acid 1294894 ester], diethylene glycol mono(meth)acrylate -C2 such as methyl styrene -6-alkenylphenol, dihydroxystyrene, vinylnaphthyl alcohol, etc.], a compound containing a carboxyl group or an acid anhydride group [such as a C3_6 alkenyl carboxylic acid such as (meth)acrylic acid, crotonic acid or 3-butyric acid, a C4-8 alkenyldicarboxylic acid or an anhydride thereof such as a benic acid, a maleic acid or a maleic acid, an unsaturated aromatic carboxylic acid such as vinylbenzoic acid or the like, a cinnamic acid or the like, or an amine group-containing compound (such as a C3.6-chain enamine such as allylamine, 4-aminostyrene, diaminostyrene, etc.), an epoxy group-containing compound (such as allyl epoxidized ether, epoxypropyl (methyl)) Acrylate or the like, an isocyanate-based compound (such as a vinyl isocyanate) or the like. Further, in the above resin (i), the resin can be modified by introducing a reactive group (B). The method of introducing the reactive group (B) into the resin can use (i-1) a monomer having a reactive group (B) (for example, a polymerizable compound exemplified above), and a resin material (or a single resin material). The method of copolymerization of the bulk or oligomer ('i-2) is introduced into various organic reactions such as a carboxyl group, a halogenation method, or a grafting method of a polymerizable monomer by an oxidation reaction. In addition, many of the vinyl polymer-based resins are usually introduced into the reactive group (B) by using a monomer having the reactive group (B) as a copolymerization component, and even a resin containing an ethylene polymer resin can have The graft reaction of the above-mentioned reactive group polymerizable compound is easily introduced into the above reactive group (B). The method of introducing an unsaturated bond in the resin (i) is, for example, a polyfunctional property as a partial reaction component (comonomer) in a condensed resin (for example, a polyamine resin or a polyester resin). Compounds with unsaturated bonds [eg aliphatic unsaturated dicarboxylic acids (maleic acid, maleic anhydride, fumaric acid, -22- 1294894, itaconol, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid) Such as C4d 0 month 曰 aliphatic unsaturated monocarboxylic acid, etc., unsaturated polycarboxylic acid; aliphatic unsaturated monoalcohol (2-butyl di-anthracene, 4 diol, etc. c4 iq aliphatic unsaturated two A method of co-condensation (or copolymerization) such as alcohol or the like. Further, a monomer having a conjugated unsaturated bond (for example, anthracene, 3-butadiene, 2-methyl) as a partial reaction component (copolymer monomer) is added to an addition polymerization resin (for example, an olefin resin). Base_ι,3-butadiene, 2,3-dimethyl d, butadiene, chlorination

A method of copolymerization such as a conjugated Cm alkadiene having a substituent such as a servant or the like. The above resin (i i i ) can be introduced into a thermoplastic resin by introducing a thermoplastic resin (a) and a resin (b) having an unsaturated bond to form a polymer mixture (or a resin composition). The thermoplastic resin (a) is not particularly limited, and examples thereof include various thermoplastic resins (for example, the following thermoplastic resins (polyamide-based resin, polyester-based resin, etc.)). Further, the thermoplastic resin (a) may be a resin having no unsaturated bond or a resin having an unsaturated bond.

The resin (b) having an unsaturated bond, for example, a thermoplastic resin into which an unsaturated bond is introduced, such as the above-mentioned resin (i), (ii) or (iv), or a rubber containing an unsaturated bond [e.g., a polyalkene (polybutylene) Polyene, polyisoprene, polyhexene, polyheptene, polyoctene, poly(3-methyloctene), polydecene, poly(3-methyldecene), polydodecene, etc. &lt;:4. (Alkene of 15 or the like), a copolymer of a C4_15 alkadiene such as a butadiene-isoprene copolymer, a rubber-modified polyolefin such as a butadiene-modified polyethylene, or the like. Moreover, the above poly C4. The 15 olefin may be substituted by a cyclic olefin (e.g., cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, etc. may have a substituent -23- 1294894 (^. It is obtained by substitution polymerization of a cycloolefin or the like, partial hydrogenation of a polyalkylene group (for example, polybutadiene, etc.). In the above resin (iv), the ratio of the above resin (b) may be selected within the range of the unsaturated bond introduced into the polymer mixture at a predetermined concentration, for example, for the resin of (a), the resin (b) It is 5 to 3 parts by weight, preferably 2 to 1 part by weight, and more preferably 5 to 8 parts by weight. In particular, when a rubber containing an unsaturated bond (for example, a poly(alkenyl) group) is used as the resin (b), the proportion of the rubber containing an unsaturated bond is selected within a range that does not impair the properties of the resin (a), for example, for 100 heavy stars. The resin containing the unsaturated bond in the resin (a) is 〇5 to cc, preferably 1 to 30 parts by weight, and most preferably 2 to 20 parts by weight. The number of no it and the number of bonds is, for example, an average of 〇 for one molecule of the resin.  One or more (for example, 1 to 1 〇 〇), preferably one or more on average (for example, 1 to 1 〇 )), and the best is an average of two or more (for example, 2 to 50). Further, the concentration of the unsaturated bond is, for example, 1 kg to 1 kg of resin, preferably 1 to 6 · 6 m, preferably 0. 01~4 Moor, the better one is 〇. 〇 2~2 Mo Er. The thermosetting resin having a crosslinkable functional group has a crosslinkable or hardenable functional group (for example, a methylol group, an alkoxymethyl group, an epoxy group, an isocyanate) in the presence of a crosslinking agent (or a hardener) or the like. Base, etc.) resin. The thermosetting resin is, for example, a polycondensation or an addition condensation resin (a phenol resin, an amine resin, an epoxy resin, a thermosetting polyimide resin, a thermosetting polyurethane resin, a polyoxyalkylene resin, etc.), plus The above-exemplified thermosetting resin is a polymerized resin (an unsaturated polyester resin, a vinyl ester resin, a diallyl phthalate resin, a thermosetting acrylic resin, or the like). These resins having an active atom or a crosslinkable group may be used singly or in combination of two or more kinds of two or more. When two or more kinds of resins are used in combination, the resin composition can form a composite resin composition such as a polymer alloy. The resin used in the present invention is preferably the above reactive resin. Specifically, the resin is preferably a resin having an active atom, a resin having a crosslinkable group, and a resin having an active atom and a crosslinkable group. When the resin having an active atom and/or a crosslinkable group is used, the sulfur-containing active agent can be used to highly improve or improve the adhesion to a wide range of rubber. Preferred thermoplastic resins and thermosetting resins are described below. (1) Polyamine-based resin Polyamine-based resin has a guanamine bond which is condensed by a carboxyl group and an amine group, and is, for example, an aliphatic polyamine-based resin, an alicyclic polyamine-based resin, or an aromatic polyfluorene. Amine resin, etc. An aliphatic polyamine-based resin is often used. An aliphatic polyamine-based resin such as an aliphatic diamine component (c4 of tetramethyldiamine or hexamethylenediamine). 1 () alkanediamine) and an aliphatic dicarboxylic acid component (hexamethylenediamine, sebacic acid, dodecanedioic acid, etc. c4. a condensate of 2 ()alkanedicarboxylic acid or the like) (for example, polyamine 46, polyamine 66, polyamine 610, polyamine 612, polyamine 1010, polyamine 1012, polyamine 1212, etc.) The indoleamine (ε-caprolactam, ω-lauric acid) and the like are used in the ring-opening polymerization of indoleamine. Separately or copolymerized with 2Q internal guanamine or the like, or aminocarboxylic acid (carbon number c4_2Q aminocarboxylic acid such as ω-aminoundecanoic acid, etc.) (for example, polyamide 6 , polyamine 1 , poly Copolyamine 1 2, etc., copolyamine copolymerized with such polyamine components (eg, polyamido 6 / 1 , polyamine 6 / 12, polyamine 66 / 1 1 , polyamine 66 / 12) and many more. An alicyclic polyamine-based resin, for example, a polyfluorene in which at least a part of the above aliphatic diamine component and/or an aliphatic dicarboxylic acid component is substituted into an alicyclic diamine and/or an alicyclic-25-294849 dicarboxylic acid amine. An alicyclic diamine such as the above aliphatic dicarboxylic acid component and an alicyclic diamine component (c5 8 cycloalkanediamine such as cyclohexanediamine; bis(aminocyclohexyl)methane, 2, 2 ·• double a condensate of a bis(aminocyclohexyl)alkane such as (aminocyclohexyl)propane. In the aromatic polyamine-based resin, for example, at least one of the above aliphatic diamine component and the aliphatic dicarboxylic acid component is a polyamine having an aromatic component. The aromatic polyamine, for example, a diamine component is a polyamine having an aromatic component [a condensate of an aromatic diamine (such as m-xylenediamine) such as MXD-6 and an aliphatic dicarboxylic acid], and a dicarboxylic acid. The acid component is a polyamine having an aromatic component [a condensate of an aliphatic diamine (such as trimethylhexaethylenediamine) and an aromatic dicarboxylic acid (such as citric acid or isodecanoic acid)], and a diamine component. And a wholly aromatic polyamine (aromatic polyamine) such as a polyamine (poly(m-phenylisophthalic acid decylamine)) having an aromatic component and the like. The polyamine-based resin further comprises a polyamine which uses a dimer acid as a dicarboxylic acid component, a small amount of a polyfunctional polyamine and/or a polycarboxylic acid component, and is introduced into a branched structure of a polyamine or a modified polyamine. (N-alkoxymethylpolyamine, etc.), modified polyolefin blended or graft polymerized high impact polyamide, polyether is a soft phase polyamine elastomer. In the polyamine-based resin, for example, a hydrogen atom bonded to an α-position carbon atom to a hydrogen atom of a terminal amino group, a terminal amine group, and a hydrogen atom bonded to a carbon atom adjacent to a sulfhydryl group. The atom (such as a hydrogen atom of a methyl group or a hydrogen atom of a methine group), particularly a hydrogen atom of a terminal amine group, constitutes an active hydrogen atom. The ratio of the terminal oxime group to the terminal COOH group in the polyamine-based resin is not particularly limited, and for example, when the hydrogen atom of the terminal group and the hydrogen atom of the α-carbon -26 - 1294894 constitute an active hydrogen atom, Terminal amine group/terminal carboxyl group = 1 ο / 90 to 100/0 (mole ratio), preferably 20/80 to 95/5 (mole ratio), more preferably 2 5 / 7 5 to 9 5 / 5 (Morbi). Further, when the hydrogen atom of the terminal amine group constitutes an active hydrogen atom, the terminal amine group/terminal carboxyl group is 50/50 to 100/0 (mole ratio), preferably 60/40 to 95/5 (mole). Better than 70/30~9 5 / 5 (Morbi). Further, when the polyamine-based resin is introduced into the unsaturated bond as the resin (i), for example, a residual carboxyl group or an amine group is used as the reactive group (B), and when the unsaturated bond is introduced as the resin (ii), the above-mentioned resin can be used. An unsaturated polycarboxylic acid (maleic acid or the like) or the like is used as a partial copolymerization component. (2) Polyester-based resin A polyester-based resin such as an aliphatic polyester-based resin or an aromatic polyester-based resin. The aromatic polyester-based resin is usually a polyalkylene acrylate resin or a saturated aromatic polyester resin. The aromatic polyester-based resin includes, for example, polyethylene C. (PET), polybutylene terephthalate (PBT), and the like. 4 alkyl phthalate; corresponding to the polyalkylene terephthalate poly C2. 4 alkyl naphthalate (e.g., polyethylene naphthalate); poly(1,4-cyclohexyldimethylparaben) (PCT)). The polyester resin may be a copolyester containing an alkylene acrylate unit as a main component (e.g., 50% by weight or more), and a copolymerization component such as ethylene glycol, propylene glycol, butylene glycol, hexanediol or the like. An asymmetric aromatic dicarboxylic acid such as a 6-alkanediol, a polyepoxy C2_4 alkanediol, a decanoic acid or an isodecanoic acid, or an acid anhydride thereof, or an aliphatic dicarboxylic acid such as adipic acid. Alternatively, a small amount of a polyhydric alcohol and/or a polycarboxylic acid may be used, and a branched structure may be introduced into the linear polyester. -27- 1294894 When the aromatic polyester-based resin does not have the above-mentioned active atom at a predetermined concentration, the modified polyester-based resin may be used as a modified compound having an active atom (for example, at least one selected from the group consisting of an amine group and an alkylene oxide) Base aromatic polyester resin). An active atom, particularly a compound having an active hydrogen atom such as a polyamine (aliphatic diamine such as ethylenediamine, trimethyldiamine, propylenediamine, tetramethylenediamine, pentaethylenediamine, hexamethyldiamine, three) a linear or branched alkyldiamine having a carbon number of 2 to 10, such as methylhexamethyldiamine, 1,7-diaminoheptane or 1,8-diaminooctane; an aliphatic diamine such as Isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, bis(aminomethyl)cyclohexane, etc.; aromatic diamines such as phenylenediamine, xylylenediamine, Diaminodiphenylmethane, etc.), polyalcohols (for example, (poly) epoxy ethene alcohol, (poly) oxidized trimethyl diol, (poly) propylene oxide alcohol, (poly) oxidized tetramethyl diol, etc. (poly) epoxy C2_4 alkanols, etc.). The modification can be carried out, for example, by heating and mixing a polyester resin and a modifying compound, and subjecting to hydrazine, esterification or transesterification. The degree of modification of the polyester resin depends on the amount of the active hydrogen atom in the above compound, and the functional group (trans group or thio group) of the 1 mol polyester resin is, for example, a modified compound oxime.  1 to 2 mo, preferably 0. 2~1. 5 Mo, better is 0. 3 to 1 mole. When using the exchange reaction (poly) epoxy C2. The amount of the 4-alkanol used is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the polyester resin. The polyester resin is usually a hydrogen atom of a methyl group in a (poly)alkylene oxide unit, and the modified polyester resin is usually a hydrogen atom of the terminal amine group or a terminal amine group. a hydrogen atom bonded to a carbon atom of the α-position carbon atom, a hydrogen atom bonded to a carbon atom of a -ΝΗ- group adjacent to the indoleamine bond (a hydrogen atom of a methyl group - a hydrogen atom of a 28- 1294894 or a methine group, etc.) In particular, the hydrogen atom of the terminal amine group constitutes an active hydrogen atom. Further, when the polyester resin is introduced into the unsaturated bond as the resin (i), for example, a residual carboxyl group or a hydroxyl group may be used as the reactive group (B), and when the unsaturated bond is introduced as the resin (ii), the above-mentioned resin may be used. An unsaturated polybasic acid (maleic acid or the like) or the above unsaturated polyol (2-butene-1,4-diol, etc.) or the like is used as a partial copolymerization component. (3) Poly(thio)ether-based resin The poly(thio)ether-based resin contains a polyalkylene oxide resin, a poly(phenylene ether) resin, and a polysulfide resin (polysulfide resin). The polyalkylene oxide-based resin comprises polyoxyethylene glycol, polyethylene oxide alcohol, polypropylene oxide alcohol, polyethylene oxide-polypropylene oxide block copolymer, polyoxytetramethane, etc. C! _4 alkanediol and the like. The preferred poly(thio)ether-based resin comprises a polyacetal resin, a poly(phenylene ether) resin, a polysulfide resin, and a polyetherketone resin. Further, when the unsaturated bond is introduced as the resin (i), a residual hydroxyl group, a S group or the like can be used as the reactive group (B). (3a) Polyacetal-based resin Polyacetal-based resin A homopolymer (formaldehyde monomer) which can be repeatedly formed by a acetal bond, or a copolymer which can also be obtained by ring-opening polymerization (trioxan) a copolymer of an alkane with ethylene oxide and/or a 1,3-dioxolane, etc.). Further, the end of the polyacetal resin can be sealed and stabilized. Examples of the polyacetal resin, such as a hydrogen atom of an oxidized methyl unit, a hydrogen atom of a terminally sealed alkoxy group (particularly a methoxy group), and particularly a hydrogen atom of an oxidized methyl group, constitute an active hydrogen atom. Further, when the polyacetal resin is introduced into the resin (i) as the unsaturated - 2 9 - 1294894 bond, a residual hydroxyl group or the like can be used as the reactive group (B). (3b) Poly(phenylene ether) resin The polyphenylene ether resin contains various resins containing 2,6-dimethylphenylene oxide as a main component, for example, 2,6-dimethylphenylene oxide A modified poly(phenylene ether) resin or the like which is a copolymer of a phenol or a styrene resin. Other modified poly(phenylene ether) resins such as poly(phenylene ether)/polyamidoline, poly(phenylene ether)/saturated polyester, poly(phenylene ether)/polyphenylene sulfide system, polyphenylene sulfide/polyolefin Department and so on. When the styrene resin is mixed, the ratio of the styrene resin to the 00 parts by weight of the poly(phenylene ether) resin is, for example, 2 to 150 parts by weight, preferably 3 to 1 part by weight, more preferably It is 5 to 50 parts by weight. The polyphenylene ether-based resin may, for example, be a hydrogen atom bonded to a methyl group on a benzene ring to constitute an active hydrogen atom. (3c) Polysulfide-based resin (polythioether-based resin) The polysulfide-based resin is not particularly limited as long as it has a sulfur group s_) in the polymer chain. The resin is, for example, a polyphenylene sulfide resin, a polydisulfide resin, a polyphenylene sulfide resin, a polyketone sulfide resin, a polythioether resin or the like. Further, the polysulfide-based resin may have a substituent such as an amine group of poly(aminophenylene sulfide). A preferred polysulfide-based resin is a polyphenylene sulfide resin. The polysulfide-based resin constitutes an active sulfur atom with a sulfur group in the main chain. (3d) polyether ketone resin rejuvenation tree B, for example, polyether ketone obtained by polycondensation of a toothed benzamidine (dibenzophenone dichloride, etc.) with dihydrobenzophenone A resin, a polyetheretherketone resin obtained by polycondensation of a dihalogenated benzophenone and hydroquinone, or the like. —30 — 1294894 (4) The polycarbonate resin The polycarbonate resin may be an aliphatic polycarbonate resin, and the aromatic polycarbonate resin is usually an aromatic dihydroxy compound (bisphenol A or bisphenol). An aromatic polycarbonate obtained by reacting a bisphenol compound such as S or the like with a phosphine or a carbonic acid diester (a diaryl carbonate such as diphenyl carbonate or a dialkyl carbonate such as dimethyl carbonate) Wait. When a polycarbonate resin is introduced into the resin (i) as an unsaturated bond, a residual hydroxyl group or the like can be used as the reactive group (B). (5) Polyimine-based resin The polyimine-based resin contains a thermoplastic polyimide resin, for example, an aromatic tetracarboxylic acid or an anhydride thereof (such as benzophenone tetracarboxylic acid) or an aromatic diamine ( Polyimine resin, polyamidimide resin, polyester phthalimide resin obtained by the reaction of diaminodiphenylmethane or the like. When the polyimine-based resin is introduced into the unsaturated bond as the above resin (i), a residual carboxyl group, an acid anhydride group, an amine group, an imine group or the like can be used as the reactive group (B). (6) Polyfluorene-based resin polyfluorene-based resin, for example, by polycondensation of diphenylphosphonium dichloride (dichlorodiphenylphosphonium) and polyfluorene (bisphenol A or a metal salt thereof) Resin, polyether oxime resin, polyallyl oxime resin (trade name: RADEL), and the like. (7) Polyurethane-based resin The polyurethane resin can be obtained by reacting a diisocyanate with a polyhydric alcohol and a chain extender as required. Diisocyanates such as hexamethylenediisoate as an aliphatic monoisoyl ester such as 2,2,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, Aromatic compounds such as alicyclic diisocyanates such as isophorone diisocyanate-31 - 1294894 acid esters, phenyl diisocyanate, tolyl diisocyanate, diphenylmethane-4, 4'-diisocyanate, etc. An aromatic aliphatic diisocyanate such as a diisocyanate or a xylyl diisocyanate. The diisocyanate may be a compound substituted with an alkyl group (e.g., methyl group) in the main chain or ring. The diols can utilize polyester diol (C4 from adipic acid, etc.).  i 2 aliphatic dicarboxylic acid component, ethylene glycol, propylene glycol, butanediol, neopentyl alcohol, etc. C2. 12 an aliphatic diol component, a polyester diol obtained by a C4_12 lactone component such as ε-caprolactone or the like, or a polyether diol (polyethylene glycol, polypropylene glycol, polyethylene oxide-polyepoxy) A propane copolymer, a polyoxytetramethylene glycol, a bisphenol A-alkylene oxide adduct, or the like, a polyester ether diol (a polyester diol using the above polyether diol as a diol component), or the like. In addition, the chain extender in addition to ethylene glycol, propylene glycol, etc. C2. In addition to the 1Q alkanediol, diamines can be used. Diamines such as ethylenediamine, trimethyldiamine, tetramethyldiamine, pentaethylenediamine, hexamethyldiamine, trimethylhexamethyldiamine, 1,7-diaminoheptane, 1,8-diamino a linear or branched polyalkylene polyamine having a carbon number of 2 to 10 such as octane or a linear or branched alkylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dipropylenetriamine; Aliphatic diamines such as isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, bis(aminomethyl)cyclohexane, etc.; aromatic diamines such as benzene Diamine, xylene diamine, diaminodiphenylmethane, and the like. a polyurethane resin such as a main chain of a diisocyanate or a hydrogen atom bonded to a ring of a ring (especially a hydrogen atom at a benzyl group), an alkyl group of a polyalcohol or a polyalkylene oxide The hydrogen atom and the hydrogen atom of the amine group of the chain extender constitute an active hydrogen atom. - 32 - 1294894 &amp; </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; When the unsaturated bond is introduced as the resin (ii), the unsaturated polyol (2-butene-1,4-diol or the like) or the like is used as a part of the copolymerization component. (8) Polyolefin-based resin Polyolefin-based resin such as polyethylene, polypropylene, ethylene-propylene copolymer, poly(methylpentene-1) or the like, or a copolymer of an olefin and a copolymerizable monomer (ethylene-vinyl acetate copolymer, ethylene methyl) acrylic copolymer, ethylene-(meth)acrylate copolymer, etc.). These polyolefin resins may be used singly or in combination of two or more. A preferred polyolefin-based resin comprises a polypropylene-based resin having a propylene content of 50% by weight or more (particularly 75 to 100% by weight), for example, a polypropylene, a propylene-ethylene copolymer, a propylene-butyl copolymer, and a propylene. Can-Ethylene-Butyl Copolymer and the like. Further, the polyolefin resin is preferably crystalline. The polyalkylene-based resin, for example, a hydrogen atom of a methyl group which constitutes a polycondensation hydrocarbon main chain, and a hydrogen atom of a methyl group branched by the above main chain constitute an active hydrogen atom. (9) halogen-containing resin halogen-containing resin such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer, etc., chlorine-containing vinyl resin, A fluorine-containing resin such as a copolymer of polyvinyl fluoride (polyvinylidene fluoride), polytrifluoroethylene trichloride or tetrafluoroethylene. A preferred fluorine-containing resin is a fluorine-containing vinyl resin (e.g., polyvinyl fluoride, polyvinylidene fluoride, etc.). - 33- 1294894 (1) styrene resin styrene resin such as styrene monomer alone or copolymer (polystyrene, styrene-vinyltoluene copolymer, styrene-methylstyrene copolymer, etc.) a copolymer of a styrene monomer and a copolymerizable monomer (for example, a cyanide vinyl compound such as (meth)acrylonitrile) (styrene-acrylonitrile copolymer (AS resin), (meth)acrylic acid) Ester-styrene copolymer (MS resin, etc.), styrene copolymer such as styrene-maleic anhydride copolymer, styrene-butadiene copolymer; acrylonitrile-butadiene styrene copolymer (ABS resin) ), impact resistant polystyrene (HIPS), acrylonitrile-acrylate-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile-ethylene propylene rubber a styrene copolymer (AES resin), a styrene-based graft copolymer such as acrylonitrile-vinyl acetate-styrene copolymer (AXS resin), or the like. (1 1 ) (meth)acrylic resin (meth)acrylic resin, for example, a single or a copolymer of a (meth)acrylic monomer, a copolymer of a (meth)acrylic monomer and a copolymerizable monomer, or the like . (Meth)acrylic monomers such as (meth)acrylic acid, methyl (meth)acrylate 'ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, (A) A methacrylic acid such as 10-alkyl (meth)acrylate or cyclohexyl methacrylate such as 2-ethylhexyl acrylate. A (meth)acrylic acid hydroxyl group such as a cycloalkyl ester or a phenyl (meth)acrylate such as a C6-1Q aryl (meth)acrylate or a hydroxyethyl (meth)acrylate. An alkyl ester, a (meth) propylene phthalamide, a vinyl cyanide compound (for example, (meth) acrylonitrile), (meth) acryl acrylate, etc. The copolymerizable monomer is, for example, a vinyl monomer such as vinyl acetate or vinyl chloride, or a styrene monomer such as styrene or α-methylstyrene. When the (meth)acrylic resin is introduced into the unsaturated bond as the resin (i), the reactive group (B) can be introduced by using a monomer having a reactive group (B) as a copolymerizable monomer. (1 2 ) Thermoplastic Elastomer The thermoplastic elastomer comprises a polyamine-based elastomer (a copolymer having a polyamine as a hard phase and an aliphatic polyether as a soft phase), and a polyester-based elastomer (a polyalkylene group) Acrylate is a hard phase, a copolymer of an aliphatic polyether or an aliphatic polyester as a soft phase), a polyurethane elastomer (a polyurethane of a short-chain alcohol is a hard phase, and an aliphatic Polyether or aliphatic polyester is a soft phase copolymer, such as polyester urethane elastomer, polyether urethane elastomer, etc.), polystyrene elastomer (hard polystyrene block) Phase, a block copolymer having a diene polymer block or a hydrogenated block thereof as a soft phase), a polyolefin elastomer (a hard phase of polystyrene or polypropylene, ethylene-propylene rubber or ethylene) The propylene-diene rubber is an elastomer of a soft phase, an olefin-based elastomer composed of a hard phase and a soft phase having different degrees of crystallization, a polychlorinated ethylene elastomer, a fluorine-based thermoplastic elastomer, or the like. As the aliphatic polyether, a (poly)alkylene oxide (c 2 _ 4) alcohol (particularly, a polyethylene oxide alcohol) described in the section of the polyester resin and the polyurethane resin can be used, and the aliphatic polymer can be used. As the ester, a polyester diol described in the section of the polyurethane resin can be used. These thermoplastic elastomers may be used singly 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 multi-block structure, a star block structure or the like. A 35- 1294894 b 'The preferred thermoplastic elastomer comprises a polyamide-based elastomer, a polyester-based elastomer, a polyurethane-based elastomer, a polystyrene-based elastomer, and a polyolefin-based elastomer. . The thermoplastic elastomer, for example, an alkylene oxide unit constituting the soft phase may constitute an active hydrogen atom. Further, 'Ethylene-fired polymer resin (for example, (meth) acrylic acid-based resin (polymethyl methacrylate, methyl methacrylate-styrene copolymer, etc.) and styrene resin (polystyrene; AS) a styrene copolymer such as a resin; a styrene-based graft copolymer such as HIPS or ABS resin; and the like, and a polyfunctional polymerizable compound having two or more functional groups (for example, ethylene glycol di(meth)acrylate, two) Ethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.) are copolymerized and crosslinked with the constituent monomers. Thermosetting resin such as polycondensation or addition condensation resin (phenol resin, amine resin, epoxy resin, polyoxyalkylene resin, thermosetting polyimide resin, thermosetting polyurethane resin, etc.), addition A polymer resin (a thermosetting acrylic resin, a vinyl ester resin, an unsaturated polyester resin, a diallyl phthalate resin, or the like). The thermosetting resins may be used singly or in combination of two or more. (1 3 ) Phenol resin The phenol resin is a phenol resin resin, a cresol resin or the like, and a phenol resin resin is usually used. The phenolic enamel resin is obtained by reacting a phenol with an aldehyde in the presence of an acid catalyst. Phenols such as phenol, hydrazine, m-, or p-cresol, 2, 5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, ethylphenol, C Phenolic and the like (^. 4-alkylphenol, dihydroxybenzene, m-phenylene 36- 1294894 phenol, naphthol, and the like. These phenols may be used singly or in combination of two or more. The aldehydes are, for example, formaldehyde, an aliphatic aldehyde such as formaldehyde, acetaldehyde or propionaldehyde, an aromatic aldehyde such as benzaldehyde or salicylaldehyde, or the like. These aldehydes may be used singly or in combination of two or more. (1) The amine resin amine resin is usually obtained by reacting an amine group-containing compound with an aldehyde (for example, an aromatic aldehyde such as formaldehyde, acetaldehyde or propionaldehyde, or an aromatic aldehyde such as phenylacetaldehyde). . The amine resin is a urea resin (a urea resin obtained by reacting urea with an aldehyde, etc.), an aniline resin (by aniline, naphthylamine, toluidine, xylylamine, N,N-dimethylaniline, benzidine) An aniline, an aniline resin obtained by reacting with an aldehyde, a melamine resin (a melamine resin obtained by reacting melamine with an aldehyde, etc.), a guanamine resin (benzoguanamine, B) A guanine guanamine, a guanamine such as guanamine, and a guanamine resin obtained by reacting with an aldehyde. (1 5) Epoxy resin The epoxy resin includes a bisphenol type epoxy resin, a phenolic enamel type epoxy resin, an amine epoxy resin, and the like. The bisphenol constituting the bisphenol type epoxy resin is, for example, a glycidyl ether such as 4,4-bisphenol, 2,2-bisphenol, a combination of F, bisphenol AD, or bisphenolphthalein. The phenolic enamel resin constituting the novolac type epoxy resin is, for example, a phenolic lacquer resin obtained by the reaction of a phenol and an aldehyde described in the above phenolic lacquer resin. An amine component constituting an amine-based epoxy resin, such as an aromatic amine such as aniline or toluidine, an aromatic diamine such as diaminobenzene or xylene diamine, or an amino group hydroxy-37- 1294894 benzene or diaminodiphenyl group Methane, etc. (1 6 ) Polyoxane resin The polyoxyalkylene resin contains the formula: RaSiO (4. a)/2 units (where the coefficient a is 1 · 9~2 · 1), and the formula: RbSiO (4. The unit shown by bW2 (where the coefficient b is 0.  9~1.  1) A polyoxyalkylene resin or the like. Among them, for example, a methyl group, an ethyl group, a propyl group, a butyl group or the like. a halogenated alkyl group such as an alkyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a vinyl group, an allyl group, a butenyl group or the like. I. al., alkenyl, phenyl, tolyl, naphthyl, etc. C6_12 aryl, cyclopentyl, cyclohexyl, etc. C3. C6 of 1Q cycloalkyl, benzyl, phenethyl and the like. 12 aryl-Cm alkyl group and the like. (1) Thermosetting Polyimine-Based Resin The thermosetting polyimide-based resin contains the resin described in the above polyimine-based resin. (18) Thermosetting Polyurethane Resin The thermosetting polyurethane resin includes the resin described in the above Polyurethane Resin. (19) Thermosetting Acrylic Resin The thermosetting acrylic resin contains the resin described in the above (meth)acrylic resin. (20) Vinyl Ester Resin Vinyl Ester Resin, for example, a polymer obtained by reacting the above epoxy resin with (meth)acrylic acid, and a polyvalent phenol and a glycidyl (meth) succinic acid ester The resulting polymer or the like is reacted. (2 1 ) Unsaturated Polyester Resin-38- 1294894 Unsaturated Polyester Resin, for example, in the above-mentioned polyester-based dicarboxylic acid or an anhydride thereof (for example, unsaturated polycondensation of maleic acid, maleic anhydride, and dicarboxylic acid component) (22) Diallyl phthalate resin The diallyl phthalate resin contains a diene propylene phthalate monomer such as diene propylene propyl isononate. Active Agent] The resin composition of the present invention contains a sulfurizing active agent for improving or improving the adhesion of the fat. The composite agent can improve the wettability of the resin and the rubber, and uniformly adhere the adhesive (for example, a radical generating agent). With unsulphurized rubber), the resin is crosslinked with the rubber to improve the resin/rubber. Therefore, the resin and the rubber are firmly bonded directly or the above-mentioned vulcanization active agent, for example, has a plurality of carbon-carbon only bonds. Organic compound [for example, a vinyl monomer (a di-Z-propyl monomer (diallyl phthalate, a triene acrylate (isocyanate), etc.), a (meth)acrylic monomer, etc., etc. Non-maleimide-based vulcanization activity when polyester resin is used as the resin An organic compound (e.g., an organic compound having a plurality of unsaturated bonds). These vulcanizations are used or used in combination of two or more. (Meth)acrylic monomers such as difunctional (b[ethylene glycol di(meth)acrylate, propylene glycol bis(methylbutylene glycol di(meth)acrylate, hexanediol di(methyl) In the case of unsaturated fumaric acid, etc.), it is used as a phthalic acid ester, a bismuth resin, etc. In the case of rubber, the sulphur is active in the tree, and the sulphur is added by vulcanization (or Crosslinking density: r ° E bond (polymerizable unsaturated L-alkenylbenzene, etc.), olefin phosphate, triallyl,], maleimide, usually mostly carbon-carbon double bond (polymeric active agent can C21 decanediol di(meth) acrylate such as acrylate) acrylate, 1,4 -g acrylate, neo-39 - 1294894 pentanol mono(meth) acrylate, etc. Diol di(meth)acrylate 'triethylene glycol di(meth) propylene I ester, polyethylene glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(a) Acrylate, polypropylene glycol di(meth) acrylate, polytetramethylene glycol di(meth)acrylate, etc. Polyalkylene di-(meth) acrylate, glycerol di(meth) acrylate, trimethylol propyl di(meth) acrylate, pentaerythritol di(meth) acrylate, double A C 2 - 4-Ethylene alkyl adduct of di(meth)acrylate, etc.], trifunctional or polyfunctional (meth) acrylate [glycerol] tris(methyl) acrylate "trishydroxyl Methyl ethane tri(meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (methyl) Acrylate, dipentaerythritol hexa(meth) acrylate, etc., etc. The maleimide compound having several maleimide groups can be obtained by reacting a polyamine with maleic anhydride. a compound such as an aromatic bismaleimide (N,N,-1,3-phenylene dimaleimide, N,N,-1,4-phenylene dimaleimide, N,N,-3 -Methyl-1,4-phenylene dimaleimide, 4,4'-bis(N,N'-maleimide)diphenylmethane, 4,4 - double (N, Ν'-maleimide) diphenyl hydrazine, 4,4'-bis (Ν, Ν'-maleimide) diphenyl ether, etc.), aliphatic double mala Imine (Ν,Ν' - 1,2-extended ethyl bismaleimide, anthracene, Ν'-1,3 - propyl bis-maleimide, ν, Ν, 1,4 - four a methyl ester or a compound having a plurality of (for example, 2 to 6, especially 3 to 6) α,β-ethylenically unsaturated bonds, A compound having a plurality of (meth)acryl fluorenyl groups having a trifunctional-40-1294894-type or polyfunctional (meth) acrylate (trimethylolpropane tri(meth)acrylate, etc.) is preferred. The amount of the sulfurizing active agent used varies depending on the sulfurizing active agent, or the type of the resin, etc. The amount of the resin to the rubber is generally promoted. For example, the sulfurizing active agent is selected from 0 for 100 parts by weight of the resin.  1 to 1 〇 by weight, preferably 0. 1 to 5 parts by weight, the best is 0. 1 to 3 parts by weight. [Stabilizer] The present invention can be characterized by the use of a sulfur-adding active agent and a stabilizer. When the above-mentioned sulfur-adding active agent is used alone, when the sulfur-adding active agent and the stabilizer are combined, even if a sulfurizing activity having a polymerizable unsaturated bond is used in a heating and mixing process (for example, a kneading process of a resin and a sulfurizing active agent) The agent still inhibits or prevents the gel (or pitting) from occurring. Therefore, the vulcanization activator can be utilized in a function that does not reduce the strength of the composite or impair the appearance, and the resin and the rubber are bonded and bonded reliably and firmly. Therefore, the present invention uses a stabilizer to stabilize the resin, but it is preferred to stabilize at least the sulfurizing active agent. The stabilizer may be an antioxidant (including a heat-resistant processing stabilizer), a photostabilizer, or the like, or may be a thermal polymerization inhibitor (hydroquinone such as hydroquinone or methylhydroquinone). The antioxidant includes, for example, a phenol-based antioxidant, an amine-based antioxidant, a pitiful antioxidant, a sulfur-based antioxidant, a hydroquinone-based antioxidant, a quinoline-based antioxidant, a ketoamine resin, or the like. Also, refer to the trade name listed in parentheses. The phenol-based antioxidant is a hindered phenol-based antioxidant, and is, for example, a single-type, a bisphenol or a polyphenol. Monophenols such as mono- or di-branched c3 6 alkylphenols 4 1 to 1294894 having a substituent [eg 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl) -4-ethylphenol, etc. C]. 4 alkyl-di-branched _c3_6 alkyl phenol; 2 alkoxy group of 3 butyl-4-methoxy phenol, 3 tert-butyl-4-methoxy phenol, etc. - single or two-branched Chain C3_6 alkylphenol; C1()_2 of stearyl 邛-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. Alkyl-(di-branched C3. 6 alkyl-hydroxyphenyl) C 2_6 carboxylate; 2-ethylhexyl-(2, 6-di-t-butyl-4-hydroxybenzylsulfonyl) acetate, etc. C3_1Q alkyl-(di- Branch chain C3. 6 alkyl-hydroxybenzyl sulfide) C2. 6 carboxylic acid ester; distearyl-(3, 5-di-3-butyl-4-hydroxybenzyl) phosphate, etc. C1Q. 2Q alkyl-(di-branched C2. 6 alkyl-hydroxybenzyl methyl phosphate, etc.], with C4. 1()alkylthio-based phenol [2,4-di(octylthio)methyl-6-methylphenol (Irganox i520 Chiba Machinery Co., Ltd.), etc.], double Monoesters of phenols and (meth)acrylic acid [eg 2-(2-hydroxy-3 tert-butyl-5-methylbenzyl)-4-methyl-6-butylphenyl acrylate (history Mirais-GM Sumitomo Chemical Co., Ltd.), 2-[1-(2-hydroxy-3-tert-butyl-5-methylphenyl)ethyl]-4-methyl-6 tert-butyl Phenyl phenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-(tripentyl)phenyl acrylate (history Mireisa - GS Sumitomo Chemical Industry Co., Ltd.), etc. c!.  4 stretch alkyl double (single or two · branching C 3. a monoester of a 6-alkylphenyl group and a (meth) acrylate, etc.]. Bisphenols such as 2,2'-methyl bis(4-methyl-6-tert-butylphenol), 2, 2, methyl bis(4-ethyl-6-tert-butylphenol), 2 , 2,·Ethylene bis(4,6-di-t-butylphenol), 2,2,-ethylenebis[4,6-di(tripentyl)phenol], 4,4' - Butylene bis(3-methyl-6th-butylphenol), 4,4,·methyl bis(2,6-t-butylphenyl hydrazine), etc. (^·6 Single or two · one 4 2 - 1294894 amended page branch C3. 6-alkylphenol); bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid 1,6-hexanediol ester, bis[3-(3 tert-butyl) -5-Methyl-4-hydroxyphenyl)propionic acid]-triethylene glycol ester (Irganox 245 Chiba Machinery Co., Ltd.), etc. (single or di-branched C3. 6-alkyl-hydroxyphenyl) (: 2-6 carboxylic acid - single or tetra (: 2. 4 alkylene glycol ester; bismuth bis(3,5-di-t-butyl-4- keto-hydrocinnamonyl) (Igganox MD-1024 Chiba Machinery Co., Ltd.) , n, N'-trisole methyl bis (3, 5_ di-t-butyl-4-hydroxy-cyanide cinnamylamine), n, N,-hexa-methyl bis (3,5 - two third Butyl-4-hydroxy-cinnamonylamine (manufactured by Irganox 1098 Chiba Machinery Co., Ltd.) (single or di-branched C3_6 alkyl-hydroxyphenyl) C3_6 carboxylic acid and CQ_8 alkylenediamine diamine; 3,9-bis{1,1-dimethyl-2- [β-(3 tert-butyl-enhydroxy-5-methylphenyl) propyleneoxy] Kib 2,4,8,1〇-four oxygen rotation [5. 5] i - alkane (Semirasa GA-80 Sumitomo Chemical Co., Ltd.), etc. (mono or di-branched C3_6 alkyl-hydroxyphenyl) C3_6 carboxylic acid and dihydroxy heterocyclic compound Diester and the like. Polyphenols contain phenols [eg hydrazine, 3,5-trimethyl-2,4,6-parade (3,5-di-second butyl-4-hydroxybenzyl)benzene (Acedica) References (single or di-branched c3_6 alkyl-hydroxybenzyl) C6. 1 () arene; ginseng (2_mercapto-4_hydroxy-5) butyl butyl) Dingyuan et al (singly or di-branched alkyl-hydroxyphenyl) C -6 alkane; a mono- or di-branched c3 such as [3-(3,5-di-t-butyl-4- hydroxydiphenyl)propionic acid] glycerol ester. 6-alkyl-hydroxyphenyl C2 6 carboxylic acid and (: 3-6 alkanediol diester, 1,3,5-para (3,5, two third 4,-hydroxybenzophenone 43~ 1294894牴2, enough for the base of the page) 4-三哄-2,4,6-(11^311,5 old triketone (Jetika Sitab 八0-20 Asahi Denki Co., Ltd.), 丨, 3, 5 - ginseng (2,6, dimethyl-3, thiol-4't-butylbenzyl), triad-2,4,6-(1h,3h,5h)5_ The ginseng (single or two-branched C3. 6-alkyl-hydroxybenzyl)-S-tritrap-trione, etc., tetraphenols [eg 肆[methyl-3-3 -(3,5,-di-tert-butyl-4, thiol) Phenyl)propionate]methane (Irono Carlos (〗 〖Rgan〇x) 1〇1〇 Chiba • Special Chemical Co., Ltd.), etc. Mono- or di-branched C3 6-alkyl-hydroxyl a tetraester of phenyl C3_6 carboxylic acid and c3_6 alkanol tetraol; bis[3,3,-bis(4,-trans-yl-3'-t-butylphenyl)butanoic acid] alcohol ester or the like (single or Di-branched alkyl-hydroxyphenyl) C3. 6 carboxylic acid - mono to tetra C 2 -4 alkylene glycol ester] and the like. The amine-based antioxidants include aromatic amines such as phenyl-i-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-l,4-phenylenediamine, N-phenyl-N , -cyclohexyl-1,4-phenylenediamine, and the like. The phosphorus-based antioxidant includes, for example, a triisodecylphosphide, a phenyl diisononylphosphide, a diphenylisodecylphosphide, a triphenylphosphide, and a bis(2,4-di-tert-butylphenyl) Phosphide (made by Yadika Sitab 2112 Asahi Chemical Industry Co., Ltd.), ginseng (nonylphenyl) phosphide, dinonylphenyl bis(nonylphenyl) phosphide, 2,2 - Bis(4,6-di-t-butylphenyl)octylphosphide (made by Yadika Stabham HP-10 Asahi Chemical Industry Co., Ltd.), 4,4'-butylidene double (3-A) -6-tert-butylphenyl)becatrialkylphosphide, ginseng (2,4-di-t-butylphenyl)phosphide, ginseng (2,t-butyl-4-methylphenyl) Phosphate, ginseng (2,4-di-t-pentylphenyl)phosphide, ginseng (2,t-butylphenyl)phosphide, bis(2,t-butylphenyl)phenylphosphide, ginseng 2-(1,1-dimethylpropyl)phenyl]phosphide, ginseng [2,4-(1,1-dimethyl-44-1294894-propyl)phenyl]phosphide, ginseng (2- Cyclohexylphenyl) phosphide, ginseng (2, tert-butyl-4-phenylphenyl) phosphide, diisodecyl Pentaerythritol diphosphide, cyclopentane tetradecyl bis(octadecyl) phosphide (made by Yadika Statab PE to 8 Asahi Chemical Industry Co., Ltd.), cyclopentane tetradecyl double (2) , 4 - di-t-butylphenyl) phosphide (Yadika Stabbe PE to 24G Asahi Chemical Industry Co., Ltd.), cyclopentane tetradecyl bis (2, 6.2 tert-butyl) a phosphide of -4-methylphenyl) phosphide (made by Yadika Statab PE to 36 Asahi Denki Kogyo Co., Ltd.); triethylphosphine, tripropylphosphine, tributylphosphine, tricyclic Hexylphosphine, diphenylvinylphosphine, allyldiphenylphosphine, triphenylphosphine, methylphenyl-p-anisylphosphine, p-anisyldiphenylphosphine, p-tolyldiphenylphosphine, two -p-anisylphenylphosphine, di-p-tolylphenylphosphine, tri-m-aminophenylphosphine, tris-2,4-dimethylphenylphosphine, tris-2,4,6-trimethyl Phenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-o-anisylphosphine, tri-p-anisylphosphine, 1,4-bis(diphenylphosphino) a phosphine compound such as butane or the like. Sulfur-based antioxidants such as dilauryl 3,3-sulfurized dipropionate, di(tridecyl) 3,3-sulfurized dipropionate, dipalmityl-2,2-sulfurized diacetate, Sulfurized C2, palmityl-3,3-sulfurized dipropionate, lauryl stearyl 3,3-sulfurized dipropionate, distearyl 3,3-sulfurized dipropionate. 4 carboxylic acid two C10. 20 alkyl ester; 3,9-bis(lauryl sulfide)-2,4,8,10-tetraoxide rotation [5, 5]undecane and the like. Hydroquinone antioxidants such as 2,5 · di-t-butylhydroquinone, 2,5-di-p-pentylhydroquinone, etc., porphyrin-based antioxidants such as 6 · ethoxy-2, 2, 4 - 3 Methyl-1,2-dihydroquinoline and the like. -45- 1294894 Remaining 2, instrument i page The light stabilizer contains a hindered amine light stabilizer (HALS), a quenching agent, and the like. Also, refer to the trade name listed in parentheses. A hindered amine light stabilizer (HALS) such as a tetramethylpiperidine which may have a substituent (for example, a methoxy-tetramethyl group such as 4-methoxy-2,2,6,6-tetramethylpiperidine or the like) Piperidine; 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc. C 6. 1Q aryloxy-tetramethylpyrazine; 4·benzhydryloxy-2,2,6,6-tetramethylpiperidinyl C6·! Oxyl-tetramethyl sulfonium b, 4-methylpropenyloxy-2, 2, 6, 6 -tetramethylpiperidine (made by Yadika Stab LA-87 Asahi Chemical Industry Co., Ltd. , 4-methylpropoxy-N-methyl-2,2,6,6·tetramethylpiperidine (made by Yadika Stab LA-82 Asahi Chemical Co., Ltd.), etc. Methyl)propenyloxy-tetramethylpiperidine, etc., a substitutable alkanedicarboxylic acid dipiperidine ester [eg bis(2,2,6,6-tetramethyl-4-piperidinyl) Oxalate, bis(2,2,6,6-tetramethyl-4-piperidyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidinyl) Azelaic acid ester (made by Yadika Stabs lA-77 Asahi Chemical Industry Co., Ltd.), bis(1,2,2,6,6-pentamethyl-4piperidinyl phthalate), double (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (manufactured by Salo LS_76 5 Sankyo Co., Ltd.), etc. c2 iq alkanedioic acid a tetraalkylpyridine dicarboxylic acid dicarboxylate (such as bis(2,2,6,6-tetramethyl-4-piperidyl)-p-citric acid (tetramethylsulfonium) Gy such as ester. Aromatic diacetyl bis(tetramethylene cyridyl) ester, etc., may have a substituted bis(piperidinyloxy)alkane [1,2 - bis (2,2,6,6 -tetrayl) One of tetrakis-piperidinyloxy)ethane (tetramethylpiperidinyloxy)C i ·4 alkane, etc.]; bis(piperidinyloxycarbonyl)hydroxyphenylalkane [eg 1- (3,5-di-tert-butyl-4-ylhydroxyphenylindole, b-bis(2,2,6,6-tetramethyl-4-fluorenyloxycarbonyl)pentane (Tinuvin 144 thousand) 46 - 1294894 \· -&gt;·&gt; Itchy Zhengyeye Machinery Co., Ltd.), etc. (tetramethylpiperidinyloxypyridinyl phenyl chain, etc.] 'tetramethylene acid to four tetrahydroquinone Alkyl esters [eg 1,2,3,4-butane ruthenium tetracarboxylate (2,2,6,6-tetramethyl-4piperidinyl) ester (Yadika Stabla la -5 7 Asahi Barium tetracarboxylate (tetramethylpiperacyl) ester, etc.; 1,2,3,4-butane tetracarboxylic acid bis(2,2,6,6·tetramethyl) -4 - pulsed U-based)-bis(dodecyl)ester (made by Yadika Stab LA0-67 Asahi Chemical Industry Co., Ltd.), 1,2,3,4·butane tetracarboxylic acid double ( N-methyl-2,2 , 6,6, tetramethyl-4-piperidinyl)-bis(tridecyl)ester (Adica Statab [A-62 Asahi Denki Kogyo Co., Ltd.), etc. Tetramethylpiperidinyl)-bis(dimercapto)ester], Ci_4 院院基双(四院基派哄酮) [1,1 -Extended ethyl bis (3,3,3 ',3 ', 5,5,5 ',5,-octamethylpiperidine·2,2'-dione) (Goodrite UV-3034 Goodrich Co., Ltd.), etc. (^"alkyl bis (tetramethylpiperidine) Ketone), etc., polymer HALS [eg Ch i ma ss 〇r b944LD (Chiba • Special Chemical Co., Ltd.), Tinuvin 622D (Chiba • Special Chemical Co., Ltd.), Yadika Stab LA-63 Asahi Denki Co., Ltd., Yadika Statab LA0-68 Asahi Chemical Industry Co., Ltd.], etc. Quenching agent such as nickel bis(octylphenyl) sulfide, [2, 2 ' - sulfurized bis(4th octyl benzoate)]-n-butylamine nickel, nickel complex-3, 5-dibutylbutyl-4-hydroxybenzyl-phosphate monoacetate, nickel Dibutyl sulfide carbonate, 1-phenyl-3-methyl-4 An organic nickel complex such as a nonazapyrazole acid or a nickel; an organic cobalt complex such as a cobalt dicyclohexyl disulfide phosphate; etc. These stabilizers may be used singly or in combination of two or more. The agent contains a phenolic antioxidant, a stabilizer having a base capture function from 1294894, such as HALS. Further, the stabilizer having a radical scavenging function can be used in combination with other stabilizers (e.g., a combination of a phenolic antioxidant and a sulfur-based antioxidant). The amount of the stabilizer used is, for example, 1 〇 0 parts by weight of the resin.  〇 1~2 parts by weight, preferably 0. 05 to 3 parts by weight, more preferably 0. 1 to 2 parts by weight (for example, 〇 · 1 to 1 part by weight). Further, when the amount of the stabilizer added is too large, the gelation of the sulfur-adding active agent can be suppressed, and the function of the sulfur-adding active agent cannot be effectively performed, and the adhesion to the rubber can be lowered. In addition, when a stabilizer (a phenol-based antioxidant, HALS, etc.) having a radical scavenging function is used in combination with other stabilizers (phosphorus-based antioxidants, sulfur-based antioxidants, etc.), the ratio of these stabilizers is the former/the latter (weight ratio) = 99/1 ~ 20 / 80 (for example 95/5~40 / 60). Further, the ratio of the sulfurizing active agent to the stabilizer may be selected depending on the type of the sulfurizing active agent or the stabilizer, the mixing kneading temperature, etc., the former/the latter (weight ratio) = 99/1 to 2 5 / 7 5 , preferably It is 98/2~3 5 / 65, and the better is 97/3 ~ 45/55 (for example, 97/3 ~ 60/40). [Vulcanization aid] The present invention may additionally use a vulcanization aid. The vulcanization aid may be added to the following unvulcanized rubber in the above composite, and is usually added to the resin composition in many cases. The vulcanization aid may be selected depending on the type of the resin, for example, the above-mentioned condensed thermoplastic resin oligo oligomer [for example, an oligomer having a number average molecular weight of 1 Å or less (for example, 100 to 100 Å), or a polyamine (for example). For example, (2) a polyamine or the like described in the polyester resin, a polyalcohol (for example, a polyalcohol described in the above (2) polyester resin), a polyvalent carboxylic acid or an anhydride thereof, and a plurality thereof An aldehyde group-48- 1294894 compound, an epoxy compound, a nitrogen-containing resin (amine resin, etc.), a compound having a trans-oxymethyl group, a polyisocyanate or the like. These sulfur additions may be used singly or in combination of two or more. A preferred vulcanization aid is a compound having an average of two or more active hydrogen atoms in the active atom represented by the above formula (1) and having a molecular weight of ruthenium, for example, an average number of the above condensed thermoplastic resins. An oligomer (for example, an oligomer of the above polyamine resin, an oligomer of a polyester resin, or the like), a polyamine or the like, or the like. The proportion of the vulcanization aid is, for example, 10 parts by weight of the resin. 1 part by weight, preferably 0. 5 to 20 parts by weight, more preferably 丨 15 , and the resin composition of the present invention further contains various additives, chelating agents or reinforcing agents, coloring agents, plasticizers, smoothing agents, flame retardant electrostatic agents and the like. The form of the above resin composition is not particularly limited, and may be in the form of a pellet or a pellet. As described above, the resin composition of the present invention is excellent in adhesion to rubber, and when a composite resin material which is directly bonded to the rubber as a constituent resin is used, the adhesion strength between the resin and the rubber can be remarkably improved. [Composite] The composite of the present invention can directly bond the above-mentioned resin composition and a vulcanized rubber formed by vulcanization with an unsulfurized rubber. For example, the resin composition comprising the resin composition and the composite directly bonded to the vulcanized rubber member, for example, (1) forming the methyl auxiliary agent by the resin composition by one or more sub-quantities The weight is, for example, a tree-like 1294894 grease component which is made of a body-shaped rubber element, a composite body directly bonded to a vulcanized rubber component composed of a vulcanized rubber, and (2) a resin phase composed of the above resin composition. A composite (or composite dispersion) directly bonded to a vulcanized rubber composed of a vulcanized rubber. [Rubber] The unvulcanized rubber which forms a vulcanized rubber by vulcanization in the above composite is various rubbers, for example, a diene rubber, an olefin rubber, an acrylic rubber, a fluorine rubber, a polyoxyalkylene rubber. , a urethane rubber, an epichloropyridine rubber (an additional epichloropyridine monomer C0, a copolymer of epichloropyridine and ethylene oxide ECO, a copolymer copolymerized with allyl epoxifene, etc.) , chloroformated polyethylene, propylene oxide rubber (GP0), ethylene-vinyl acetate copolymer (EAM), polyprocarbene rubber, and modified rubber (acid-modified rubber, etc.). When the resin is a resin composed of a vinyl cyanide compound (for example, (meth)acrylonitrile) (for example, an ABS resin), the rubber is usually a non-cyanide vinyl rubber. These rubbers may be used singly or in combination of two or more. Among these rubbers, a diene rubber, an olefin rubber, an acrylic rubber, a fluorine rubber, a polyoxyalkylene rubber, a urethane rubber or the like is generally used in practical use. A diene rubber such as a non-cyanide vinyl rubber [for example, natural rubber (NR), isoprene rubber (IR), isobutylene isoamene rubber (butene rubber) (IIR), butadiene rubber (BR), chlorine a polymer of a diene monomer such as a olefinene rubber (CR), a styrene butadiene rubber (SBR, for example, a random copolymer of styrene and butadiene, a styrene block and a butadiene block) a styrene-diene copolymer rubber such as styrene chloride pentene rubber (SCR) or styrene isoprene rubber (SIR), or a vinyl cyanide-based copolymer. 1294894 Rubber [eg acrylonitrile butadiene rubber (nitrile rubber) (NBR), nitrile chlorinated butadiene rubber (nitrile rubber) (NCR), nitrile isopentene rubber (NIR), acrylonitrile isopentenyl An acrylonitrile-diene copolymer rubber such as olefin rubber (NBIR). The diene rubber includes a hydrogenated rubber, for example, a hydrogenated nitrile rubber (HNBR). The olefin-based rubber is, for example, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM or the like), polyoctene rubber or the like. Acrylic rubbers include rubbers containing alkyl acrylate as a main component, such as copolymer ACM of acrylate ester and chlorine-containing crosslinkable monomer, copolymer ANM of alkyl acrylate and acrylonitrile, alkyl acrylate and carboxyl group-containing / or a copolymer of a monomer of an epoxy group, an ethylene acrylic rubber or the like. The fluorine-based rubber is a rubber having a fluorine-containing monomer, for example, a copolymer of vinylidene fluoride and perfluoropropane and a tetrafluoroethylene as required, a copolymer of tetrafluoroethylene and propylene, and a tetrafluoroethylene. Copolymer FFKM with perfluoromethyl vinyl ether. The polyoxyalkylene rubber (Q) is an organopolysiloxane having a unit of the formula: RaSiO (4_aW2), wherein R is, for example, a Cm such as a methyl group, an ethyl group, a propyl group or a butyl group. - a halogenated CV1 such as a propyl chloride or a 3,3,3-trifluoropropyl group (C2_1Q alkenyl group such as an alkyl group, a vinyl group, an allyl group or a butenyl group, a phenyl group, a tolyl group, a naphthyl group or the like) C6. C3 of 12 aryl, cyclopentyl, cyclohexyl, etc. C6 of IQ cycloalkyl, benzyl, phenethyl and the like. 12 aryl-alkyl and the like. Among them, the coefficient a is 1. 9~2. 1. Preferred R is methyl, phenyl, alkenyl (vinyl, etc.), fluorine C!.  6 alkyl. The molecular structure of the polyoxo rubber is, for example, generally linear, and may have a branched structure or a branched structure. The main chain of the polyoxyalkylene rubber is, for example, a di-5 1- 1294894 methyl polyoxyalkylene chain, a methyl vinyl polyoxyalkylene chain, a methylphenyl polyoxyalkylene chain, and the like. Copolymer chain [dimethyl methoxy oxane-methyl vinyl fluorene copolymer chain, dimethyl methoxy oxane - methyl phenyl siloxane copolymer chain, dimethyl methoxy oxane - methyl (3,3,3 -trifluoropropyl)oxyl copolymer chain, dimethyloxane-methylvinyloxirane-methylphenyloxime copolymer chain, etc. Both ends of the polyoxyalkylene rubber are, for example, a trimethylaxyl group, a dimethylvinyl formyl group, a stanol group, a tri-Ci 2 alkoxy group, and the like. The polyoxyalkylene rubber (Q) includes, for example, methyl polyoxyalkylene rubber (Mq), vinyl polyoxyalkylene rubber (VMQ), phenyl polyoxyalkylene rubber (PMQ), phenyl vinyl polyoxyl Alkane rubber (PVMQ), fluorinated polyoxyalkylene rubber (FVMQ), etc. In addition, 'polyoxane oxime rubber contains high temperature vulcanizable high temperature Vulcanizable solid rubber, room temperature vulcanizable RTV (Room Temperature Vulcanizable) or low temperature vulcanizable LTV (Low Temperature Vulcanizable) polyoxyalkylene rubber For example, it contains a rubber in the form of a liquid or a slurry. The urethane rubber (U) includes, for example, a polyester urethane elastomer, a polyether urethane elastomer, and the like. The modified rubber comprises a non-cyanide-based modified rubber (for example, carboxylated styrene butadiene rubber (X-SBR), carboxylated ethylene propylene rubber (x_ep(d)m)), and vinyl cyanide-modified rubber ( For example, a residual nitrile rubber (X _ NBR ) or the like has a thiol group or an acid anhydride group. Further, in the composite (2), a resin (or resin composition) or a rubber component can be used in a powdery form. The shape of the resin (or resin composition) or rubber powder -52 to 1294894 is not particularly limited, and examples thereof include an amorphous shape, a spherical shape, an elliptical shape, and a rod shape. The average particle size of the granules is, for example, 〇. 丨~8〇〇 _, preferably 0. 5~500μΐη, the best one is 〇. 8~3〇〇μπι. Further, the ratio of the above resin to the above rubber in the above composite (2) can be appropriately set within the range of characteristics having an effective composite dispersion, for example, a resin phase/sulfur rubber phase (weight ratio) = 90/1 〇 1 〇/9〇 (eg 9〇/1〇~ 30 / 70), preferably 7 5 / 2 5 ~ 2 5 / 7 5 (eg 75/25~50 / 50), the best is 60/40 ~40/60. [Vulcanizing agent] The vulcanizing agent not only vulcanizes (or crosslinks) the unvulcanized rubber, but also activates the resin depending on the kind of the resin or the vulcanizing agent (for example, the above-mentioned active atom is removed and radicalized) The resin is activated, and the crosslinkable group of the crosslinkable resin is activated. The adhesiveness between the resin and the rubber is improved, and the resin is bonded to the rubber. The vulcanizing agent may be a type of the above-mentioned resin or rubber, and a radical generating agent or sulfur may be used, and the above-mentioned radical generating agent such as an organic peroxide, an azo compound, or a sulfur-containing organic compound may be used. The sulfur-adding agents may be used singly or in combination of two or more. The vulcanizing agent may be added with at least one unsulfurized rubber and resin, or two components may be added. Organic peroxides such as dioxonium peroxides (laurel-based peroxide, benzhydryl peroxide, 4-benzyl benzhydryl peroxide, 2,4-dichlorobenzylidene) Oxide, etc.), dialkyl peroxides (di-t-butyl peroxide, 2,5-di(t-butylperoxy)-2,5-dimethylhexane, 1, bu-double ( Tert-butylperoxybu-3,3,5-trimethylcyclohexane, etc.), peroxyester-53- 1294894 (tert-butyl peracetate, tert-butyl permethylacetate, etc.) The azo compound includes azoisobutyronitrile, etc. The sulfur-containing organic compound includes an amine scorpion (tetramethylamine sulphate monosulfide (TMTM), tetramethylamine sulphur disulfide (TMTD), Tetraethylamine deuterated disulfide (TETD), tetrabutylamine depleted disulfide (TBTD), diammonium methylamine depleted tetrasulfide (DPTT), morpholine disulfide, alkylphenol Sulfur, etc., etc. Sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, etc. Further, sulfur contains sulfur chloride such as sulfur monochloride or sulfur dichloride. versus When bonding, it is also possible to use a photopolymerization initiator as a radical generator during light irradiation. A photopolymerization initiator such as benzophenone or a derivative thereof (3,3'-dimethyl-4-methoxy group) Benzophenone, 4,4-dimethoxybenzophenone, etc., alkyl benzophenone or a derivative thereof (acetophenone, diethoxy phthalic acid, 2-hydroxymethyl-2-methyl- 1-phenylpropene-1-reparent, benzyl dimethyl acetal, 1-hydroxycyclohexyl benzophenone, 2-benzyl-2-aminomethyl-1-(morpholinylphenyl) )-butanone, etc., hydrazine or its derivatives (2-methylhydrazine, etc.), thioxanthone or its derivatives (2-thiothioxanthone chloride, alkylthioxanthone, etc.), benzene An ether or a derivative thereof (such as a benzene or a benzene alkyl ether), a phosphine oxide or a derivative thereof, etc. Further, the radical generator includes a persulfate (ammonium persulfate, potassium persulfate, etc.). The preferred vulcanizing agent is an organic peroxide. The vulcanizing agent is preferably at least containing unvulcanized rubber, usually mostly unvulcanized rubber. The proportion of the vulcanizing agent is, for example, 100 parts by weight of unsulphurized rubber. And/or resin selected from 0. 1 to 15 parts by weight, usually 0. 1 to 10 parts by weight, preferably 0. 1 to 8 parts by weight (e.g., 1 to 7 parts by weight). -54 - 1294894 [Chane coupling agent] The present invention may contain a decane coupling agent when the adhesion between the resin and the vulcanized rubber can be improved. The decane coupling agent may be added with at least one unsulfurized rubber (or unvulcanized rubber composition) and a resin (or resin composition), or both components may be added. The decane coupling agent includes a compound having a reactive group (e.g., a hydroxyl group, an alkoxy group, a vinyl group, an amine group, an epoxy group, a decyl group, a carboxyl group, an isohydroester group, a (meth) acryl group, etc.). For example, an alkoxy decane (for example, a tetra-oxyalkyl decane such as trimethoxy decane or triethoxy decane, such as tri-c- 4 alkoxy decane, tetramethoxy decane or tetraethoxy decane); Alkoxy decane (vinyl trimethoxy decane, vinyl triethoxy decane, etc. vinyl three 1. 4-alkoxydecane); alkoxydecane having an amine group (for example, 2-aminoethyltrimethoxydecane, 2-aminoethyltriethoxydecane, 3-aminopropyltriethoxylate) Amino C 2_4 alkyl di C, such as decane, such as an amine C 2_4 alkyl tri-Ci_4 alkoxy decane, 3-aminopropyl methyl dimethoxy decane, 3-aminopropyl methyl ethoxy decane _ 4 院电砂砂院··, an alkoxy decane having an epoxy group (for example, a glycidoxy C2 such as 3-glycidoxypropyltrimethoxydecane. 4 three. _4 alkoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc. (epoxycycloalkyl)C2. 4 alkyl triple C 1. 4 alkoxy decane); alkoxy decane having a mercapto group (for example, a fluorenyl group such as 3-mercaptopropyltrimethoxydecane). 4-alkyltri-C^4 alkoxydecane, 3-mercaptopropylmethyldi- 5 5 - 1294894 methoxy decane, etc. 4 alkyl two C!. 4 alkoxy decane); alkoxy decane having a carboxyl group (for example, carboxymethyltrimethoxydecane, carboxymethyltriethoxydecane, carboxyethyltrimethoxydecane, carboxypropyldimethoxysilane) Wait for the base C!.  4 院基二[^4院氧砂院); alkoxy decane having an isocyanate group (e.g., isocyanate ethyltrimethoxydecane, isocyanate ethyltriethoxydecane, isocyanate propyltrimethoxydecane, etc.) Isocyanate Ch4 alkyltrialkoxydecane); alkoxydecane having (meth)acrylinyl group (for example, N-(3-(methyl)propenyloxy-2-hydroxypropyl)-3-amine Propyl triethoxy decane, 3-(methyl)propenyloxypropyl monomethyl methoxy 5, 3-(methyl) propylene methoxy propyl dimethyl ethoxy Decane, 3-(methyl)propanyloxypropylmethyldiethoxydecane), and the like. The amount of the decane coupling agent used is usually such that the amount of the resin bonded to the rubber is, for example, 1 to 1 part by weight of the rubber or resin, and may be selected from 1 to 1 part by weight of the decane coupling agent, preferably 2 to 8 parts by weight. More preferably, it is 2 to 6 parts by weight. [Other Additives] The above rubber (or rubber composition) may be blended with various additives such as a sulfurizing active agent (such as a sulfurizing active agent described in the above resin composition), a chelating agent, a plasticizer or a softening agent. a vulcanizing agent (such as a metal oxide such as zinc oxide), an antioxidant (a heat-resistant aging agent, an anti-ozone deterioration agent, the above-mentioned antioxidant, the above-mentioned ruthenium absorbing agent, etc.), a binder, a processing aid, and a smoothing agent ( Stearic acid, metal stearate, paraffin, etc.), coloring agents, foaming agents, dispersing agents, flame retardants, antistatic agents, and the like. a 5 6 - 1294894 Moreover, most of the rubber does not contain a sulfur-containing active agent (for example, a bisphenol-based sulfur-adding active agent such as a di(meth)acrylate of a c2_3 alkylene oxide adduct of bisphenol A, Malay醯imine-based sulphur active agent, etc.). The above-mentioned sputum agent (or reinforcing agent) includes, for example, a powdery granule filler or a reinforcing agent (mica, clay, talc, decanoic acid, cerium oxide, calcium carbonate, magnesium carbonate, carbon black, pure iron particles, etc.), fiber A medicinal agent or a reinforcing agent (organic fiber such as Thunder, Nylon, and aromatic polyamine, inorganic fiber such as carbon fiber or glass fiber). When the rubber is a polyoxyalkylene rubber, the most general chelating agent added as a reinforcing agent is cerium oxide powder. Generally, the cerium oxide powder used in the polyoxyalkylene rubber is classified into wet cerium oxide produced by wet method and dry cerium oxide manufactured by dry type. The cerium oxide powder suitable for the polyoxyalkylene rubber is dry cerium oxide, and when the dry cerium oxide is used, the high bonding strength between the resin component and the rubber component can be easily obtained. In the case of wet ruthenium dioxide, the moisture contained in the ruthenium dioxide powder is a crosslink between the resin component and the rubber component. However, even wet cerium oxide is not only a fatal resistance to the adhesion of rubber parts and resin parts, but also depending on the resin used or the type of polyoxyalkylene rubber used, the type of sulphur active agent or its use, forming conditions. Wet ceria can be used as the case may be. Dry cerium oxide and wet cerium oxide can be used in combination. The plasticizer can be imparted to the rubber composition, and is not particularly limited, and a general softener (vegetable oil such as linoleic acid, oleic acid, castor oil, palm oil, etc.; stone enamel, engineering oil, supplement, etc.) can be used. Mineral oil, etc.), plasticizer (phthalic acid ester, aliphatic dicarboxylic acid ester, sulfur-containing plasticizer, polyester-57- 1294894 polymer plasticizer, etc.). The amount of the sulfur-containing active agent used is, for example, 〇1 to 10 parts by weight, preferably 0 to 8 parts by weight, and most preferably 〇 to 5 parts by weight, per 100 parts by weight of the rubber. The content of the ruthenium is, for example, 〇 to 300 parts by weight, preferably 0 to 20 parts by weight, more preferably 0 to 1 〇 〇 by weight, per 100 parts by weight of the rubber. The content of the plasticizer or softener is, for example, 〇 to 200 parts by weight, preferably 0 to 150 parts by weight, more preferably 〇 to 120 parts by weight, per 100 parts by weight of the rubber. In addition, the content of the co-sulfurizing agent, the anti-aging agent, the processing agent or the smoothing agent, the coloring agent and the like may be an effective amount, for example, the content of the co-sulfurizing agent is 0 to 20 parts by weight for 1 part by weight of the rubber. Preferably, it is 0. 5 to 15 parts by weight, more preferably 1 to 10 parts by weight. Further, the continuous phase (or the matrix phase) constituting the composite dispersion in the above composite dispersion (2) may be formed of either a resin or a rubber. The composite dispersion has, for example, (2a) a composite phase composed of a continuous phase composed of a rubber phase and a dispersed phase composed of a resin phase, (2b) a continuous phase composed of a resin phase, and a dispersed phase composed of a rubber phase. Composite dispersions, etc. The form of the above (2 a ) may produce characteristics (elasticity, cushioning property, flexibility, etc.) of the vulcanized rubber, and may impart properties (for example, smoothness, abrasion resistance, etc.) to the resin, and the form of the above (2b) may produce a resin. Characteristics (mechanical properties such as rigidity and toughness), and characteristics of the vulcanized rubber (slip resistance against friction, adhesion to a target material, etc.). Further, the composite dispersion (2) may have a sea-island structure in which dispersed phases are independently dispersed in a continuous phase, and the shape of the dispersed phase may be a particle shape, an elliptical shape, a rod shape, a fiber shape or the like. The preferred shape of the dispersed phase is spherical, and the -58 to 1294894 dispersed phase is preferably dispersed uniformly in the continuous phase. Further, the average particle diameter of the dispersed phase may be such that it has a property of forming a dispersed phase, for example, ruthenium. 丨~ ΙΟΟΟμηι, preferably 1 to 75 μm, and more preferably 1 to 500 μm (for example, 50 to 1 50 μm). Further, when crosslinked or hardened particles are used as the rubber, the average particle diameter of the above dispersed phase corresponds to the average particle diameter of the crosslinked or hardened particles. Further, the composite dispersion (2) can bond the resin phase to the rubber in a state where the dispersed phase particles are partially exposed on the surface. For example, when the resin phase is a dispersed phase particle, it has a rubber property of a continuous phase (e.g., high flexibility and cushioning property), and has a resin property (e.g., a low friction coefficient) on the surface. Further, the composite of the present invention can be a composite of the composite dispersion (2) and other molded bodies (e.g., a resin molded body, a vulcanized rubber molded body, etc.) bonded to a contact surface. [Method for Producing Resin Composition] The resin composition of the present invention can be produced by mixing (particularly kneading) a resin with a vulcanization active agent and a stabilizer. The kneading is carried out using a general kneading machine (e.g., an extruder, a kneader, a Banbury mixer, etc.). Further, the kneading may be carried out first, and then the mixing treatment may be carried out by a general mixer (manual mixer, tumbler mixer, ribbon blender, etc.). The kneading temperature may be selected depending on the kind of the resin, so that the resin can be at a meltable temperature, for example, 1 20 to 40 CTC, preferably 1 30 to 3 50 ° C, and most preferably 1 50 to 300 ° C. C. When the present invention contains a stabilizer, it can be a kneading temperature at which the sulfur-adding active agent crosslinks itself, does not inactivate the sulfur-adding active agent, and can knead the resin with the sulfur-containing active agent. [Method for Producing Complex] 59- 1294894 The method for producing a composite can be distinguished by the form of the composite (complex (1), composite (2)). (i) in the production of the composite (1), the resin composition (resin composition composed of a resin and a vulcanization active agent and a stabilizer) and a vulcanizing agent (particularly a radical generator) are not provided. The vulcanized rubber is contacted and molded to produce a composite (1) in which a resin component composed of the above resin composition is bonded to a rubber component composed of a vulcanized rubber. The composite can be produced by forming a molded resin material in contact with a shaped rubber material and vulcanizing or cross-linking the above-mentioned formed rubber material. Further, the molded resin material may be the above resin composition, or may be a resin component (or a resin molded body) obtained by molding the above resin composition in advance. Further, the above-mentioned molded rubber material is active in a vulcanizing agent in contact with the molded resin material, and contains at least a rubber which is not vulcanized, and is not particularly limited, and may be a non-sulfurized rubber composition or a part. A vulcanized or crosslinked rubber preparation body or the like. In other words, the resin composition may be formed in contact with an unvulcanized rubber composition composed of an unsulfurized rubber and a vulcanizing agent (or an unvulcanized rubber composition further containing the above-described vulcanizing active agent) The vulcanized rubber composition is vulcanized or crosslinked to produce a composite in which the resin part and the rubber part are bonded. Further, only the vulcanizing agent may be active, and at least one of the resin member (or the resin molded body) and the rubber member (rubber molded body) may be previously formed. For example, (a) a resin member composed of the above resin composition is brought into contact with an unsulfurized rubber composition, and an unsulfurized rubber composition is formed and vulcanized or crosslinked to produce a composite. (b) A composite body can be produced by contacting the above-mentioned resin composition on a rubber preparation molded body prepared by vulcanization or cross-linking of a rubber composition to form a composite of the resin composition -60-1294894, (C) The resin component _h composed of the above resin composition is brought into contact with a rubber preparation molded body in which the rubber composition is vulcanized or crosslinked to produce a composite. Further, the rubber-prepared molded body may be any rubber-prepared molded body in which a vulcanizing agent remains, as long as it is active at least on the contact surface with the molded resin material. More specifically, the method of the present invention comprises forming each of the above resin composition and the unsulfurized rubber composition, and bringing the resin composition into contact with the unsulfurized rubber composition during the forming process, and joining the resin parts. a method of bonding or bonding a sulfur rubber component (one-stage method); contacting a resin component previously formed of the above resin composition with an unsulfurized rubber composition, forming an unsulfurized rubber composition, and vulcanizing or crosslinking to cause a resin a method of bonding or bonding a part to a vulcanized rubber part (two-stage method); preparing a resin part previously formed of the above resin composition, and a rubber preparation of an unsulfurized rubber composition until midway and forming (partially vulcanized or crosslinked) A method in which a molded body is brought into contact with a rubber-prepared molded body by adding sulfur or cross-linking to bond or bond the resin component to the vulcanized rubber component (three-stage method). The preferred method includes a one-stage method and a two-stage method (especially a two-stage method). In the one-stage method, for example, a general multicolor molding machine (multicolor injection α-opening machine 'multilayer extruder, etc.) can be used to make the resin The composition and the unsulfurized rubber composition are each melt-kneaded and extruded or extruded into a forming mold of a predetermined shape, and the composite rubber is formed by vulcanization or cross-linking after forming or forming. Molded body). Further, a resin composition and an unsulfurized rubber composition may be mixed in the contact interface between the resin composition and the unsulfurized rubber group. -61- 1294894 In addition, in the two-stage method, a general molding machine (injection molding machine, extrusion molding machine, hot press molding machine, etc.) can be used for molding a resin part, and a general molding machine can be used for molding a rubber part. (Injection molding machine, press molding machine, transformation molding machine, extrusion molding machine, etc.). For example, a mold (or a cavity) corresponding to the shape of the composite accommodates a resin component, and the unsulphurized rubber composition is injected or extruded to the resin component by sulfurizing or crosslinking the unsulfurized rubber composition. , the vulcanized rubber parts can be bonded to the resin parts. Further, when the composite is a plate-like or sheet-like member having a wide width of a second element, it is possible to laminate a plate-like or sheet-like unsulfurized rubber composition to the resin member without using the above-described mold (or a cavity). The composite is produced by vulcanization or crosslinking. Further, when the resin component (or the resin composition) is brought into contact with the unsulfurized rubber composition (such as adhesion), the volatile component or the gas component in the unsulfurized rubber composition can be removed by hot pressing or injection. The pressure may be suitably formed by press molding or the like under pressure in a reduced pressure atmosphere. The vulcanization or crosslinking temperature (or the bonding temperature of the rubber part to the resin part) is, for example, selected from the group consisting of 70 to 250 ° C, preferably 100 to 230. The optimum is 150 to 220 ° C. The pressure acting between the rubber/resin is selected, for example, from hydrazine.  ~ 3 5 0 MPa, preferably 1 to 150 MPa, and most preferably 2 to 100 MPa. Further, at least one of the components in the production of the composite is selected from the components of the unsulfurized rubber and the resin composition, and may contain the above-mentioned vulcanization aid (for example, the above polyamine). Usually, a vulcanization aid is often added to the resin composition. Further, after the surface of the resin component on which the resin composition is formed is treated with a solvent capable of dissolving or swelling the resin component (by coating, dipping, etc.), the treated surface of the resin component may be composed of unsulfurized rubber. Effective -62- 1294894 Ground contact. The solvent may be appropriately selected from the group consisting of hydrocarbons (aliphatic hydrocarbons such as hexanol or octane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), and the like. Alcohols (alcohols such as isopropanol, butanol or cyclohexanol, halogenated alkanols such as tetrafluoroethanol and hexafluoroisopropanol), phenols (benzoquinone, formazan, etc.), organic acids (formic acid, Acetic acid, trifluoroacetic acid, trichloroacetic acid, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (dioxane, Diethyl ether, tetrahydrofuran, etc.), flavonoids (dimethyl hydrazine, etc.), guanamines (dimethylformamide, dimethylacetamide, etc.) or a mixed solvent of these. For example, when the resin is a polyamide resin, benzene (phenol, cresol, etc.), organic acid (formic acid, etc.), ketones (hexafluoroacetone, etc.), alcohols (six) can be used on the contact surface with the rubber parts. Fluoroisopropanol or the like is mixed or coated alone or in combination with a general organic solvent. Further, when the resin is a polyphenylene ether resin, a solvent or a swelling agent such as a hydrocarbon (such as toluene), a ketone (such as acetone, methyl ethyl ketone or hexafluoroacetone), an ether (such as tetrahydrofuran), or a hydrazine. An amine (such as dimethylformamide) or an alcohol (such as hexafluoroisopropanol). Further, after the treatment with the above solvent, the solvent is removed from the resin part by washing, drying, etc., by making the above resin parts. The contact between the surface and the unsulfurized rubber composition allows the vulcanized rubber parts to be firmly bonded to the resin parts. (11) In the production of the composite (or composite dispersion) (2), the resin composition can be produced by kneading and molding the rubber composition. Moreover, the rubber may be an unvulcanized rubber (especially an unvulcanized rubber containing a vulcanizing agent) or a vulcanized rubber. The vulcanization or cross-linking of any 'un-vulcanized rubber may be in the appropriate step 63- 1294894, For example, it is carried out in a forming process, a post-forming process, and the like. Further, at least one of the vulcanized rubber phase and the resin phase (particularly a vulcanized rubber phase) may be formed of a composition containing a vulcanizing agent (particularly a radical generating agent), and the vulcanized rubber phase may contain a composition of a vulcanizing active agent. Object formation. Further, the sulfurizing agent and/or the sulfurizing active agent may be added to the rubber in advance or may be added in the kneading process. More specifically, the composite (2) of the present invention can be formed into a predetermined shape by kneading the above resin composition with an unsulfurized rubber (particularly, an unvulcanized rubber composition containing a sulfurizing agent). The vulcanized rubber is produced by adding sulfur or cross-linking after the forming process or after forming. Further, the composite dispersion (2) of the present invention can be obtained by kneading the above resin composition and a vulcanized rubber (sulfurized rubber composition) to form a predetermined shape. In this method, in general, the sulfur-added rubber may be in the form of a powder or granule which is vulcanized by a method such as pre-freezing and pulverization, or a polymerization method using a sulfurizing agent. Kneading can be carried out using a conventional kneader (for example, an extruder or the like). Further, when the thermosetting resin or a composition thereof is kneaded with an unsulfurized rubber or a vulcanized rubber, it is usually kneaded in a non-hardened state in the thermosetting resin. Further, the kneading of the unsulfurized rubber is carried out except that the dispersed phase is formed by the vulcanized rubber phase, and usually the rubber is carried out in an unsulfurized state. The forming method is, for example, extrusion molding, injection molding, flow molding, or the like, and extrusion molding or injection molding is usually used. The shape of the molded article is not particularly limited, and may be a plate shape, a sheet shape, a tubular shape or the like. Further, the 'forming temperature is appropriately set depending on the raw materials used (for example, resin and rubber)', for example, 50 to 300 T: preferably 75 to 250 ° C, and most preferably 100 to 22 5 ° C. (eg 150 _ 6 4 - 1294894 ~ 2 Ο 0 〇 C ). The composite dispersion can be obtained by subjecting the shaped article to vulcanization or crosslinking by a forming process or after forming. The vulcanization can be carried out under a reduced pressure atmosphere, generally under normal pressure. Further, the vulcanization or crosslinking temperature is, for example, selected from the range of 70 to 2 50 ° C, preferably 100 to 230 ° C, and most preferably 150 to 220 ° C. Further, at least one of the components of the composite (2) is selected from the group consisting of unsulphurized rubber and a resin composition, and may contain the above-mentioned vulcanization aid (e.g., the above polyamine). Usually, a vulcanization aid is often added to the resin composition. In the present invention, since the combination of the sulfur-adding active agent and the stabilizer constitutes a resin composition, the resin can be surely and firmly bonded to a wide range of rubber without using a binder. Further, by using the above resin composition as a resin material, it is possible to stabilize the rubber and industrially manufacture a composite of a resin and a rubber in which the resin is reliably and strongly bonded. Industrial use price 复合 The composite system thus obtained adheres rubber and resin with high strength by vulcanization. Therefore, it has the characteristics of an effective thermoplastic resin and the characteristics of rubber, and can be utilized as various applications, such as automotive parts (vibration absorption brushes, spring plates, door lock parts, heat sinks, etc.), anti-vibration rubber, valves, electrical plugs, and the like. Various parts. [Embodiment] [Embodiment] The present invention will be more specifically described by the following examples, but the present invention is not limited by the embodiments. Further, in the examples and the comparative examples, the following resin composition and rubber composition were used in -65 to 1294894. Resin A 1 to A 3 Polyamide 6 1 2 (polycondensation product of hexamethyldiamine and dodecanedicarboxylic acid) was produced as a thermoplastic resin, and the following resin or resin composition (A 1 to A3 ) was prepared. Moreover, the calculation of M0PACPM3 is performed based on the following basic units.

With the factory (CH2) 6-NH-C ( = 0) - (CH2) 1 (rC (=0) -0H Resin (A 1 ): Modulation of A1: salt of hexamethyldiamine and dodecanedicarboxylic acid 80% by weight of the aqueous solution was heated (220 ° C) in a nitrogen-substituted autoclave under pressure (17.5 kg / cm2 (1 7 15 MPa)), so that the nitrogen gas and the moisture in the system were simultaneously discharged in 4 hours. Then, after the water residue was discharged to the outside of the system by heating for 1 hour (2 7 5 ° C), the internal pressure of the autoclave was returned to normal pressure. After cooling, polyamide 612 was obtained. The number average molecular weight (Μη) of the substance is 20,000 to 25,000, the ratio of the terminal of the amine group to the terminal of the carboxyl group is about 丨/丨, and the energy coefficient S of the orbital interaction when the sulfurizing agent is used as the radical generating agent is 0. 006 or more. The number of active hydrogens is four in one molecule. The polymer is used alone as the resin (A 1 ). Resin (A2): Modification of the resin (A2): the above resin (a 1 ), and the following resin (A3) The mixture was kneaded by a 2-axis extruder at a weight ratio of 1/1 to obtain a polyanthracene having a number average molecular weight (?η) of 22,000 and an amine terminal to carboxyl terminal ratio of about 3/7. Amine 6 1 2 . The orbital interaction energy coefficient S when the sulfur-adding agent is used as a radical generating agent in the obtained polymer is 2.4 活性·〇〇6 or more of the active hydrogen atom in a 'molecule. Resin (Α2). 1294894 Resin (A 3 ) = Resin (A 3 ) Modification: Adding the quantified 12-dose di-residue acid to an 8 〇 wt% aqueous solution of hexamethyldiamine and dodecanedicarboxylic acid salt, In a nitrogen-substituted autoclave, pressurize (17. 5kg/cm2 (i7i5MPa)) and heat (220 °C), so that the nitrogen gas and the moisture in the system are discharged to the outside of the system at the same time for 4 hours. Then, for 1 hour. After heating (2 7 5 °C), the water residue is discharged to the outside of the system, and the internal pressure of the autoclave is returned to normal pressure. After cooling, the polyamine 6丨2 is obtained. The number average molecular weight of the obtained polymer (Μη) The ratio of the amino group terminal to the carboxyl group terminal is about 1 / 9, and the number of active hydrogen having an orbital interaction energy coefficient S of 0.006 or more in the case of a sulfurizing agent as a radical generating agent is 0.8 in one molecule. This polymer is used alone as the resin (A3). Resin (Β) Manufacture of polyamine 6 as Plastic resin. Moreover, the calculation of MOPACPM3 is based on the following basic units: Problem 2-(CH2) 5-C (=0) -ΝΗ- (CH2) 5-c (=0) -0Η Modification of Resin B: 8-caprolactam salt 80% by weight aqueous solution, in the presence of a small amount of phosphoric acid in a nitrogen-substituted autoclave heated to 25 (rc ~ 260C' so that the gas hot gas and the moisture in the system is discharged in 4 hours Out of the system. Then, the water residue was discharged to the outside of the system by heating at a temperature of 1 hour (27 5 ° C), and after cooling, the polyamide 6 was obtained. The number average molecular weight (?η) of the obtained polymer is from 2,000 to 2,500 Å, and the ratio of the terminal of the amine group to the terminal of the carboxy group is about 1/3. The orbital interaction when the sulfur-adding agent acts as a radical generator The energy coefficient S is 〇. The number of active hydrogens above 〇〇6 is four in one molecule. This polymer is used alone as a resin (Β). 1294894 Resin (c) Polybutylene terephthalate is prepared as a thermoplastic resin. Moreover, the calculation of MOPACPM3 is based on the following basic units. H〇-(CH2)4 -〇-C(=〇)

C(=0)-0H Modification of Resin C: 8.2 g of calcium acetate, 3.64 g of cerium oxide, with a blender, was added to 8 8 3 g of distilled purified dimethyl phthalate and 8 1 9 g of butanediol. A nitrogen introduction tube, a side tube for distillation, and a polymerization tube connected to a vacuum system. The polymerization tube was heated to 18 Torr by an oil bath and slowly passed through a nitrogen gas. When the amount of distilled methanol reached the theoretical enthalpy, stirring was started, and the temperature in the system was gradually increased to 205 to 260 ° C, and the degree of vacuum was gradually increased to less than 100 Pa. The produced butanediol is distilled off in a small amount and subjected to a condensation reaction for 2 to 3 hours, and the relative viscosity in a mixed solvent of tetrachloroethane/phenol bismuth/6 fluorene is measured, and the number average molecular weight is reached. When the time is up, the reaction is finished. When the sulfur-adding agent in the obtained polymer is used as the radical generating agent, the number of active hydrogens having an orbital phase interaction energy coefficient S of 0.006 or more is one in one molecule. This polymer was used alone as the resin (C). Resin (D) Polyphenylene sulfide (manufactured by Polyplastics Co., Ltd., Fluorene 22〇A9) was used as the resin (D). When the sulfurizing agent is used as a radical generating agent, the number of active sulfur atoms per molecule is 2 or more, and the calculation of M0PACPM3 is performed based on the following basic unit. r * C l - C6H4- S - C6H,4-S - - C 1 Resin (Ε ) 68 1294894 Modulation of alicyclic polydecylamine [bis(4-aminocyclohexyl)methane], with dodecane = residual The acid polycondensate is used as a thermoplastic resin. Moreover, the calculation of m〇PACPM3 is performed based on the following basic units. H2n—&lt;^^-ch2—^^nh-(c=〇)-(ch2)10-c(=〇)-〇h Modification of Resin E: In addition to the combination monomer as bis(4-aminocyclohexyl) In addition to methane and dodecanedicarboxylic acid, the number average molecular weight (?n) is 20,000 to 25,000, and the ratio of the terminal of the amine group to the terminal of the carboxyl group is about 1 / in the same preparation method as the above resin (A 1 ). 1 polymer. When the sulfur-adding agent is used as a radical generator, the orbital interaction energy coefficient S is 0.006 or more of active hydrogen &gt; the number is 3 in one molecule. This poly compound is used alone as a resin. [Unvulcanized rubber composition (R)]:: The following components are blended in a predetermined ratio, and an unsulfurized rubber composition (R 1 to R 2 ) is prepared. The rubber composition (R 1 ) (i) ethylene propylene II Ethylene rubber ("Kenruta 509 X 100" manufactured by DSM Co., Ltd.) 100 parts by weight (1 1 ) of a radical generator [organic peroxide (dicumyl peroxide)] 5. 5 parts by weight (iii)塡物物 ("N582" manufactured by Asahi Carbon Co., Ltd.) 1 part by weight (1 v ) of plasticizer ("Ryananabu Engineering Oil NS 1 0 0" manufactured by Idemitsu Kosan Co., Ltd.) 5 parts by weight (v ) zinc oxide 3 parts by weight -69 - 1294894 (V i ) 1 part by weight of stearic acid rubber composition (R2) (i) vinyl polyoxyalkylene rubber (made by East Relais Nikko Co., Ltd.)矽 烷 胶 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 851 In the resin, the sulfur-adding active agent (TR I Μ : trimethylolpropane trimethacrylate) and the stabilizer [Ν, Ν, - hexamethylene bis (3, 5 -) were added in the proportions shown in Table 1. a second butyl-4-trans-hydro-cinnamoylamine (manufactured by Irga η ο X ) 1 0 9 8 Chiba Machinery Co., Ltd.), melt-kneaded and (temperature conditions) - Resin Α 1 to A3, Resin Β and Resin C at 260 ° C, Resin D at 300 ° C, and Resin E at 280 ° C) The state of the monofilament extruded from the mold was observed and evaluated by the method shown below. X: There will be a single filament jump up and down in the mold part, and there will be a rough feeling on the surface of the monofilament drawn by the extractor, resulting in a majority of protrusions △: there is no monofilament in the mold part, but the extractor draws There is a raised sensation on the surface of the monofilament: there is no monofilament in the mold part, and there is no protrusion on the surface of the monofilament drawn by the extractor (adhesion test). Adding sulfur in the above-mentioned resin in the proportion shown in Table 1 Active agent (TR I Μ : trimethyl cellulose propane trimethacrylate) and stabilizer (Ν, Ν, - 六伸甲-70- 1294894 bis (3, 5 - di- 3 - butyl - 4-hydroxy-hydrocinnacinamine (Irganox 1 09 8 Chiba Machinery Co., Ltd.)), according to the temperature conditions shown in Table} (2 30 °C, 260 °C, 190 ° C, 3 20 ° C) melt-kneaded, supplied to the injection molding, to make a variety of thermal experience of 100mmX lOOmmx 3mm resin plate. The plate is housed in a horizontal mold having a diameter of 1 0 0 m m x 1 0 0 m x 6 m ι

The rubber mold for press forming of the groove was placed on the upper portion thereof to obtain the above-mentioned unsulfurized rubber composition as shown in Table 1, and the mixture was heated and compressed at 170 ° C for 1 minute to make the rubber and vulcanized and the resin plate was Rubber bonding. Further, in the above bonding, the 1/3 area of the resin flat plate is covered with an aluminum alloy to secure the grip. The flat plate composed of the resin/rubber composite thus obtained was cut into the above-mentioned width of 30 mm to prepare a test piece. The grasping position of the test piece was fixed to the upper and lower lattices, and the tensile test was performed at a tensile speed of 50 mm/min using a universal tensile tester, and a peel test of 18 ° C was performed, and evaluated by the following method.

A: There is agglomeration failure of the rubber layer on the entire peeling surface B: 7% of the peeling surface is the agglomeration damage of the rubber layer, and there is a 30% interface peeling between the rubber/resin C: 5 with the peeling surface 0% is the agglomeration failure of the rubber layer, and there is a 50% interface peeling between the rubber/resin. D: There is a large amount of interfacial peeling on the peeling surface, and there is no sufficient adhesive strength. The results are shown in Table 1. Further, it is described in Table 1 that no sulfurizing active agent is added to the resin. As can be seen from Table 1, since the sulfur-adding active agent and the stabilizer are added to the resin in the examples, the sulfur-adding active agent has an effective function, and the resin is firmly bonded to the rubber -7 1- 1294894. -72- 1294894 - 73丨胆室μ—^ Ο Comparative Example 8 ! Example 9 Comparative Example 7 Example 8 Comparative Example 6 Example 7 Comparative Example 5 Example 6 Comparative Example 4 Example 5 Comparative Example 3 Comparative Example 2 Embodiment 4 Embodiment 3 Embodiment 2 Embodiment 1 Comparative example ιΠ m σ ο ο ο txi tx) &gt; LO &gt; OJ &gt;&gt; to &gt; H_* &gt;&gt;&gt; Η-1 &gt; Η—* &gt; Η—» Resin resin composition OJ 2 or more 1 2 or more 1 ο ο -Ρ- 0.8 0.8 2.4 4^· 4^ 1 Active atom 1 〇〇L〇ο LO ο UO L〇O LO LO 〇 〇UJ LO parts by weight sulphur active agent 〇o Ο ο Ο ο ο ο 0.5 oo Lyn 〇1—» &gt;~ι 0.5 Ο 1» 重量 Weight parts stability [J 86/14 1 86/14 1 86/14 1 86/14 1 86/14 1 86/14 1 23/77 38/62 75/25 86/14 97/3 1 Weight ratio sulfur addition active agent / stabilizer 〇X 〇〇〇〇〇X 〇〇〇X 〇〇〇〇0 X Gelation test 1 b〇c〇Pd to to ι&gt;〇Pd 1~^ μ-a )~it-1 Ρ〇ι—^ Rubber composition i ] Resin/rubber composite 1 1 1 σ &gt; σ &gt;&gt; o σ &gt;&gt; ϋ ο &gt;&gt;&gt;&gt; 230 〇C resin kneading temperature &gt; σ 1 σ &gt; ϋ &gt;&gt; oo &gt; Dd σ ο &gt;&gt;&gt; Dd 260〇C &gt; σ &gt; ο &gt; ο &gt;tx&gt; Oo &gt; 〇ο ο ϋϋ &gt; W bd 290〇C tx) σ Dd σ W ο dd tx) oo tx) 〇σ ο W ω ω td 320〇C

Claims (1)

1294894 No. 92125555 "Resin composition, composite using the same, and method of using the same" Patent case (corrected on February 8, 2007) Pickup, patent application scope: 1. A resin composition characterized by a resin, a sulfur-adding active agent for improving the adhesion between rubber and resin, and a stabilizer to form 'the sulfur-adding active agent&lt; is a compound having several (meth)acryl fluorenyl groups. The stabilizer has a free radical trapping function. The ratio (weight ratio) of the sulfur active agent to the stabilizer is the former / the latter = 99 / 1 ~ 25 / 7 5 . 2. A composite body characterized in that a resin composition as claimed in claim 1 is directly bonded to a vulcanized rubber formed by vulcanization of an unvulcanized rubber. 3. A composite according to claim 2, wherein the resin member composed of the resin composition as in the first aspect of the patent application is directly bonded to the vulcanized rubber member. 4. The resin composition according to claim 1, wherein the resin has at least two hydrogen atoms and/or sulfur having an orbital interaction energy coefficient S of 0.006 or more represented by the following formula (1) in one molecule. Atom, Lu S = (CΗΟΜΟιη) V | Ec&quot;EHOMOtn I +(CLUMOin)VI Ec~E!LUM〇tn I (1) (where E., CHOMO, n, E_0, n, CLUMO.n, ELliMO, n is obtained by the semi-empirical molecular orbital method MOPACPM3, Ed is the radical generating orbital energy (eV) of the radical generating agent, CHQM〇, and n is the nth hydrogen atom constituting the basic unit of the resin or The molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of the sulfur atom, Εηομο, π represents the orbital energy (eV) of the above HOMO, CLUM〇, and n represents the lowest empty molecular orbital of the nth hydrogen atom or sulfur atom - The molecular orbital coefficient of 11294894 (LUMO), Ειιηιο, η represents the orbital energy (e V ) of the above LUMO). 5. The resin composition according to claim 1, wherein the resin is at least one selected from the group consisting of polyamine resins, polyester resins, poly(thio)ether resins, polycarbonate resins, and polyphthalamides. Amine resin, polyfluorene resin, polyurethane resin, polyolefin resin, halogen-containing vinyl resin, styrene resin, (meth)acrylic resin, thermoplastic elastomer, phenol resin, amine Resin, epoxy resin, thermosetting polyimide resin, thermosetting polyurethane resin, polyoxyalkylene resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate Resin and thermosetting acrylic resin. 6. The resin composition of claim 1, wherein the resin is at least one crosslinkable resin selected from the group consisting of a thermoplastic resin having an unsaturated bond and a thermosetting resin having a crosslinkable functional group. 7. The resin composition of claim 1, wherein the stabilizer is at least one selected from the group consisting of a phenolic antioxidant and a hindered amine light stabilizer. 8. The resin composition of claim 1, wherein the proportion of the sulfur-adding active agent is 0.1 to 1 part by weight of the resin, and the ratio of the stabilizer is to 100 parts by weight of the resin. It is 0. 0 1~5 parts by weight. 9) The resin composition of claim 1, wherein the oxidizing active agent is contained in an amount of 0.1 to 5 parts by weight, the stabilizer 〇· 〇 5 to 8 parts by weight, and sulfur is added to 100 parts by weight of the resin. The ratio of the active agent to the stabilizer (weight ratio) is the former / the latter = 98/2 ~ 3 5 / 6 5 . 1 0. The composite of claim 2, wherein the rubber is at least one of -2- 1294894 selected from the group consisting of diene rubber, olefin rubber, acrylic rubber, fluorine rubber, polyoxyalkylene rubber, And urethane rubber. A composite according to claim 2, wherein the unvulcanized rubber is formed by containing at least one sulfurizing agent selected from the group consisting of a radical generating agent and sulfur. 1 2 The composite of claim n, wherein the radical generator is at least one selected from the group consisting of organic peroxides, azo compounds, and sulfur-containing organic compounds. 1 3 . The composite of claim π, wherein the proportion of the sulfur-adding agent is 1 to 10 parts by weight based on 100 parts by weight of the unsulfurized rubber. 1 4 The resin composition according to claim 1 of the patent application, which further comprises, in the third aspect of the patent application, having two or more hydrogen atoms having an orbital interaction energy coefficient S of 0.006 or more in one molecule, and a molecular weight It is a compound of less than 1,000. A method of producing a resin composition as claimed in the ninth aspect of the invention, characterized in that the resin is kneaded with a vulcanization active agent and a stabilizer. a method for producing a composite body which is formed by contacting a resin composition of the first aspect of the patent application with an unvulcanized rubber composition containing a sulfurizing agent, and comprising a resin part and a vulcanized rubber. In the composite in which the rubber component is bonded, the molded resin material which is one of the resin composition and the resin component, and the sulfur-containing agent in the contact surface with the molded resin material are active, and the rubber composition containing the unsulfurized rubber and The formed rubber material in one of the preliminary molded bodies is contact-molded, and the formed rubber is vulcanized or crosslinked to bond the resin member to the rubber member. A method of producing a composite of a vulcanized rubber phase and a resin phase -3- 1294894, which is characterized in that the resin composition of the first aspect of the patent application and the sulphur-containing agent are used. The unsulphurized rubber is kneaded and formed. a 4-