WO2004007194A1

WO2004007194A1 - Composite and process for producing the same

Info

Publication number: WO2004007194A1
Application number: PCT/JP2003/008569
Authority: WO
Inventors: Toru Ikuta; Mitsuteru Mutsuda; Yasumasa Negoro
Original assignee: Daicel-Degussa Ltd.
Priority date: 2002-07-12
Filing date: 2003-07-04
Publication date: 2004-01-22
Also published as: TW200404878A; AU2003252471A1; CN1678453A; JP2004042486A

Abstract

A resin/rubber composite comprising a vulcanized rubber member and a resin member bonded to each other through a vulcanized rubber layer is produced by bringing a rubber element and a resin element into mutual contact through an unvulcanized rubber layer, the unvulcanized rubber layer containing a vulcanizing agent, under pressure and effecting heating and molding thereof while maintaining the pressurized contact. The resin member may consist of a thermoplastic resin or resin having a crosslinkable group, and may consist of a resin having active atom. The components of at least one of the unvulcanized rubber composition for forming the vulcanized rubber layer and the resin member may contain a polyfunctional polymerizable compound having multiple polymerizable groups. Thus, there can be obtained a composite wherein the resin member and the vulcanized rubber member are strongly bonded to each other in a wide range of combination.

Description

Description Composite and its manufacturing method

TECHNICAL FIELD The present invention relates to a composite (or a composite member) in which a resin and a vulcanized rubber are bonded to a body and are useful as a mechanical part, an automobile part, and the like, and a method for producing the same. Background art

As a method for integrally integrating a resin molded member and a rubber molded member, a method of bonding a resin molded body and a rubber molded body using an adhesive is known. However, the method using an adhesive requires a complicated process and complicated process control, which not only increases the cost but also lowers the characteristics such as heat resistance and water resistance, so that sufficient adhesiveness cannot always be obtained. Absent.

A composite in which a resin and a rubber are directly joined has been proposed. For example, Japanese Patent Application Laid-Open No. 50-25882 discloses that a thermoplastic component such as a polyformaldehyde olefin polymer and a vulcanized rubber component compatible with the thermoplastic component are disclosed. Discloses a method for producing a composite in which a plastic surface is melted by frictional contact with a plastic component and a plastic component and a rubber component are solidified while being kept in contact with each other.

As a method for producing a composite utilizing the compatibility of a thermoplastic resin and a rubber, Japanese Patent Application Laid-Open No. Sho 61-204,600 discloses a polyphenylene ether resin and a synthetic rubber. A method for heat treatment in the presence of a vulcanization system has been disclosed. Japanese Patent Application Laid-Open No. 9-124803 proposes obtaining a composite member by heating and bonding an acrylonitrile-containing thermoplastic resin and an acrylonitrile-containing rubber.

As a method for producing a composite by utilizing a chemical reaction between a thermoplastic resin and rubber, Japanese Patent Application Laid-Open Nos. 2-150304 and 3-313 No. 631, JP-A-3-138114 discloses a polyamide resin, a rubber containing a propyloxyl group or an acid anhydride group as a rubber component, a peroxide and vulcanization activation. It has been proposed to use a rubber component containing an agent. Japanese Patent Application Laid-Open No. 8-156618 / 88 discloses that a composite member can be obtained by bringing an epoxy group-containing resin member and a carboxyl group or acid anhydride group-containing rubber member into close contact and vulcanizing them. Proposed. Further, as a method for obtaining a composite by using a specific additive, Japanese Patent Application Laid-Open No. 7-11013 discloses a polyamide molded product, a rubber, a peroxide vulcanizing agent, and a silane compound. A method of vulcanizing by contacting a rubber compound containing a vulcanizing activator as required is disclosed. Further, a thermoplastic polyester is used as a hard component, and a rubber component containing a rubber, a peroxide vulcanizing agent, a bifunctional or polyfunctional maleimide and, if necessary, a vulcanizing activator is used as a soft component ( Japanese Unexamined Patent Publication (Kokai) No. 7-304880), a rubber component containing rubber, a peroxide vulcanizing agent, a silane compound and, if necessary, a vulcanizing activator is used (Japanese Patent Laid-Open No. 7-166600). 43 No. 3) has been proposed.

However, in these methods, the types of thermoplastic resin and rubber are limited in order to obtain high adhesive strength. In particular, it is difficult to obtain a composite of a poorly reactive vulcanized rubber and a thermoplastic resin.

Japanese Patent Application Laid-Open No. H10-58605 discloses that a base film (such as a polyester film) and a rubber film containing a polyfunctional methacrylate as an adhesion improver (such as silicone rubber and ethylene propylene rubber) are laminated. A method for obtaining a composite film by vulcanizing and vulcanizing is disclosed. However, in this method, it is necessary to use a rubber containing a large amount of an adhesion improver in order to obtain sufficient bonding strength with the base film, and the base film is subjected to corona discharge treatment or easy adhesion. Need to be processed. Furthermore, in the examples of this document, it is described that irradiation is performed using an electron beam, which is a high-energy beam, for bonding, and is used for joining a thick, three-dimensional rubber molded body to a resin molded body. Is difficult to do.

As described above, a highly versatile technique for joining a resin member and a rubber member with high adhesive strength has not been known. In particular, the bonding strength varies greatly depending on the type and prescription of rubber, so that a large change in rubber prescription is required, and high bonding strength may not be obtained even if the rubber prescription is changed. For example, from the viewpoint of the performance of rubber members, rubber formulations in which the amount of additives such as fillers, fillers, and plasticizers must be increased, and rubber formulations in which the type of vulcanizing agent is restricted (for example, sulfur In rubber formulations that require a vulcanizing agent), the range of choices for formulations to increase joint strength is severely limited. In addition, changing rubber formulations is often difficult in practice.

Accordingly, an object of the present invention is to provide a composite in which a resin molded article and a vulcanized rubber molded article are firmly joined in a wide range of combinations, and a method for producing the same.

Another object of the present invention is to provide a composite in which a resin molded article and a vulcanized rubber molded article are firmly joined without subjecting the surface of the resin molded article to an easy adhesion treatment, and a method for producing the same. .

Still another object of the present invention is to provide a composite firmly bonded to a resin member without changing the rubber composition of the vulcanized rubber member, and a method for producing the same.

Another object of the present invention is to provide a composite in which a resin member and a vulcanized rubber member are firmly joined even in a three-dimensional structure, and a method for producing the same. Disclosure of the invention

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above-mentioned object. When the unvulcanized rubber layer is vulcanized by means of heating or the like, It has been found that the rubber member and the resin member can be firmly integrated, and a resin-rubber composite can be obtained efficiently, and the present invention has been completed.

That is, in the composite of the present invention, the vulcanized rubber member and the resin member are joined via the vulcanized rubber layer vulcanized with the vulcanizing agent to form a resin-rubber composite. In the present invention, since the bonding strength can be improved regardless of the type of vulcanizing agent, the vulcanizing agent may be a sulfur vulcanizing agent (such as sulfur or a sulfur compound) or a peroxide vulcanizing agent (organic peroxide). Radical generator vulcanizing agent). The resin member can be composed of at least one selected from a thermoplastic resin and a resin having a bridging group. The resin having a bridging group is a thermosetting resin and / or a thermoplastic resin having an unsaturated bond. It may be a resin. Further, the unvulcanized rubber composition and the resin member for forming the vulcanized rubber layer often satisfy at least one of the following conditions (i) to (iii).

(i) An active atom (or at least one active atom selected from a hydrogen atom and a sulfur atom) in which the resin member has an orbital interaction energy coefficient S represented by the following formula (1) of not less than 0.006. ) Is composed of a thermoplastic resin having at least two on average in one molecule

^{^{S = (C H0M0, n)}} , I E C- E H0M0, nl + (C LUM0, n), I E c - E LUMO.n I (1)

( _Where E _c , C _{H0M0) I 1} , E _H 0M0, n, ^C LUM0, n, ^E LUM0, n are all values calculated by the semiempirical molecular orbital method M〇P AC PM 3. hand,

E c indicates the orbital energy (e V) of the radical generator as a vulcanizing agent, and C and o and _n are the highest occupied molecular orbitals of the nth hydrogen atom constituting the basic unit of the thermoplastic resin. (HOMO) indicates the molecular orbital coefficient, E _H0M0 , _n indicates the orbital energy (e V) of H〇M〇, and C LUM0, _n indicates the lowest unoccupied molecular orbital (LUMO) of the nth hydrogen atom. It indicates the molecular orbital coefficient, and E _LUM0 , _n indicates the orbital energy (e V) of the LUMO.)

(ii) At least one of the unvulcanized rubber composition and the resin member Contains a polyfunctional polymerizable compound having a plurality of polymerizable groups

(ii) The resin member is composed of a thermosetting resin or a resin having an unsaturated bond in a molecule, and the unvulcanized rubber composition contains a polyfunctional polymerizable compound having a plurality of polymerizable groups.

In the composite, at least one of the vulcanized rubber layer, the vulcanized rubber member and the resin member may be formed of a composition containing a vulcanization activator. The vulcanization activator may be composed of a polyfunctional polymerizable compound having a plurality of polymerizable groups. For example, the vulcanized rubber layer is formed of an unvulcanized rubber composition containing a vulcanizing agent and a vulcanizing activator, and at least one of a vulcanized rubber member and a resin member (for example, a resin member) is vulcanized. It may be formed of a composition containing a sulfur activator. The amount of the vulcanization activator may be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin and / or rubber, for example, 2 parts by weight with respect to 100 parts by weight of rubber. It may be as follows. The resin member may further contain a stabilizer for the vulcanization activator (for example, an antioxidant, a light stabilizer, a thermal polymerization inhibitor, etc.), and the ratio between the vulcanization activator and the stabilizer is the former Z The latter (weight ratio) may be about 9 9 Z 1 to 25/75. Examples of the resin member include a polyamide resin, a polyester resin, a polyacetal resin, a polyphenylene ether resin, a polysulfide resin, a polyether ketone resin, a polycarbonate resin, a polyimide resin, and a polysulfone. Resin, polyurethane resin, polyolefin resin, halogen-containing vinyl resin, styrene resin, (meth) acrylic resin, thermoplastic elastomer, phenol resin, amino resin, epoxy resin, thermosetting polyimide It is composed of resin, thermosetting polyurethane resin, silicone resin, unsaturated polyester resin, vinyl ester resin, diaryl phthalate resin, and thermosetting (meth) acrylic resin. Further, the vulcanized rubber layer may be vulcanized with a sulfur-based vulcanizing agent. For example, the vulcanized rubber layer is composed of gen-based rubber (such as styrene-gen-based rubber vulcanized with a sulfur-based vulcanizing agent), and the resin member is It may be composed of a refinylene ether-based resin.

In the method of the present invention, a rubber element selected from an unvulcanized rubber composition, a semi-vulcanized rubber member and a vulcanized rubber member is provided via an unvulcanized rubber layer containing a vulcanizing agent; A non-vulcanized rubber or semi-vulcanized rubber, and vulcanized unvulcanized rubber or semi-vulcanized rubber. Through the layers, a resin Z rubber composite in which the vulcanized rubber member of the rubber element and the resin member of the resin element are joined is manufactured. In this method, the unvulcanized rubber or the semi-vulcanized rubber may be vulcanized, and the rubber element and the resin element may be molded if necessary. Further, a layer of an unvulcanized rubber composition containing a vulcanizing agent is formed on at least one of the bonding surfaces of the rubber element and the resin element, and the rubber is interposed via the unvulcanized rubber composition layer. The element and the resin element may be heated under pressure contact. Further, the unvulcanized rubber composition layer containing the vulcanizing agent may be formed of a film or a coating material of the unvulcanized rubber composition. In this method, the unvulcanized rubber composition of the intermediate layer is interposed between the molded resin member and a rubber element selected from the unvulcanized rubber composition and the semi-vulcanized rubber member. Crosslinking or vulcanization may be performed while molding the semi-vulcanized rubber. At least one of the unvulcanized rubber composition layer, the rubber element and the resin element may contain a vulcanizing activator. When the resin element contains a vulcanization activator, the amount of the vulcanization activator may be about 0.1 to 5 parts by weight based on 100 parts by weight of the resin element. Further, an unvulcanized rubber composition containing an organic peroxide and a multifunctional polymerizable compound having a plurality of polymerizable groups is provided between a rubber element containing a vulcanizing agent and a resin element. The molding may be performed by heating under pressure with a layer interposed. Further, at least one of the rubber element and the resin element may include a polyfunctional polymerizable compound having a plurality of polymerizable groups.

In the present specification, “rubber” means a vulcanized rubber layer Rubber or a rubber for forming a vulcanized rubber member (the rubber element). The term “resin” is used to include a resin (the resin element) for forming a resin member. Detailed description of the invention

[Resin material]

In the composite of the present invention, the resin member is made of at least one selected from a thermoplastic resin and a resin having a crosslinkable group (hereinafter, may be simply referred to as a resin).

(Thermoplastic resin)

Examples of the thermoplastic resin include polyamide resin, polyester resin, poly (thio) ether resin (polyacetal resin, polyphenylene ether resin, polysulfide resin, polyetherketone resin, etc.), and polycarbonate. -Based resins, polyimide-based resins, polysulfone-based resins, polyurethane-based resins, and other condensed thermoplastic resins; polyolefin-based resins, halogen-containing vinyl-based resins, styrene-based resins, and vinyl polymers such as (meth) acrylic-based resins Examples thereof include a thermoplastic resin; and a thermoplastic elastomer. These resins can be used alone or in combination of two or more. When two or more resins are used in combination, the resin composition may form a composite resin composition such as a polymer alloy.

(1) Polyamide resin

Examples of the polyamide resin include an aliphatic polyamide resin, an alicyclic polyamide resin, and an aromatic polyamide resin. The aliphatic polyamide-series resin, (C _4, such as hexamethylene diamine Tetoramechire Njiamin to - ₁₀ Arukirenjia Min) aliphatic Jiamin component carbon atoms such as an aliphatic dicarboxylic acid component (adipic acid, sebacic acid, dodecane force Nni acid Condensates with alkylene dicarboxylic acids having a number of about 4 to 20 (for example, Polyamide 46, Polyamide 66, Polyamide) Amide 610, polyamide 612, etc.), lactam (e.g., lactam having about 4 to 20 carbon atoms such as e-prolactam, ω-laurolactam) or aminocarboxylic acid (ω-aminoundecanoic acid) Homo- or copolymers (e.g., aminocarboxylic acids having about 4 to 20 carbon atoms) (for example, Polyamide 6, Polyamide 11, Polyamide 12, etc.), and copolymers obtained by copolymerizing these polyamide components. (For example, polyamide 6/11, polyamide 6Z12, polyamide 6611, polyamide 612, etc.).

Examples of the alicyclic polyamide-based resin include polyamides using an alicyclic diamine and / or an alicyclic dicarboxylic acid as at least a part of the aliphatic diamine component and / or the aliphatic dicarboxylic acid component. . The alicyclic made of Polyamide, for example, the aliphatic dicarboxylic acid components amount and alicyclic Jiamin component [C ₅ _ ₈ consequent opening such Kishirujiamin cyclohexylene Arukirujiamin; bis (cyclohexyl amino cyclo) methane, 2, 2 - Bis (amino C) such as bis (aminocyclohexyl) propane

₅ - ₈ cycloalkyl) alkanes (e.g., bis (to amino cyclo key Sil) include condensates of alkanes), etc.].

The aromatic polyamide resin includes a polyamide in which at least one of the aliphatic diamine component and the aliphatic dicarboxylic acid component is an aromatic component, for example, a polyamide in which the diamine component is an aromatic component [ Condensates of aromatic diamines such as MXD-6 (such as meta-xylylenediamine) with aliphatic dicarboxylic acids, etc.), and polyamides whose dicarboxylic acid component is an aromatic component [aliphatic diamines (trimethylhexamethylenediamine) Condensates of aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.)], polyamides in which diamine and dicarboxylic acid components are aromatic [poly (m-phenylene isophthalamide), etc.] Wholly aromatic polyamides (aramids).

In the polyamide resin, dimer monoacid is further added to the dicarboxylic acid component. Using a small amount of a polyamide, a small amount of a polyfunctional polyamine and a di- or poly-carbonic acid component to mix or graft-polymerize a polyamide having a branched structure, a modified polyamide (such as N-alkoxymethylpolyamide), and a modified polyolefin. Also included is a high-impact polyamide which has been subjected to high impact.

In the polyamide resin, the ratio between the terminal NH ₂ group and the terminal CO OH group is not particularly limited. For example, when an active hydrogen atom is constituted by a hydrogen atom of a terminal amino group and a hydrogen atom of α-carbon position, Terminal amino group Z-terminal carboxyl group = about 10Z90 0 to 100ZO (molar ratio), preferably about 20/80 to 955 (molar ratio), more preferably 25/75 to 95 / It can be selected from a range of about 5 (molar ratio). Further, when an active hydrogen atom is constituted only by the hydrogen atom of the terminal amino group, the terminal amino groupΖthe terminal carboxyl group = 50/50 to about L 0/0 (mol ratio), preferably 60 It may be about 40 to 95 to 5 (molar ratio), more preferably about 70 to 30 to 955 (molar ratio).

(2) Polyester resin

The polyester-based resin may be an aliphatic polyester-based resin, but usually, an aromatic polyester-based resin, for example, a poly (alkylene) arylate-based resin or a saturated aromatic polyester-based resin is used. The aromatic polyester resins, polyalkylene § Relay preparative resin (e.g., polyethylene terephthalate (Ρ ΕΤ), polybutylene terephthalate evening rate (Ρ ΒΤ) poly C ₂ such as - ₄ Arukirentere phthalate; this polyalkylene Lev Poly C4 alkylene naphthalate corresponding to the sauce (eg, polyethylene naphthalate); poly 1,4-cyclohexyl dimethylene terephthalate (PC

Ii)); polyarylate resin (for example, polyarylate resin) obtained by polycondensation of bisphenols (such as bisphenol Α) and aromatic dicarboxylic acids (such as terephthalic acid); wholly aromatic or liquid And crystalline aromatic polyesters (for example, liquid crystalline polyesters using paraoxybenzoic acid). The polyester-based resin may be a copolyester containing an alkylene arylate unit as a main component (for example, 50% by weight or more). The copolymerizable component of the copolyester, ethylene glycol, propylene glycol, C ₂ _ ₆ alkylene glycols such as hexanediol to butanediol ol, (Po Li) Okishi C ₂ - ₄ alkylene render recall, phthalic acid, isophthalic Yurusan which asymmetric aromatic dicarboxylic acids or their anhydrides, C _6, such as adipic acid Do - such as _{1 2} aliphatic dicarboxylic acids can be exemplified. Further, a branched chain structure may be introduced into the linear polyester by using a small amount of polyol and / or polycarboxylic acid.

When the aromatic polyester resin does not have the active atom at a predetermined concentration, a modified polyester resin modified with a modifying compound having an active atom (for example, at least one selected from an amino group and an oxyalkylene group) Aromatic polyester-based resin). Compounds having an active atom, particularly an active hydrogen atom, include polyamines (aliphatic diamines such as ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylene). Alicyclic diamines such as diamines, trimethylhexamethylene diamine, 1,7-diaminoheptane, 1,8-diaminooctane, etc .; linear or branched alkylenediamines having about 2 to 10 carbon atoms; , Isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, etc .; aromatic diamines such as phenylenediamine, xylylenediamine, diaminodiphenylmethane ), Polyols (eg, ethylene glycol, Propylene glycol, C ₂ _ ₆ alkylene render recalls such butanediol hexanediol to, (poly) O carboxymethyl ethylene glycol, (poly) O · The shea trimethylene glycol, (poly) O carboxymethyl propylene glycol, (Poly) oxy C such as (poly) oxytetramethylene glycol

2- ₄ alkylene glycols), and others. The modification can be carried out, for example, by heating and mixing the polyester resin and the modifying compound, and utilizing amidation, esterification or transesterification. Depending on the amount of active hydrogen atoms in the compound, the degree of modification of the polyester-based resin may be, for example, 0.1 mol of the modified compound per 1 mol of the functional group (hydroxyl group or hydroxyl group) of the polyester-based resin. It may be about 2 to 2 mol, preferably about 0.2 to 1.5 mol, and more preferably about 0.3 to 1 mol. When used in a transesterification reaction, the amount of the polyols used may be about 1 to 50 parts by weight, preferably about 5 to 30 parts by weight, based on 100 parts by weight of the polyester resin.

(3) Poly (thio) ether-based resin

The poly (thio) ether resins include polyoxyalkylene resins, polyphenylene ether resins, polysulfide resins (polythioether resins), and polyetherketone resins. The Porioki Shiarukiren resins, polyoxymethylene glycols, Po Rio carboxymethyl ethylene da recall, polyoxypropylene da recall, polyoxyethylene - polyoxypropylene block copolymers, polyoxy C ₂ such as port re oxytetramethylene da recalled — Includes ₄ Archi render recalls. Preferred polyether resins include polyacetal resins, polyphenylene ether resins, polysulfide resins, and polyetherketone resins.

(3a) Polyacetal resin

The polyacetone-based resin may be a homopolymer (a homopolymer of formaldehyde) or a copolymer (such as a copolymer of trioxane and ethylenoxide and / or 1,3-dioxolane). Is also good. Further, the terminal of the polyacetal resin may be blocked and stabilized.

(3b) Polyphenylene ether resin Polyphenylene ether resins include various resins containing 2,6-dimethylphenylene oxide as a main component, for example, a copolymer of 2,6-dimethylphenylene oxide and phenols, styrene. A modified resin obtained by blending or grafting a system resin is included. Other modified polyphenylene ether resins include polyphenylene ether Z polyamide, polyphenylene ether / saturated polyester, polyphenylene ether Z polyphenylene sulfide, and polyphenylene ether / polyolefin. Is mentioned.

Note that the modification with the styrene-based resin lowers the heat resistance of the polyphenylene ether-based resin and may be deformed by heating in the vulcanization process. Further, the addition of a styrene resin may adversely affect the adhesion between the rubber and the polyphenylene ether resin, and excessive addition of the styrene resin is not preferable. On the other hand, polyphenylene ether-based resin has low melt fluidity, and if used without being combined with styrene-based resin, moldability decreases. From these points, the ratio of the styrene resin is 2 to 150 parts by weight, preferably 3 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the polyphenylene ether resin. About 50 parts by weight.

(3c) Polysulfide Resin (Polyether Resin) The polysulfide resin is not particularly limited as long as it has a thio group (—S—) in a polymer chain. Examples of such a resin include a polyphenylene sulfide resin, a polydisulfide resin, a polyphenylene sulfide resin, a polyketone sulfide resin, and a polythioether sulfone resin. Further, the polysulfide resin may have a substituent such as an amino group as in poly (aminophenylene sulfide). A preferred polysulfide resin is a polyphenylene sulfide resin.

(3d) Polyetherketone resin

Dihalogenobenzophenone (poly) Examples thereof include polyether ketone resins obtained by polycondensation of dihydrobenzozophenone and dihydrobenzozophenone, and polyether ether ketone resins obtained by polycondensation of dihalogenobenzophenone and hydroquinone.

(4) Polycarbonate resin

The polycarbonate resin may be an aliphatic polycarbonate resin, but is usually an aromatic polycarbonate resin, for example, an aromatic dihydroxy compound (bisphenol A, bisphenol, bisphenol AD, bisphenol S, etc.). And aromatic polycarbonates obtained by the reaction of phosgene or carbonic acid diester (dialkyl carbonate such as diphenyl carbonate, dialkyl carbonate such as dimethyl carbonate).

(5) Polyimide resin

Polyimide resins include thermoplastic polyimide resins such as aromatic tetracarboxylic acids or their anhydrides (such as benzophenonetetracarboxylic acid) and aromatic diamines (such as diaminodiphenylmethane). The resulting polyimide resin, polyimide imide resin, polyester imide resin and the like are included.

(6) Polysulfone resin

Polysulfone resins include polysulfone resins, polyethersulfone resins, and polyallyl sulfones obtained by polycondensation of dihalogenodiphenylsulfone (such as dichlorophenylsulfone) and bisphenols (such as bisphenol A or a metal salt thereof). An example is a sulfone resin (trade name: RADEL).

(7) Polyurethane resin

The polyurethane resin can be obtained by reacting a diisocyanate, a polyol (particularly, a diol) and, if necessary, a chain extender. Hexamethylene diisocyanate as a diisocyanate , Aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as 1,4-cyclohexanediisocyanate and isophorone diisocyanate, and phene Examples thereof include aromatic diisocyanates such as range isocyanate, tolylene diisocyanate, diphenylmethane-1,4'-diisocyanate, and aromatic aliphatic diisocyanates such as xylylene diisocyanate. As the diisocyanates, compounds in which an alkyl group (for example, a methyl group) is substituted on the main chain or the ring may be used.

The diols, C ₄ _ _{1 2} aliphatic dicarboxylic acid component such as polyester diol (of adipic acid, ethylene glycol, propylene glycol, butanediol, C ₂ _ _{1 2} aliphatic diol component such as neopentyl glycol, .epsilon. force such as caprolactone C ₄ - _{1 2} such as polyester diols obtained from such a lactone component), Porieteruji ol (polyethylene glycol, polypropylene glycol, port Riokishechiren one polyoxypropylene proc copolymer, poly old alkoxy tetramethylene da recall, bisphenol A-alkylene oxide adducts, etc.), polyester ether diols (polyester diols using the above polyether diols as part of the diol component), and the like can be used.

Furthermore, as the chain extender, ethylene glycol, C _2, such as propylene grayed recalls - ₁ other ₍₎ alkyl render recall, Jiamin acids can also be used. Examples of diamines include aliphatic diamines, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1 , 7-diaminoheptane, 1,8-diaminooctane and other linear or branched alkylenediamines having about 2 to 10 carbon atoms, such as alkylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and dipropylenetriamine. Alicyclic diamines, for example, isophoronediamine, bis (4-amino-13-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, etc .; aromatic diamines, For example, phenylenediamine, xylylenediamine, diaminodiphenylmethane and the like can be exemplified.

(8) Polyolefin resin

Polyolefin resins include, for example, homo- or copolymers of olefins such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (methylpentene-11), and copolymers of olefins and copolymerizable monomers. (E.g., ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer). These polyolefin resins can be used alone or in combination of two or more.

Preferred polyolefin resins are polypropylene resins having a propylene content of 50% by weight or more (particularly 75 to 100% by weight), for example, polypropylene, propylene-ethylene copolymer, propylene butene copolymer. Propylene-ethylene-butene copolymer. Also, the polyolefin resin is preferably crystalline.

(9) Halogen-containing vinyl resin

Examples of halogen-containing vinyl resins include polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, chlorine-containing biel resin such as vinylidene chloride-vinyl acetate copolymer, polyfluoride bifluoride, and polyfluoride. Examples include fluorine-containing vinyl resins such as vinylidene, polychloroethylene, and copolymers of tetrafluoroethylene and a copolymerizable monomer. Preferred halogen-containing vinyl resins are fluorine-containing vinyl resins (eg, polyvinyl fluoride, polyvinylidene fluoride, etc.).

(10) Styrene resin Examples of the styrene-based resin include homo- or copolymers of styrene-based monomers (such as polystyrene, styrene-vinyltoluene copolymer, and styrene-α-methylstyrene copolymer), and copolymerizable monomers with styrene-based monomers. Copolymers with styrene (styrene-acrylonitrile copolymer (AS resin), (meth) acrylate-styrene copolymer (MS resin, etc.), styrene-maleic anhydride copolymer, styrene-butadiene Styrene copolymers such as copolymers; impact-resistant polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (acrylonitrile-acrylic acid) Ester-styrene copolymer) (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS tree ), Acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), acrylonitrile- (ethylene-pinyl acetate copolymer) -styrene copolymer (acrylonitrile-monoacetate biel-styrene copolymer) (AXS resin) Styrene-based graft copolymer).

(1 1) (meth) Acrylic resin

Examples of the (meth) acrylic resin include a single or copolymer of a (meth) acrylic monomer, and a copolymer of a (meth) acrylic monomer and a copolymerizable monomer. (Meth) acrylic monomers include (meth) acrylic acid, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) isopropyl acrylate, (meth) butyl acrylate, and (meth) acryl. (meth) acrylic acid C i_ ₁₀ alkyl esters, such as hexyl acid 2- Echiru, (meth) (main evening), such as cyclohexyl acrylate cycloalkyl acrylate C ₅ _ ₁₀ cycloalkyl ester, (meth) phenyl acrylate, etc. of (meth) Akuriru acid C ₆ _ _{1 0} § Li one glycol ester, (meth) acrylic acid hydroxy E chill (meth) hydroxy acrylate

C ₂ _ ₁₀ alkyl esters, (meth) acrylamide, (meth) acrylonitrile, glycidyl (meth) acrylate and the like. Shared weight Examples of the compatible monomer include vinyl monomers such as vinyl acetate and vinyl chloride, and styrene monomers such as styrene and -methylstyrene.

(1 2) Thermoplastic elastomer

Thermoplastic elastomers include polyamide-based elastomers (copolymers with polyamide as a hard phase and aliphatic polyether as a soft phase), and polyester-based elastomers (polyalkylene acrylate as a hard phase, and Copolymer with aliphatic polyether or aliphatic polyester as the soft phase), polyurethane-based elastomer (copolymer with short-chain Dalicol polyurethane as the hard phase, and aliphatic polyether or aliphatic polyester as the soft phase) For example, polyester urethane elastomers, polyether urethane elastomers, etc.), polystyrene-based elastomers (block copolymers using a polystyrene block as a hard phase and a gen-polymer block or a hydrogenated block thereof as a soft phase), polyolefin Elastomer (Polyethylene or PO Elastomers with propylene as the hard phase and ethylene-propylene rubber or ethylene-propylene diene rubber as the soft phase, olefin-based elastomers composed of hard and soft phases with different degrees of crystallinity, etc., polyvinyl chloride And fluorinated thermoplastic elastomers. Examples of the aliphatic polyether include (poly) oxy C ₂ _ ₄ alkylene glycols (for example, (poly) oxyethylene glycol, (poly) oxytrimethylene dalicol, (poly) oxypropylene glycol, (Poly) oxytetramethylene glycol, in particular, polyoxyethylene render glycol) and the like can be used. As the aliphatic polyester, the polyester diol described in the section of the polyurethane resin can be used. These thermoplastic elastomers can be used alone or in combination of two or more.

When the thermoplastic elastomer is a block copolymer, the block structure is not particularly limited, and the triblock structure, the multiblock structure, A star block structure or the like may be used.

Preferred thermoplastic elastomers include polyamide-based elastomers, polyester-based elastomers, polyurethane-based elastomers, polystyrene-based elastomers, and polyolefin-based elastomers.

(Resin with crosslinkable group)

The resin having a crosslinkable group can be roughly classified into a thermoplastic resin having an unsaturated bond (polymerizable or crosslinkable unsaturated bond) and a thermosetting resin having a crosslinkable functional group. It may have an unsaturated bond and a crosslinkable functional group.

(Thermoplastic resin having unsaturated bond)

The present invention can also be used for bonding rubbers with various thermoplastic resins containing a radical-active unsaturated bond at a predetermined concentration. Therefore, if the thermoplastic resin is a resin that does not have an unsaturated bond or a resin whose unsaturated bond concentration does not reach a predetermined concentration, use it as a modified resin or a modified resin into which an unsaturated bond has been introduced. Is also good. The unsaturated bond is not particularly limited as long as it can be activated by a vulcanizing agent (such as a radical generator), and various bonds exhibiting crosslinkability or polymerizability by application of heat or light (for example, polymerizable unsaturation). (Saturated bond). Such an unsaturated bond or a unit having an unsaturated bond includes a linking group (ether bond (-0-), ester bond (-0C O0)-, -C (= 0) 0-), amide bond ( -NHC0-, -C0NH-), imino bond (-NH-), urethane bond (-NHC (= 0) 0-), urea bond, piuret bond, etc. You may. Further, the unsaturated bond or a unit thereof may be located at the terminal (end of the main chain) and / or a side chain of the resin, or may be located at the main chain of the resin, or a combination thereof. It may be located in a different part.

Examples of the group having an unsaturated bond include a vinyl group, a 1-propyl group, an isopropyl group, a 1-butenyl group, an aryl group and a 2-methyl group. Lou 2- propenyl group, 2-C ₂ _ ₆ alkenyl groups such as butenyl; 4 one Binirufueniru group, C ₂ _ 6 alkenyl one C ₆ _ ₂₀ § Li Ichiru group such as 4 Isopuro Bae Nirufueniru group; a styryl C Ariru one C ₂ _ ₆ alkenyl group such as a group; Echiniru group, 1-Puropieru group, 1-Petit two group, propargyl group, 2-butynyl group, such as 1-methyl-2-propyl sulfonyl group C ₂ - ₆ Alkynyl group; mono- or di-C such as vinylene group, methylvinylene group, ethylvinylene group, 1,2-dimethylvinylene

! _ _{6 A} vinylene group which may have a substituent such as a halovinylene group such as an alkylvinylene group and a chlorovinylene group; a vinylidene group; an ethinylene group;

Examples of the thermoplastic resin having an unsaturated bond include: (1) a reactive group (A) and a compound having an unsaturated bond; and a reactive group (B) capable of reacting with the reactive group (A). (2) thermoplastic resin with unsaturated bond introduced by copolymerization or co-condensation, (3) resin with unsaturated bond and resin Polymer blends, (4) Various organic reactions (for example, introduction of vinyl groups by Leppe reaction using acetylene, introduction of unsaturated bonds using organometallic reagents such as vinyllithium, and unsaturation by force ringing reaction) Thermoplastic resin into which an unsaturated bond has been introduced. Preferred resins are the above-mentioned resins (1), (2) and (3).

In the resin (1), a polymerizable compound having at least one reactive group (A) and at least one unsaturated bond is reacted with the reactive group (A) of the polymerizable compound. By reacting with a resin having a functional group (B), an unsaturated bond can be introduced into the resin. Representative reactive groups (A) of the polymerizable compound include (A1) a hydroxyl group, (A2) a carbonyl group or an acid anhydride thereof, (A3) an amino group, (A4) an epoxy group, and (A5) ) Isocyanate group and the like, and a combination of the reactive group (A) of the polymerizable compound and the reactive group (B) of the resin For example, the following combinations can be exemplified. The form in parentheses indicates the bonding form between the reactive group (A) and the reactive group (B).

(A1) hydroxyl group:

(B) carboxylic group or its anhydride group (ester bond), isocyanate group (ester bond)

(A2) a lipoxyl group or its anhydride group:

(B) hydroxyl group (ester bond), amino group (amide bond), epoxy group (ester bond), isocyanate group (amide bond) (A3) amino group:

(B) Roxypoxyl group or its acid anhydride group (amide bond), epoxy group (imino bond), isocyanate group (amide bond)

(A4) Epoxy group:

(B) Carboxyl group or its acid anhydride group (ester bond), amino group (imino bond)

(A5) Isocyanate group:

(B) hydroxyl group (ester bond), carboxylic acid group or its anhydride group (amide bond), amino group (amide bond)

Regarding the reactive group (B) of the resin, in a polyamide resin, for example, a remaining carboxyl group or an amino group can be used as the reactive group (B). In a polyester resin, for example, the remaining hydroxyl group can be used. The hydroxyl group can be used as the reactive group (B). The remaining hydroxyl groups and mercapto groups may be used as the reactive group (B) in the poly (thio) ether resin, and the remaining hydroxyl groups may be used as the reactive group (B) in the polyacetal resin. Available. Furthermore, in a polycarbonate resin, the remaining hydroxyl group can be used as a reactive group (B), and in a polyimide resin, the remaining carboxyl group, acid anhydride group, amino group, imino group, or the like can be used as a reactive group (B). ) Is available. Furthermore, in the case of polyurethane resins, for example, residual hydroxyl groups, amino groups, isocyanate groups, etc. And the like. The reactive group (B) may be used as the reactive group (B). In the case of the (meth) acrylic resin, the monomer having the reactive group (B) is used as a copolymerization component to thereby form the reactive group (B). ) Can be introduced.

As the polymerizable compound, hydroxyl group-containing compound [for example, § Lil alcohol, 2-butene one 1-ol, 3-buten - C ₃ _ ₆ such as 2-Saiichi C ₃ _ ₆ Arukenoru include Le, propargyl alcohol alkyno Ichiru, 2-hydroxy-E chill (meth) Akurireto, 2 - hydroxypropyl (meth) Akurireto, butanediol mono (main evening) Akurireto C ₂ such as - ₆ alkyl render Rico one mono (meth) § acrylate, diethylene glycol Polyoxy C ₂ _ ₆ alkylenedaricol mono (meth) acrylates such as (meth) acrylates, C ₂ _ ₆ alkenylphenols such as 4-hydroxystyrene, 4-hydroxy-1-methylstyrene, dihydroxystyrene, vinyl naphthol, etc.] , Containing carboxyl group or acid anhydride group For example things [, (meth) acrylic acid, crotonic acid, ₃ - C 3 _ ₆ § Rukenkarubon acids such as butenoic acid, Itakon acid, maleic acid, C ₄ _ ₈ alkene dicarboxylic acid or its anhydride such as maleic anhydride unsaturated aromatic carboxylic acids such as vinyl benzoate, Kei cinnamic acid, amino group-containing compound (eg if, C _3, such as Ariruamin - ₆ Arukeniruamin, 4 one Aminosuchi Ren, etc. Jiaminosuchiren), epoxy group-containing compound ( For example, aryl glycidyl ether, glycidyl (meth) acrylate, and the like, and isocyanate group compounds (for example, vinyl isocyanate) can be exemplified.

In the case where a resin having no reactive group (B) or a resin having a low concentration of the reactive group (B) is used as the resin in the resin (1), the reactive group (B) may be introduced. May be used to modify or modify the resin. Examples of the method for introducing the reactive group (B) into the resin include: (i) in the production of the resin, a monomer having the reactive group (B) (for example, the polymerizable compound described above); Materials (or monomers, (Ii) introduction of carboxyl groups by oxidation, halogenation, grafting of polymerizable monomers, and various other organic reactions. In the case of the Bier polymer resin, the monomer having the reactive group (B) is usually used as a copolymer component to introduce the reactive group (B) in many cases. In any resin including the above, the reactive group (B) can be easily introduced by a graft reaction of the polymerizable compound having the reactive group. In the resin (2), as a method for introducing an unsaturated bond, for example, in the preparation of a condensation resin (for example, a polyamide resin, a polyester resin, or the like), as a part of the reaction component (comonomer), Compounds having a functional unsaturated bond [for example, aliphatic unsaturated dicarboxylic acids (for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous itaconic acid, citraconic acid, citraconic anhydride, mesaconic acid, etc. aliphatic unsaturated diol _{(1 (-} - C _4, such as 1, 4 Jioru _2-butene) aliphatic unsaturated diol; - ₄ _{1 ()} unsaturated polyvalent carbonitrile phosphate such as such as aliphatic unsaturated dicarboxylic acid) And the like)), and a method of co-condensing (or copolymerizing) unsaturated polyhydric alcohols such as In addition-polymerized resins (eg, olefin-based resins), a monomer having a conjugated unsaturated bond (eg, -1,3-butadiene, 2-methyl) is part of the reaction component (comonomer). — Copolymerization of optionally substituted conjugated C ₄ _ _{1 ()} alkadiene such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene and chloroprene). Can be illustrated.

In the resin (3), the thermoplastic resin (A) and the resin (B) having an unsaturated bond are mixed to form a polymer blend (or a resin composition), whereby the thermoplastic resin is unsaturated. A bond can be introduced. The thermoplastic resin (A) is not particularly limited, and examples thereof include various thermoplastic resins [for example, thermoplastic resins (polyamide-based resins, polyester-based resins, and the like described below) and the like]. In addition, thermoplastic resin (A) May be a saturated resin having no unsaturated bond or a resin having an unsaturated bond.

As the resin (B) having an unsaturated bond, a thermoplastic resin having an unsaturated bond introduced therein, such as the resin (1), (2) or (4), or a rubber containing an unsaturated bond (for example, polybutadiene, polybutadiene, or polybutadiene). isoprene, polygonal pen Tenama one, Poriheputenama, Poriokutenama mono-, poly (3-methylcarbamoyl Ruokutenama I), Poridesenama, poly (3-Mechirudesenama one), poly C _4, such as poly Dodesenama - ₁₅ alkenylene, C _4, such as butadiene-I isoprene copolymer — ₁₅ alkadiene copolymer, rubber-modified polyolefin such as butadiene-modified polyethylene, etc.). Incidentally, the poly-C ₄ - ₁₅ Aruke two Ren, Shikuroorefi emissions (such, good cyclopentene, cycloheptene, Shikurookuten, cyclodecene, which may have a substituent such as cyclododecene C

_It may be obtained by metathesis polymerization of _{5 to} ₂₀ cycloolefin, or partial hydrogenation of polyalkenedylene (for example, polybutadiene).

In the resin (4), the proportion of the resin (B) is within a range where unsaturated bonds can be introduced into the polymer blend at a predetermined concentration, for example, the resin

(A) Resin (B) (weight ratio) = 595-95 / 5, preferably 30Z70-95Z5, more preferably about 50Z50-95 / 5. When an unsaturated bond-containing rubber (for example, polyoctenylene) is used as the resin (B), the proportion of the resin (B) can be selected within a range that does not impair the properties of the resin (A). ) / Resin (B) (weight ratio) = 50 / 50-95Z5, preferably 6040-95 / 5, more preferably about 70 / 30-95Z5.

In the resin composition of the resin (4), the resin (A) and the resin

(B) may form a polymer alloy (eg, a polymer alloy having a sea-island structure).

Examples of the thermoplastic resin include polyamide resin and polyester resin. Resin, poly (thio) ether resin (polyacetal resin, polyphenyleneether resin, polysulfide resin, polyetherketone resin, etc.), polycarbonate resin, polyimide resin, polysulfone resin, polyurethane Thermoplastic resins such as polyolefin resins, halogen-containing vinyl resins, styrene resins, and (meth) acrylic resins; and thermoplastic elastomers. . These resins can be used alone or in combination of two or more. When two or more resins are used in combination, the resin composition may form a composite resin composition such as a polymer alloy.

The ratio of unsaturated bonds depends on the type of the resin and the degree of activation of the unsaturated bonds. For example, the ratio is, for example, 0.1 or more per one resin molecule (for example, 0.1 to 0.1). 100), preferably 1 or more (for example, 1 to 100) on average, and more preferably 2 or more (for example, about 2 to 50) on average. The concentration of the unsaturated bond is, for example, 0.01 to 6.6 mol, preferably 0.01 to 4 mol (for example, 0.01 to 1 mol) per 1 kg of the resin, More preferably, it is about 0.02 to 2 mol (for example, 0.05 to 0.5 mol).

In addition, in the introduction of unsaturated bonds by the polymer friend, the number of unsaturated bonds can be calculated as an average value of the unsaturated bonds according to the weight fraction of each resin, but the number of unsaturated bonds in the resin composition can be calculated. It is convenient to calculate the number as the molar concentration Z kg.

(Thermosetting resin having a crosslinkable functional group)

Examples of the thermosetting resin include a resin having a functional group (eg, a methylol group, an alkoxymethyl group, an epoxy group, an isocyanate group, etc.) exhibiting a crosslinking property or a curability in the presence of a crosslinking agent (or a curing agent). Are listed. Examples of such thermosetting resins include polycondensation or addition condensation resins (phenolic resins, amino resins, epoxy resins, thermosetting polyimide resins, thermosetting polyurethane resins, silicone resins). ), And addition polymerization resins (unsaturated polyester resins, vinyl ester resins, diaryl phthalate resins, thermosetting (meth) acrylic resins, etc.). The thermosetting resins may be used alone or in combination of two or more.

(13) Phenol resin

The phenolic resin includes a nopolak resin, a resol resin and the like, and a nopolak resin is usually used. Nopolak resin is obtained by reacting phenols with aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, o-, m-, or p-cresol, 2, 5-, 3, 5- or 3,4-xylenol, 2, 3, 5-trimethyl phenol, ethyl phenol, propyl phenol C Bok ₄ alkylphenol, dihydroxy benzene such as resorcinol, naphthol can be exemplified. These phenols may be used alone or in combination of two or more. Examples of the aldehydes include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde and propionaldehyde, and aromatic aldehydes such as benzaldehyde and salicylaldehyde. These aldehydes may be used alone or in combination of two or more.

(14) Amino resin

The amino resin is usually obtained by reacting an amino group-containing compound with an aldehyde (for example, an aliphatic aldehyde such as formaldehyde, acetate aldehyde, propionaldehyde, or an aromatic aldehyde such as phenylacetaldehyde). Can be Amino resins include urea resins (such as urea resins obtained by the reaction of urea and aldehydes) and aniline resins (aniline such as aniline, naphthylamine, toluidine, xylidine, N, N-dimethylaniline, and benzidine). Resins and aldehydes), and melamine resins (melamine obtained by the reaction of melamines and aldehydes) And guanamine resins (such as guanamine resins obtained by the reaction of guanamines such as benzoguanamine, acetoguanamine and formoguanamine with aldehydes).

(15) Epoxy resin

Epoxy resins include bisphenol epoxy resins, nopolak epoxy resins, and amine epoxy resins. Examples of the bisphenol-type epoxy resin include glycidyl ethers such as 4,4-biphenol, 2,2-biphenol, bisphenol F, bisphenol AD, and bisphenol A.

Examples of the nopolak resin constituting the nopolak-type epoxy resin include, for example, the nopolak resin obtained by the reaction of the phenols and the aldehydes described in the section of the nopolak resin. Examples of the amine component constituting the amine-based epoxy resin include aromatic amines such as aniline and toluidine, aromatic diamines such as diaminobenzene and xylylenediamine, aminohydroxybenzene, and diaminodiphenylmethane.

(16) Thermosetting polyimide resin

The thermosetting polyimide-based resin includes the resins described in the paragraph of the polyimide-based resin (for example, a curable resin composition having a plurality of ring-closable imido groups).

(17) Thermosetting polyurethane resin

Examples of the thermosetting polyurethane resin include the resins described in the section of the polyurethane resin (for example, a curable resin composed of a prepolymer having a plurality of free isocyanate groups and a polyol component such as polyester polyol). Composition).

(18) Silicone resin

The silicone resin has a unit represented by the formula: R _a S i 0 (4— _{a) / 2} (where the coefficient a is about 1.9 to 2.1) and a formula: R _b S i O ( ₄ _ _{b) / 2} Silicon resin composed of units (where the coefficient b is about 0.9 to 1.1) is included. In the formula, R represents, for example, a C!-! O alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a halogen group such as a 3-chlorobutyryl group or a 3,3,3-trifluoropropyl group. of C -!! o alkyl group, pinyl group, Ariru group, C ₂ _ ₁₀ alkenyl groups such as butenyl group, phenyl group, a tolyl group, C ₆ _ ₁₂ § aryl group such as a naphthyl group, a cyclopentyl group, cyclohexyl C ₃ _ ₁₀ consequent opening alkyl group such as a group, a benzyl group, C _6, such as phenethyl - such as ₁₂ Ariru one C Bok ₄ alkyl group.

(19) Unsaturated polyester resin

As the unsaturated polyester resin, an unsaturated polyester obtained by using an unsaturated dicarboxylic acid or an anhydride thereof (for example, maleic acid, maleic anhydride, fumaric acid, etc.) as the dicarboxylic acid component in the polyester resin described above. And the like.

(20) Vinyl ester resin

Examples of the vinyl ester resin include a polymer obtained by reacting the epoxy resin with (meth) acrylic acid and a polymer obtained by reacting polyhydric phenols with daricidyl (meth) acrylate. Can be

(21) Diaryl phthalate resin

Examples of the diaryl phthalate resin include resins obtained from diaryl phthalate monomers such as diaryl orthophthalate and diaryl isophthalate.

(2 2) Thermosetting acrylic resin

The thermosetting (meth) acrylic resin includes the resin described in the section of the above (meth) acrylic resin (a (meth) acrylic resin having a reactive group such as a hydroxyl group, and a curing agent). Resin compositions, etc.).

The resin is a thermoplastic resin or a resin having a crosslinkable group (particularly, In the case of a crosslinkable resin excluding the curable resin), a plurality of hydrogen atoms (active hydrogen atoms) or sulfur atoms (active sulfur atoms) exhibiting high activity against radicals (hereinafter referred to as hydrogen and sulfur atoms) (May be referred to as an active atom). The resin only needs to have at least one active atom selected from the above active hydrogen atoms and active sulfur atoms, and may have both active hydrogen atoms and active sulfur atoms.

When the resin having the active atom is used, the bonding with the vulcanized rubber layer and, eventually, the vulcanized rubber member can be further strengthened. That is, a resin having an active atom has an active atom whose orbital interaction energy coefficient S represented by the following formula is equal to or larger than a fixed value (for example, 0.06, preferably 0.08). May be. A preferable orbital interaction energy coefficient S of the active atom is about 0.006 to 0.06, preferably about 0.007 to 0.05 (particularly 0.01 to 0.045). is there. The number of active atoms depends on the binding site of the functional group having an active atom (terminal, branched chain, main chain, etc.). For example, in a resin molecule, an average of two or more (2 to 100,000) ), Preferably an average of 2.5 or more (about 2.5 to 500), more preferably an average of 3 or more (about 3 to 1000)].

S =, then HOMO, n), IE c- ^E H0M0, n I + then LUMO'n) ZIE _c — E

LUMO, n I (top)

_{(Wherein, E (;, C H 0M0} , n, E H0M0, n, C LUM0, n, E LUM0, n also Re Les 9 calculated by the semiempirical molecular orbital method MO P AC PM 3 values And

E _c indicates the orbital energy of the radical of the radical generator (e V), and C _H0M0 , _n is the n-th active atom constituting the basic unit of the thermoplastic resin

The molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of (hydrogen or sulfur atom), E _{H0MO> n} indicates the orbital energy (e V) of the HOMO, and C _LUM0 , _n indicates the n-th activity Indicates the molecular orbital coefficient of the lowest unoccupied molecular orbital (LUMO) of an atom (hydrogen or sulfur), and E _{LUM ()} , _n is Orbital energy (eV) of LUM〇

The basic unit in the formula (1) means a model molecular structure formed by a polymer terminal and about 1 to 3 repeating units. In other words, when calculating a polymer using M で PAC PM 3, it is difficult to calculate the molecule itself because the number of atoms constituting the molecule is too large. Therefore, the calculation may be performed on a molecular structure model (basic unit) formed of the terminal of the polymer and about 2 to 3 repeating units. For example, the molecular structure of the polybutylene terephthalate evening rate (PBT) (repeating unit), in general, the chemical formula one _{_{(CH 2 - CH 2 - CH}} 2- CH 2 - O- C (= 0) - C 6 H 4 - C (= 0) - O) n - but it expressed in the in formula (1), the base unit, for convenience _{_{HO- CH 2 - CH 2 - CH}} 2 - CH 2 -〇-C (= 〇 )-It may be calculated as C ₆ H ₄ -C (= 0) -OH.

The orbital energy E _e (e V) of the radical of the radical generator is preferably calculated by MOP AC PM3 based on the molecular structure of the radical. However, for convenience, a predetermined value is determined based on the type of the radical generator. May be used. For example, E is a radical generating agent an organic peroxide _c = - 8 e V, in § zone Compound E _c = - 5 e V, a sulfur-containing organic organic compound except the sulfur E _c = - calculated as 6 e V You may.

As the hydrogen atom (active hydrogen atom) whose orbital interaction energy coefficient S is equal to or more than a predetermined value (for example, 0.06), when the radical generator is an organic peroxide, an amino (1-NH ₂ ) group ( for example, terminal amino group), imino (one NH-) groups (e.g., main chain or terminal imino group, such as single NH- group amide binding), mercapto (- SH) groups, methyl (one CH ₃₎ group, Examples include hydrogen atoms such as a methylene (one CH ₂ —) group (a methylene group adjacent to an electron-withdrawing group, that is, an active methylene group) and a methylidyne (—CH =) group (a main chain or terminal methylidyne group).

In addition, as a sulfur atom (active sulfur atom) whose orbital interaction energy coefficient S is equal to or more than a predetermined value (for example, 0.06), radical generation is considered. When the raw material is an organic peroxide, thio group (-S-), mercapto '(-SH) group, alkylthio group (alkylthio group such as methylthio group, ethylthio group, etc.), sulfiel group (-SO-), etc. Of sulfur atoms.

Examples of the methyl group include a methyl group bonded to an alkylene chain, a cycloalkylene chain or an aromatic ring, and a methyl group bonded to an oxygen atom (a methyl group of a methoxy group). Examples of the methylene group include a methylene group adjacent to an oxygen atom of a (poly) oxyalkylene unit such as a (poly) oxymethylene unit and a (poly) oxyethylene unit, and a nitrogen atom adjacent to an amino group or a dimino group. Examples of such a group include a methylene group. Examples of the methylidyne group include a methylidyne group at the 1-position adjacent to an amino group or an imino group, for example, a methylidyne group at the -position to the amino group of the aminocycloalkyl group.

Since the number of active atoms is not a single molecule but a mixture of many molecules having slightly different structures and chain lengths, the number of active atoms may be calculated for a plurality of expected basic units. For example, repeat unit

_{_{(NH- (CH 2) 6 -NH}} -C (= 0) - (CH 2) 4 - (C = 0)) n - number of active hydrogen atoms contained in the polymer (polyamide 6 6) with the model Basic unit NH _2- (CH ₂ ) 6-NH-C (= 0)-(CH ₂ ) ₄ -C (= 〇)-Can be calculated based on -OH. When the radical generator is an organic peroxide, the terminal The two hydrogen atoms of the NH ₂ group are active hydrogen atoms (ie, S≥0.006). In this case, the average number N of active hydrogen atoms in one molecule of polyamide 66 is determined by the following formula according to the ratio of terminal NH ₂ groups to terminal COOH groups of the polymer (polyamide 66) as an aggregate. It can be calculated based on (2).

N = 2 X A (2)

(Where A represents the average number of terminal NH ₂ groups in one molecule)

For example, if the terminal NH ₂ group Z terminal COOH group = 1 1 (molar ratio) In this case, the number of terminal NH ₂ groups in one molecule is A = 1, and the number of active hydrogen atoms in one molecule is N = 2. When the terminal NH ₂ group / terminal C〇〇H group = 1/2 (molar ratio), the number of terminal NH ₂ groups in one molecule A = 23, the number of active hydrogen atoms in one molecule N = 4 Z 3 pieces.

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 represented by an average value of the number of active atoms of each resin. In other words, the number of active atoms is individually calculated from the basic unit of each resin constituting the mixed resin, and the average of the number of active atoms is calculated based on the weight ratio of each resin. Can be calculated. For example, the mixed resin is composed of the aforementioned N = 2 polyamides 66 (A) and the aforementioned N = 4Z3 polyamides 66 (B), and (A) NO (B) = 1/1 (Molar ratio), the number of active atoms in one mixed resin molecule can be regarded as N = 5Z3. Further, the mixed resin is composed of the N-2 polyamide 66 (A) and a polyamide 66 (C) having a carboxyl group at all terminals (that is, N = 0), wherein (A) When (C) = 3Z1 (molar ratio), the number of active atoms in one mixed resin molecule can be regarded as N = 3/2.

Among the resins exemplified above, examples of the resin having such an active atom include a polyamide resin, a polyester resin, a polyacetal resin, a polyphenylene ether resin, a polysulfide resin, and a polyolefin resin. Resins, polyurethane resins, thermoplastic elastomers, amino resins, epoxy resins, etc. are included.

In a polyamide resin, for example, a hydrogen atom at the terminal amino group, a hydrogen atom bonded to a carbon atom at the α-position to the terminal amino group, or a carbon atom adjacent to one of the amide bond groups Hydrogen atoms (eg, a hydrogen atom of a methylene group 原子 a hydrogen atom of a methylidine group), and particularly, a hydrogen atom of a terminal amino group constitutes an active hydrogen atom.

In polyester-based resins, usually, (poly) oxyalkylene units The hydrogen atom of the methylene group adjacent to the oxygen atom constitutes an active hydrogen atom. In a modified polyester resin, usually, a hydrogen atom of a terminal amino group or a hydrogen atom bonded to a carbon atom at a position higher than the terminal amino group A hydrogen atom bonded to a carbon atom adjacent to one NH— group of an amide bond (eg, a hydrogen atom of a methylene group 水素 a hydrogen atom of a methylidyne group), particularly a hydrogen atom of a terminal amino group, constitutes an active hydrogen atom.

In a polyacetal resin, for example, a hydrogen atom of an oxymethylene unit, a hydrogen atom of an alkoxy group (especially a methoxy group) whose terminal is blocked, particularly a hydrogen atom of an oxymethylene unit constitutes an active hydrogen atom, and in a polyphenylene ether resin, For example, a hydrogen atom of a methyl group bonded to a benzene ring forms an active hydrogen atom, and in a polysulfide resin, for example, a thio group in a main chain forms an active atom. In polyurethane resins, for example, hydrogen atoms of alkyl groups (particularly, hydrogen atoms at the benzyl position) bonded to the main chain or ring of diisocyanates, hydrogen atoms of alkylene groups of polyols and polyoxyalkylene glycols, chains The hydrogen atom of the amino group of the extender constitutes an active hydrogen atom.

In the polyolefin resin, for example, a hydrogen atom of a methylene group constituting the main chain of the polyolefin, a hydrogen atom of a methyl group branched from the main chain, and the like constitute an active hydrogen atom. In the thermoplastic elastomer, for example, a hydrogen atom of an oxyalkylene unit constituting the soft phase may constitute an active hydrogen atom.

In the amino resin, for example, an amino group (for example, an amino group constituting melamine, guanamine, etc.) constitutes an active hydrogen atom. In the epoxy resin, for example, a hydrogen atom bonded to a carbon atom constituting the epoxy group constitutes an active hydrogen atom.

The resin composition for forming the resin member (particularly, a resin having a crosslinkable group) may contain a crosslinking accelerator for promoting crosslinking. The crosslinking accelerator can be selected according to the type of resin, for example, resin When is a resin having a crosslinkable functional group, crosslinking (or curing) can be remarkably promoted by using an acid, a base, or a curing agent (such as an organic curing agent or an inorganic curing agent).

Examples of such a cross-linking accelerator include radical generators (radical generators described below), acids (fatty acids such as acetic acid, sulfonic acids such as p-toluenesulfonic acid, and aromatic fatty acids such as benzoic acid). Acids, inorganic acids such as hydrochloric acid, etc.), bases (aliphatic amines such as triethylamine, aromatic amines such as aniline, heterocyclic amines such as pyridine), organic curing agents [polyvalent carboxylic acid] Acids or acid anhydrides thereof (eg, dalioxal, malondialdehyde, daltaraldehyde, terephthalaldehyde, etc.), compounds having a plurality of aldehyde groups, epoxy compounds (eg, alkylene glycol diglycidyl ether, polyoxyalkylene) Dalicol diglycidyl ether, glycerol triglycidyl ether, A compound having a plurality of epoxy groups such as methylolpropanthridicidyl ether; a nitrogen-containing compound (for example, an amino resin such as a urea resin, a guanamine resin, a melamine resin, etc .; described in (7) Polyurethane resin). Diamines, etc.), compounds having a methylol group or an alkoxymethyl group (eg, a polymer having an N-methylol (meth) acrylamide group, etc.), polyisocyanates, etc.), inorganic curing agents [ Boric acid or borate (borax, etc.), zirconium compounds, titanium compounds, aluminum compounds, phosphorus compounds, silane coupling agents, etc.], curing catalysts (organotin compounds, organoaluminum compounds, etc.) It is. These crosslinking accelerators may be used alone or in combination of two or more.

In addition, the resin composition for forming the resin member includes various additives such as a filler or a reinforcing agent, a stabilizer (an ultraviolet absorber, an antioxidant, and a heat stabilizer), a coloring agent, a plasticizer, a lubricant, It may contain flame retardants, antistatic agents and the like. [Rubber members (vulcanized rubber members)]

(Rubber)

The rubber member (vulcanized rubber member) is obtained by molding (vulcanizing) a rubber composition containing a vulcanizing agent and rubber. In the present invention, since various rubbers can be firmly joined, the type of the rubber is not particularly limited. Examples of the rubber include gen-based rubber, olefin rubber, acrylic rubber, fluoro rubber, silicone rubber, urethane rubber, epichlorohydrin rubber (epichlorohydrin homopolymer C0, epichlorohydrin and ethylene oxide) EC0, copolymers obtained by further copolymerizing aryl glycidyl ether, etc.), chlorosulfonated polyethylene, propylene oxide rubber (GPO;), ethylene monoacetate vinyl copolymer (E AM), polynor Examples thereof include polene rubber and modified rubbers thereof (acid-modified rubber and the like). These rubbers can be used alone or in combination of two or more. Of these rubbers, generally, gen rubber, olefin rubber, acrylic rubber, fluorine rubber, silicone rubber, urethane rubber and the like are widely used from a practical viewpoint.

Gen-based rubbers include, for example, polymers of gen-based monomers such as natural rubber (NR), isoprene rubber IR), isobutylene isoprene rubber (butyl rubber) (IIR), bush gen rubber (BR), and chloroprene rubber (CR). Acrylonitrile-butadiene rubber (nitrile rubber) (NBR), nitrile chloroprene rubber (NCR), nitrile isoprene rubber (NIR) and other acrylonitrile-gen copolymer rubbers; styrene butadiene rubber (SBR, Random copolymers of styrene and butadiene, SB block copolymers composed of styrene and butadiene blocks, etc.), styrene-one copolymers such as styrene chloroprene rubber (SCR) and styrene isoprene rubber (SIR) Rubber and the like are included. Gen-based rubber also includes hydrogenated rubber, for example, hydrogenated nitrile rubber (HNBR). Styrene-di The ene copolymer rubber may be a random copolymer or a block copolymer. The proportion of the styrene component in the styrene-gen copolymer rubber is, for example, 10 to 80% by weight, preferably 20 to 70% by weight, and more preferably 30 to 60% by weight (for example, 40 to 50% by weight). %).

Examples of the olefin rubber include, for example, ethylene propylene rubber (EPM), ethylene-propylene-gen rubber (such as EPDM), and polypropylene rubber.

Acrylic rubbers include rubbers containing alkyl acrylate as a main component, for example, copolymer ACM of alkyl acrylate and chlorine-containing crosslinkable monomer, and copolymer of alkyl acrylate and alkyl nitrile. Copolymer ANM, a copolymer of an alkyl acrylate and a monomer containing a carboxyl group or Z or an epoxy group, and ethylene acryl rubber can be exemplified.

Examples of the fluorine rubber include rubbers containing a fluorine-containing monomer, for example, a copolymer of vinylidene fluoride and polyfluoropropene and, if necessary, a copolymer of ethylene tetrafluoride FKM, and a copolymer of ethylene tetrafluoride and propylene And FF KM, a copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether.

Silicone rubber (Q) is of the formula: R _a S I_〇 (4- _{a) / 2} organopolysiloxane composed of units represented by. In the formula, R is a halogen such as a C!-! O alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 3-chloropropyl group, and a 3,3,3-trifluoropropyl group. of C -!! o alkyl group, hexyl vinyl group, Ariru group, C ₂ _ ₁₀ alkenyl groups such as Buteni group, phenyl group, a tolyl group, C ₆ _ ₁₂ Ariru group such as a naphthyl group, a cyclopentyl group, cyclohexylene C ₃ _ _{1 ()} cycloalkyl group such group, a benzyl group, such as phenethyl

C ₆ -12 aryl and Ci- ₄ alkyl groups. Where the coefficient a is about 1.9 to 2.1. Preferred R is a methyl group, phenyl Group, alkenyl group (vinyl group, etc.) and fluoro C ^ e alkyl group.

The molecular structure of the silicone rubber is usually linear, but may have a partially branched structure or may be a branched chain. The main chain of the silicone rubber is, for example, a dimethylpolysiloxane chain, a methylvinylpolysiloxane chain, a methylphenylpolysiloxane chain, or a copolymer chain of these siloxane units [dimethylsiloxane-methylvinylsiloxane copolymer. Copolymer chain, dimethylsiloxane-methylphenylsiloxane copolymer chain, dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer chain, dimethylsiloxane-methylpinylsiloxane-methylphenylsiloxane Copolymer chain, etc.]. Both ends of the silicone rubber may be, for example, a trimethylsilyl group, a dimethylvinylsilyl group, a silanol group, a tri-C j- ₂ alkoxysilyl group, or the like.

Silicone rubber (Q) includes, for example, methyl silicone rubber (MQ), pinyl silicone rubber (VMQ;), phenyl silicone rubber (P MQ), phenyl vinyl silicone rubber (PVMQ), fluorinated silicone rubber ( FVMQ). Silicone rubber is not limited to the above-mentioned high temperature vulcanizable HTV (High Temperature Vulcanizable) solid rubber, but may be room temperature vulcanized RTV (Room Temperature Vulcanizable) or low temperature vulcanized LTV (Low Temperature Vulcanizable) silicone. Rubber, for example, liquid or pasty rubber is also included.

Examples of the urethane rubber (U) include a polyester type urethane elastomer and a polyether type urethane elastomer.

Examples of the modified rubber include acid-modified rubbers such as carboxylated styrene butadiene rubber (X-SBR;), carboxylated nitrile rubber (X-NBR), and carboxylated ethylene propylene rubber (X-EP (D) Rubbers having a carboxylic group or an acid anhydride group such as M) are included. (Vulcanizing agent)

The rubber can be vulcanized with various vulcanizing agents, and the type of the vulcanizing agent is not particularly limited. For example, as the vulcanizing agent, sulfur vulcanizing agents such as sulfur and sulfur-containing compounds, and non-sulfur vulcanizing agents (for example, radical generating vulcanizing agents such as organic peroxides) are used. it can. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.

Among sulfur-based vulcanizing agents, the sulfur-containing compounds include, for example, sulfur chloride (sulfur monochloride, sulfur dichloride, etc.), dithio heterocyclic compounds (dithio group-containing compounds such as 4,4′-dithiomorpholine), and mercapto group-containing compounds. Triazines (such as mercapto group-containing compounds such as 2-di-n-butylamino-4,6-dimercapto-S-triazine, 2,4,6-trimercapto-S-triazine), and thiurams (tetramethylthiuram monosulfuric acid) (TMTM), tetramethylthiuram disulfide (T MTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TB TD), dipentamethylenethiuram tetrasulfide (DP TT), etc.) , Jichiokarupamin acid salts (di-methyl di Chio Scarpa Min acid, di _0} _4 alkyl such geminal chill di Chio Scarpa Min acid Salts of dithiorubamic acid with metals such as alkali metals (sodium, potassium, etc.), transition metals (iron, copper, zinc, etc.), Periodic Table 6 Group B elements (selenium, tellurium, etc.), thiazo -2- (4'-morpholinodithio) benzothiazole, etc. (2-mercaptobenzothiazole, etc.).

Preferred vulcanizing agents are radical generator-based vulcanizing agents that can be combined with a wide range of resin components. The vulcanizing agent functions as a radical generator and activates the rubber to form a strong bond.

Various radical generators can be used as the radical generator as a vulcanizing agent, and examples thereof include organic peroxides, azo compounds, and sulfur excluding sulfur. It can be selected from contained organic compounds. Sulfur is not included in the radical generator because it causes an ionic reaction and not only has a very low radical generation efficiency, but also traps the generated radicals. The radical generators can be used alone or in combination of two or more. Examples of organic peroxides include diacyl peroxides (lauroyl peroxide, benzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, etc.). , Dialkyl peroxides (di-t-butylperoxide, 2,5-di (t-butylperoxy) -1,2,5-dimethylhexane, 1,1-bis (t-butylperoxy) —3,3, 5—Trimethylcyclohexane, 2,5-di (t-butylperoxy) —2,5-monodimethylhexene—3,1,3-bis (t—butylperoxyisopropyl) benzene, dicumylperoxide Alkyl peroxides (t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropyl Benzene hydroperoxide, etc.), alkylidene peroxides (ethyl methyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t-butylperoxy) —3,3,5-trime Tert-butyl peracetic acid, t-butyl perpiate, etc.).

The azo compound includes azobisisobutyronitrile and the like. Note that, among the above-mentioned sulfur-containing organic compounds, thiurams, dithiolbamates, and thiazoles can also function as radical generators.

If light irradiation is possible, a photopolymerization initiator can also be used as a radical generator. Examples of the photopolymerization initiator include benzophenone or a derivative thereof (eg, 3,3′-dimethyl-14-methoxybenzophenone, 4,4-dimethoxybenzophenone), alkylphenylketone or a derivative thereof (acetophenone, diethoxya). Setofenone, 2—hi Droxy-2-methyl-1-phenylpropane-1-one, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-11- (morpholinophenyl) -butanone, etc.), Anthraquinone or a derivative thereof (such as 2-methylanthraquinone), thioxanthone or a derivative thereof (such as 2-chloro thioxanthone or alkylthioxanthone), benzoin ether or a derivative thereof (such as benzoin or benzoin alkyl ether), phosphinoxide or a derivative thereof And the like. Radical generators also include persulfates (such as ammonium persulfate and persulfate).

The preferred radical generator among these compounds is an organic peroxide.

The ratio of the vulcanizing agent can be selected, for example, from a range of about 0.5 to 15 parts by weight with respect to 100 parts by weight of the unvulcanized rubber, and is usually about 1 to 10 parts by weight, preferably about 1 to 10 parts by weight. It is about 1 to 8 parts by weight (for example, 2 to 7 parts by weight), and more preferably about 3 to 5 parts by weight.

The ratio of the radical generator can be selected from, for example, about 0.5 to 15 parts by weight, based on 100 parts by weight of the unvulcanized rubber, and is usually about 1 to 10 parts by weight, preferably about 1 to 10 parts by weight. It is about 1 to 8 parts by weight (for example, 2 to 7 parts by weight).

The vulcanizing agent (for example, sulfur-based vulcanizing agent) includes various compounds, for example, metal oxides (polyvalent metal oxides such as zinc oxide, magnesium oxide, and lead oxide), quinone dioxime (p-quinone dioxime, It may be used in combination with p, p'-benzoylquinonedioxime, polyρ-dinitrobenzene, modified phenolic resin (alkylphenol formaldehyde resin, brominated alkylphenol formaldehyde resin, etc.).

[Vulcanized rubber layer (or middle layer)]

In the present invention, the vulcanized rubber member and the resin member are vulcanized with a vulcanizing agent. (A vulcanized rubber layer or a middle layer of an unvulcanized rubber composition containing a vulcanizing agent). In such a configuration, by utilizing the fact that rubber and rubber easily adhere to each other, even if the vulcanized rubber member has a different type or prescription of rubber, it can be securely and firmly bonded to a wide range of resins. This means that a composite in which a vulcanized rubber member and a resin member are firmly joined can be easily and reliably manufactured without changing the prescription of a rubber member that has already been put into practical use.

The rubber in the vulcanized rubber layer has a wide range as in the case of the above-described vulcanized rubber member, for example, gen rubber, olefin rubber, acrylic rubber, fluorine rubber, silicone rubber, urethane rubber, and epichlorohydrin. Rubber, chlorosulfonated polyethylene, propylene oxide rubber (GPO), ethylene-vinyl acetate copolymer (EAM), polynorporene rubber, and modified rubbers (such as acid-modified rubber). These rubbers can be used alone or in combination of two or more.

If a rubber of the same type (preferably the same type) as the rubber of the vulcanized rubber member is used as the rubber of the vulcanized rubber layer, the joining strength can be reliably improved. For example, even if the rubber member is a sulfur-vulcanized gen-based rubber (IIR, NBR, SBR, etc.), the rubber of the vulcanized rubber layer is of the same type (rubber with a similar molecular structure, such as EPDM or other olefins). Rubber can be used. If the same type of rubber (gen-based rubber) is used instead of the same rubber, higher bonding strength can be obtained.

As the vulcanizing agent, any of a sulfur-based vulcanizing agent (sulfur or a sulfur-containing compound) and a radical generator-based vulcanizing agent (a peroxide-based vulcanizing agent such as an organic peroxide) may be used. However, it is preferable to select a vulcanizing agent of the same type (particularly the same type) as the vulcanizing agent used for vulcanizing the vulcanized rubber member. Examples of the sulfur-based vulcanizing agent and the radical-generating agent-based vulcanizing agent include the same compounds as described above. Preferred vulcanizing agents are radical generator-based vulcanizing agents (particularly organic peroxides) capable of bonding with a wide range of resins.

The ratio of the radical generator vulcanizing agent is 100 parts by weight of the unvulcanized rubber. Then, for example, it can be selected from a range of about 0.5 to 15 parts by weight, usually about 1 to 10 parts by weight, preferably about 1 to 8 parts by weight (for example, about 2 to 7 parts by weight). .

[Vulcanizing activator]

In order to securely join the vulcanized rubber member and the resin member, at least one layer or member of the vulcanized rubber layer, the vulcanized rubber member and the resin member is preferably formed of a composition containing a vulcanization activator. It is. That is, at least one component of the unvulcanized rubber composition, the vulcanized rubber member, and the resin member for forming the vulcanized rubber layer may include a vulcanization activator. Usually, the vulcanization activator may be contained in at least one of the unvulcanized rubber composition (composition for the intermediate layer) and the resin member. In particular, when at least the unvulcanized rubber composition (composition for the intermediate layer) contains a vulcanization activator (sometimes referred to as a curing agent) together with a radical generator vulcanizing agent, the vulcanization activator becomes In addition to accelerating the vulcanization of the rubber, the cross-linking between the rubber molecules of the intermediate layer and the resin molecules of the resin member is promoted, so that the bonding between the vulcanized rubber member and the resin member is made easier. For example, when the resin is a polyamide resin, when a radical generator and a vulcanization activator are used in combination, a crosslinking reaction proceeds between the resin member and the vulcanized rubber member via an intermediate layer, and both are reacted. Can be connected securely and firmly. The vulcanization activator only needs to be present in an amount necessary for accelerating the vulcanization of the rubber and forming a cross-link between the rubber and the resin. Therefore, an appropriate amount can be selected as appropriate.

Examples of the vulcanization activator include an organic compound having a carbon-carbon double bond (polymerizable unsaturated bond) [for example, a pinyl-based monomer (such as divinylbenzene) or an acryl-based monomer (such as divinylbenzene)]. Ryl phthalate, triallyl phosphate, triaryl (iso) cyanurate, etc.), (meth) acrylic monomers, etc.), and maleimide compounds. These vulcanizing activators can be used alone or in combination of two or more. As the vulcanizing activator, usually, two or more polymerizable groups (polymerizable unsaturated bonds) Is used.

(Meth) acrylic monomers include, for example, bifunctional (meth) acrylates [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol (meta) C, such as acrylate, hexanediol di (meth) acrylate, and neopentyl dalichol di (meth) acrylate

2-10 Alkylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol (meth) acrylate, Poly C ₂ _ ₄ alkylene glycol di (meth) acrylate, glycerin di (meth) such as propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate Akurireto, Torimechiro Rupuropanji (meth) Akurireto, pen evening erythritol Toruji (main evening) Akurireto, the C ₂ _ ₄ alkylene O wherein de adduct of bisphenol a di (meth) Akurireto etc. , Trifunctional or polyfunctional (meth) acrylates [glycerin tri (meth) acrylate, trimethylol ester (meth) acrylate, trimethylolpropanetri (meth) acrylate, penyerythritol tri (meth) acrylate, pentaerythritol Thortetra (meth) acrylate, dipentyl erythritol, tetra (meth) acrylate, dipentaerythritolhexa (meth) acrylate, etc.]. A maleimide compound having a plurality of maleimide groups can be obtained by reacting a polyamine with maleic anhydride. Maleimide compounds include, for example, aromatic bismaleimides (N, N'-1,3-phenylenediimide, N, N'-1,4-phenylenediimide, Ν, Ν '— 3 —Methyl-1,4-phenylenedimaleimide, 4, 4' —Bis (Ν, Ν, maleimide) diphenylmethane, 4, 4 ' 1-bis (N, N, 1-maleimide) diphenylsulfone, 4,4, -bis (N, Ν'-maleimide) diphenyl ether, etc.), aliphatic bismale-imide (Ν, Ν '), 1, 2 — Ethylene bismaleimide, Ν, Ν '— 1, 3 — propylene bismaleimide, Ν, Ν' — 1, 4-tetramethylene bismaleimide, etc.).

Preferred vulcanization activators are compounds having a plurality of (for example, about 2 to 6, especially about 3 to 6) carbon-carbon double bonds (polymerizable unsaturated bonds) in one molecule, such as triallyl. (Iso) cyanurate, bifunctional to polyfunctional (meth) acrylate (especially trifunctional or polyfunctional (meth) acrylate), and aromatic maleimide compounds. In the present invention, the addition of a vulcanization activator is not essential. For example, depending on the number of resins having a crosslinkable group, the number of crosslinkable groups, and the type of rubber material used, joining of both members is possible without the presence of a vulcanizing activator. However, in many cases, it is more advantageous to add a vulcanization activator in order to securely join the rubber member and the resin member. The vulcanizing activator is often added to at least one of the unvulcanized rubber (or unvulcanized rubber composition) and the resin (or resin composition) of the intermediate layer (the rubber layer). And may be added to both components. Further, a vulcanization activator may be added to rubber (unvulcanized rubber) for forming the vulcanized rubber member. When the resin is a resin having a crosslinkable unsaturated bond-containing group, the crosslinking between the resin and the rubber is activated by adding a vulcanizing activator to the resin component, so that the resin member and the intermediate layer can be combined with each other. In many cases, it is possible to firmly join the joints.

The amount of vulcanization activator used depends on the type of vulcanization activator used and the type of component added (unvulcanized rubber and Ζ or resin), but usually it can promote adhesion between resin and rubber Amount, for example, from rubber [rubber for forming a vulcanized rubber layer or rubber (rubber element) for forming a vulcanized rubber member] and resin [resin for forming a resin member (resin element)] For 100% by weight of selected at least one component The vulcanization activator can be selected from the range of about 0.1 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, and more preferably about 0.1 to 3 parts by weight. For example, when the vulcanization activator is a polyhydric alcohol methacrylate, the amount of the vulcanization activator is 0.1 per 100 parts by weight of at least one component selected from rubber and resin. About 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, practically 0.1 to 1.9 parts by weight (for example, 0.5 parts by weight or 1 part by weight) 0.0 parts by weight). When added to both the rubber and the resin, the addition amount to the resin may be small, and the vulcanization activator is 0.1 to 7 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the resin. It may be about 1 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight. The addition of the vulcanization activator, whether added to the rubber component or the resin component, should exceed 10 parts by weight with respect to 100 parts by weight of the material to be added (rubber or resin). However, it is necessary to pay attention to the addition of more than 5 parts by weight, and it is necessary to examine the effect on the added material in advance. In order to obtain sufficient bonding strength between the rubber member and the resin member without giving special consideration to the influence on the material to be added, the amount of the vulcanizing activator to be added is as follows when the material to be added is rubber. 100 parts by weight of rubber, 2 parts by weight or less, for example, 0.1 to 1.9 parts by weight (for example, 0.5 to 1.9 parts by weight), and when the material to be added is resin 5 parts by weight or less, for example, 0.1 to 5 parts by weight (for example, 3 to 5 parts by weight) with respect to 100 parts by weight of the resin.

When a vulcanizing activator is added to rubber, the ratio between the vulcanizing agent (particularly a radical generator vulcanizing agent) and the vulcanizing activator is, for example, the former Z the latter = 0.3 / Ί-20 / About 1 (for example, 0.5 / 1 to 201) (weight ratio), preferably about 0.4Z1 to 15Z1 (for example, 1 1 to 151) (weight ratio), more preferably 0.5 No. 1 to 10/1 (for example, 2/1 to 10/1) (weight ratio).

[Vulcanization aid] In the present invention, a vulcanization aid may be further used in order to increase the efficiency of adhesion. Depending on the type of rubber or resin, the addition of a vulcanization aid can further strengthen the joining between the rubber member and the resin member. The vulcanization aid includes the unvulcanized rubber (or unvulcanized rubber composition) of the intermediate layer, the unvulcanized rubber (or unvulcanized rubber composition) of the vulcanized rubber member, and the resin (or resin composition). It may be added to at least one of the components, and it is added to all components and to both the unvulcanized rubber (or unvulcanized rubber composition) and the resin (or resin composition) in the intermediate layer. May be. Usually, the vulcanization aid is added to at least one of the unvulcanized rubber (or the unvulcanized rubber composition) and the resin (or the resin composition) (particularly the resin or the resin composition) of the intermediate layer. Often. In this case, if necessary, a vulcanization aid may be added to the unvulcanized rubber of the vulcanized rubber member.

The vulcanization aid can be selected according to the type of resin or rubber. For example, an oligomer of a condensation thermoplastic resin (for example, a number average molecular weight of the oligomer of the polyamide resin or the oligomer of the polyester resin) Oligomer of about 100 to 100. However, when used as a vulcanization aid, the oligomer does not necessarily have to have a crosslinkable group as described above.) Polyamines (for example, (7) diamines and the like described in the section of the polyurethane-based resin), polyols (for example, the polyols and the like described in the section (2) of the polyester-based resin described above), polyvalent carboxylic acids or acid anhydrides thereof, Compounds with multiple aldehyde groups, epoxy compounds, nitrogen-containing resins (such as amino resins), compounds with methylol or alkoxymethyl groups, polyiso An example is cyanate. These vulcanization aids may be used alone or in combination of two or more.

Preferred vulcanization aids are compounds having an average of two or more active hydrogen atoms in one molecule of the active atoms represented by the formula (1), for example, a condensation thermoplastic resin (for example, polyamide Oligomers, and the above-mentioned polyamines. The ratio of the vulcanization aid is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably 1 to 1 part by weight based on 100 parts by weight of the rubber and / or the resin. About 5 parts by weight.

[Other additives]

The rubber composition for forming the vulcanized rubber member / intermediate layer may contain various additives, for example, fillers, plasticizers or softeners, and co-vulcanizing agents (metals such as zinc oxide). Oxides), vulcanization accelerators (reaction products of aldehydes such as hexamethylenetetramine diacetaldehyde and ammonia with ammonia, condensation products of aldehydes and amides, guanidines, thiopereas, thiazoles, Sulfenamides, thiurams, dithiolbamates, xanthates, etc., anti-aging agents (heat aging inhibitors, ozone deterioration inhibitors, antioxidants, ultraviolet absorbers, etc.), tackifiers, processing aids , Lubricants (stearic acid, metal stearate, wax, etc.), coloring agents, foaming agents, dispersants, flame retardants, antistatic agents, etc. It may be.

The filler (or reinforcing agent) includes, for example, powdery or granular fillers or reinforcing agents (such as my strength, clay, talc, caicic acids, silica, calcium carbonate, magnesium carbonate, carbon black, ferrite, etc.), and fibrous materials. Filaments or reinforcing agents (organic fibers such as rayon, nylon, vinylon, and aramide, and inorganic fibers such as carbon fiber and glass fiber) are included.

If the rubber is silicone rubber, the most common filler added as a reinforcing agent is silica powder. Generally, silica powders used for silicone rubber are roughly classified into wet silica produced by a wet process and dry silica produced by a dry process. Silicium powder suitable for silicone rubber is dry silica. When dry silica is used, high bonding strength between the resin member and the rubber member can be easily obtained. In the case of wet-type silica, it is considered that the water contained in the silica powder inhibits crosslinking between the resin member and the rubber member. Even if wet silica is fatal If it does not hinder the bonding between the rubber member and the resin member, depending on the type of resin used, the type of silicone rubber used, the type and amount of vulcanizing activator used and the molding conditions, etc., even when wet silica can be used There is. Mixed use of dry silica and wet silica is also acceptable.

The plasticizer is not particularly limited as long as it can impart plasticity to the rubber composition. Conventional softeners (eg, vegetable oils such as linoleic acid, oleic acid, castor oil, and palm oil; minerals such as paraffin, process oil, and extender) Oils, etc.), and plasticizers (phthalate esters, aliphatic dicarbonate esters, sulfur-containing plasticizers, polyester polymer plasticizers, etc.) can be used.

The content of the filler is, for example, about 0 to 300 parts by weight, preferably about 0 to 200 parts by weight, and more preferably about 0 to 100 parts by weight, based on 100 parts by weight of the rubber. It may be. The content of the plasticizer or the softener is, for example, about 0 to 200 parts by weight, preferably about 0 to 150 parts by weight, and more preferably 0 to 120 parts by weight with respect to 100 parts by weight of the rubber. It may be about parts by weight. The content of the co-vulcanizing agent, anti-aging agent, vulcanizing agent or lubricant, coloring agent, etc. may be any effective amount. For example, the content of the co-vulcanizing agent is 100 parts by weight of rubber. To about 0 to 20 parts by weight, preferably about 0.5 to 15 parts by weight, and more preferably about 1 to 10 parts by weight.

Furthermore, a system containing an active ingredient such as a vulcanization activator (unvulcanized rubber composition for an intermediate layer, unvulcanized rubber composition for a vulcanized rubber member, composition for a resin member, particularly a composition for a resin member) In this case, by using a vulcanization activator having a polymerizable unsaturated bond in a heating and mixing process (for example, a kneading process of a resin and a vulcanization activator) by combining with a stabilizer, a gel (or a block) can be obtained. ) Can be suppressed or prevented. For this reason, the vulcanization activator can be made to function effectively and the resin and the rubber can be securely and firmly bonded or adhered without lowering the strength or deteriorating the appearance of the composite. From such a point, the stabilizer may stabilize the resin or rubber. It is preferred to stabilize the sulfur activator.

As the stabilizer, an antioxidant (including a heat-resistant processing stabilizer) and a light stabilizer can be used, and a thermal polymerization inhibitor (hydroquinones such as hydroquinone and methylhydroquinone) may be used. Antioxidants include, for example, phenolic antioxidants, amine antioxidants, phosphorus antioxidants, zeotype antioxidants, hydroquinone antioxidants, quinoline antioxidants, and ketone amine resins. included.

The phenolic antioxidants include hindered phenolic antioxidants, for example, monophenols, bisphenols, polyvalent phenols and the like. Examples of the monophenols include mono- or di-tert-butylphenol which may have a substituent [for example, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-1 4 — Ci- ₄ alkyldi-t-butylphenol such as ethyl phenol; 2-alkoxy-mono or di-t-butylphenol such as t-butyl-4-methoxy-phenol, 3-tert-butyl-4-methoxyphenol; stearyl- / 3 - (3, 5-di - t - butyl - 4-hydroxyphenyl) propionate C ₁₀ _ _{2 ()} alkyl, such as - (di t - butyl - hydroxyphenyl) C ₂ - ₆ force Rupokishire DOO; 2- Echiru Hexyl (2,6-di-tert-butyl-4-hydroxybenzylthio) acetate and other C ₃ _{—1 ()} alkyl- (di-t-butyl-hydroxybenzylthio) C ₂ _ ₆ Karupokishireto; Jisute Ariru one (3, 5-di - t - butyl - 4-hydroxybenzyl) di such host Suhone one preparative (3 _{1 ()} - alkyl - (Gee branched C ₂ _ ₆ alkyl one etc. hydroxybenzyl) phosphonate], such as phenol having a C ₄ _ ₁₀ alkylthio group [2, 4-di (Okuchiruchio) methyl one 6- methylcarbamoyl Rufuwenoru (Irganox 1520 Ciba Geigy one Ltd.)], bis phenols and (meth ) Monoester with acrylic acid [for example, 2- (2-hydroxy-3- 3-t-butyl-5-methylbenzyl)-4-methyl-6-t-butyl phenyl acrylate (Sumilyzer-G M Sumitomo Chemical Co., Ltd.), 2— [1— (2-hydroxy-3-t-butyl-5-methylphenyl) ethyl] —4-methyl-6—t—butylphenyl acrylate, 2-—1— ( 2-hydroxy-3,

C! Alkylene bis (mono or mono) such as 1,4-, 6-di (t-pentyl) phenyl acrylate (Sumilyzer-1 GS, manufactured by Sumitomo Chemical Co., Ltd.) Monoester of di-t-butylphenol) and (meth) acrylic acid, etc.].

Bisphenols include 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-ethylidenebis (Four,

6-di-t-butylphenol), 2,2'-ethylidenebis [4,6-di (t-pentyl) phenol], 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4 '- methylenebis (2, 6-di-one t one-butylphenol) C _ ₆ alkylene bis (such as mono- or di-t- butylphenol); 4, 4' Chiobisu (three to methyl - 6 t one-butylphenol) Thiobis (mono- or di-t-butylphenol); bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] 1,6-hexanediolester, bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionic acid] triethylene glycol ester (Irganox 245 manufactured by Ciba-Geigy Corporation) and other (mono- or di-t-butyl-hydroxy) Enyl) C ₂ _ _6-carboxylic acid - mono- to tetra C ₂ _ ₄ alkyl render recall ester; Hidorazobisu (3, 5-di one t - butyl-4-hydroxy-hydro cinnamoyl) (Irganox MD - 1024 Ciba Geigy one Corporation ), Ν, Ν'-trimethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamide), N, N'-hexamethylenebis (3,5-di-t-butyl) (Mono- or di-tert-butyl) such as 4-hydroxy-hydrocinnamamide Hydroxyphenyl) c ₃ - - ₆ carboxylic acid and c ₀ ₈ diamine de with alkylene § Min; 3, 9 one bis {1, 1 one dimethyl 2- [β - (3 - t one-butyl - 4-hydroxy-5 —Methylphenyl) propionyloxy] ethyl} 1,2,4,8,10-tetraoxaspiro [5,5] indecan (Sumilyzer-1 GA80, manufactured by Sumitomo Chemical Co., Ltd.) - butyl chromatography hydroxyphenyl) C ₃ - such as ₆ Cal Bonn acid and diester of dihydroxy heterocyclic spiro compounds can be exemplified.

Polyhydric phenols include trisphenols {for example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (ADK STAB AO-330 Asahi) tris (mono or di t one-butyl, such as Denka Kogyo Co., Ltd.) - hydroxy Shibenjiru) C ₆ _ ₁₀ Aren; 1, 1, 3- tris (2-methyl - 4-hydroxy-5-t-Puchirufueniru) Bed evening Tris (mono or di-t-butyl-hydroxyphenyl) CH alkane; tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propyl ionic acid] mono- or di-like Dali serine ester - triesters of t one-butyl-hydroxyphenyl C ₂ _ ₆ carboxylic acids with C ₃ _ ₆ Al force Ntorioru; 1, 3, 5-tris (3 ', 5, over-di — T-butyl — 4, monohydroxybenzyl ) — S-triazine-2,4,6- (1H, 3H, 5H) trione (ADK STAB AO-20 manufactured by Asahi Denka Kogyo Co., Ltd.), 1,3,5-tris (2,6 ′ Dimethyl-3, -hydroxy-4, -t-butylbenzyl)-S-triazine-2,4,6- (1H, 3H, 5H) trione such as trione (mono or di-t-butyl) Hydroxybenzyl) -S-triazine-trione, etc.}, tetrafenols {eg, tetrakis [methylene-13- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane (Irganox 1010 Tipa Specialty Chemicals Ltd. Co.) mono- or di-t one Petit root hydroxyphenyl C ₃ _ ₆ Cal such Tetraester of boric acid and C ₆ alkanetetraol; bis (3: 3'-bis (4'-hydroxy-3, -t-butylphenyl) butyric acid) di (mono- or di-t-butyl) such as dalicol ester Ruhidoroki Shifueniru) C ₃ - ₆ force carboxylic monobasic mono- to tetra C ₂ - ₄ Arukirengu recall ester} and the like.

Amine-based antioxidants include aromatic amines, for example, phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N'-diphenyl-1,4-phenylenediamine, N-phenyl-1-N '— Phosphorus antioxidants, including cyclohexyl-1,4-phenylenediamine, etc., include, for example, triisodecyl phosphite, phenyldisodecyl phosphite, diphenyl isodecyl phosphite Ait, trifenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite (ADEKA STAB 2112 made by Asahi Denka Kogyo Co., Ltd.), tris (noelphenyl) phosphite, dinonylphenylbis (nonylphenyl) Phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (Adekas HP-1 0, manufactured by Asahi Denka Kogyo Co., Ltd.), 4,4'butylidenebis (3-methyl-6_t_butylphenyl) ditridecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2 t-Phtyl-4-methylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, bis (2-t-butylphenyl) phenylphosphite Phyto, tris [2- (1,1-dimethylpropyl) phenyl] phosphite, tris [2,4- (1,1-dimethylpropyl) phenyl] phosphite, tris (2-cyclohexylphenyl) phosphite, Tris (2-t-butyl-4-phenylphenyl) phosphite, diisodecyl pentaerythritol diphosphine Wells, (manufactured by ADEKA STAB PEP-8 manufactured by Asahi Denka Co.) cyclic neopentanetetraylbis (O click evening deci Le) Hosufai bets, Sa Cyclic neopentanetetraylbis (2,4-di-t_butylphenyl) phosphite (ADK STAB PEP-24G manufactured by Asahi Denka Kogyo Co., Ltd.), cyclic neopentanetetraylbis (2,6-g Phosphite compounds such as butyl-4-methylphenyl) phosphite (ADEKA STAB PEP-36 manufactured by Asahi Denka Kogyo Co., Ltd.); triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylvinylphosphine, arylyl phosphine Phenylphosphine, triphenylphosphine, methylphenyl p-anisylphosphine, p-anisyldiphenylphosphine, p-tolyldiphenylphosphine, G-p-anisylphenylphosphine, di-p-tolylphenylphosphine, Bird m Aminophenylphosphine, tri-2,4-dimethylphenylphosphine, tri2,4,6-trimethylphenylphosphine, tree o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri — Includes phosphine compounds such as —o—anisylphosphine, tri-p-anisylphosphine, and 1,4-bis (diphenylphosphine) butane.

Examples of the zwitterion-based antioxidants include dilauryl 3,3-thiodibution pionate, di (tridecyl) 3,3-thiodipropionate, dimyristyl 2,2-thiodiacetate, dimyristyl 3,3-thiodipropion Thiol, laurylstearyl 3,3-thiodipropionate, distearyl 3,3-thiodipropionate

C ₂ - ₄ force Rupon di C _{1 0} - 20 alkyl ester; 3, and the like 9- di (lauryl Ruchioechiru) one 2, 4, 8, 1 0-tetraoxaspiro [5 5.] Undekan.

Hydroquinone-based antioxidants include, for example, 2,5-di-tert-butylhydroquinone, 2,5-di-t-amylhydroquinone, and quinoline-based antioxidants include, for example, 6-ethoxy 2, Includes 2,4-trimethyl-1,2-dihydroquinoline. Light stabilizers include hindered amine light stabilizers (HAL S), quenchers and the like. Hindered amine light stabilizers (HAL S) include, for example, optionally substituted tetramethylpiperidine (eg, C !! such as 4-methoxy-2,2,6,6-tetramethylpiberidine). - ₄ alkoxycarbonyl Kishi tetramethyl piperidine; 4 _ Fuenoki shea one .2, 2, 6, 6-tetramethylpiperidine C, such as ₆ - ₁₀ Ari Ruo Kishi tetramethylpiperidine; 4 one Benzoiruokishi one 2,

2, 6, 6-tetramethylpiperidine C ₆ _ ₁₀ Aroiruokishi such - Tetoramechirupi Bae lysine; 4-methacryloyloxy Ruo carboxymethyl one 2, 2, 6, 6-tetramethylpiperidine (ADK STAB LA- 87 Asahi Denka Industry Co., (Meth) acryloyloxy-1-tetramethyl such as 4-methacryloyloxy-N-methyl-2,2,6,6-tetramethylpiperidine (ADEKA STAB LA-82 manufactured by Asahi Denka Kogyo KK) Piperidine, etc.), dipiperidyl ester of arnic acid optionally having a substituent [for example, bis (2,2,6,6-tetramethyl-14-piberidyl) oxalate, bis (2,2, 6,6-tetramethyl-1-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-4-piperidyl) Sepagate (ADEKA STAB LA-77, manufactured by Asahi Denka Kogyo Co., Ltd.), bis (1,2,2,6,6-pentanomethyl-4-piperidyl) sebagate, bis (N-methyl-2,2,6,6-tetrame C ₂ _{-1 ()} bis (tetramethylpiperidyl) ester such as tyl-4-piperidyl) packet (Sanol LS-765 manufactured by Sankyo Co., Ltd.), etc., and may have a substituent. Aromatic dicarboxylic acid dipyridyl ester [for example, bis (2,2,6,6-tetramethyl-

C ₆ _—1Q aromatic dicarboxylic acid bis (tetramethylpiperidyl) ester such as 4-piperidyl) terephthalate, etc., and di (piperidyloxy) alkane [1,2-bis (2 Di (te), such as 2,2,6,6-tetramethyl-1-piperidyloxy) Tramethylbiperidyloxy) (: ₄ alkanes, etc.); di (piveridioxycarbonyl) hydroxyphenylalkane {for example, 1—

(3,5-di-t-butyl-1-hydroxyphenyl) 1,1,1-bis (2,2,6,6-tetramethyl-4-piperidyloxycarponyl) pentane (Tinuvin 144 Ciba-Geigy ) Made

(Tetramethylpiperidyloxycarbonyl) —hydroxyphenylalkane, etc.}, di- or tetrapiperidyl ester of tetrapyruponic acid [for example, 1,2,3,4-butanetetrapyrutonic acid tetrakis

1,2,3,4-butane tetracarboxylic acid tetrakis (tetramethylpiperidyl) ester such as (2,2,6,6-tetramethyl-4-piperidyl) ester (Adecastab LA-57 manufactured by Asahi Denka Kogyo Co., Ltd.) Bis (2,2,6,6-tetramethyl-1-piperidyl) -bis (tridecyl) ester tetracarboxylate (ADEKA STAB LA-67, manufactured by Asahi Denka Kogyo Co., Ltd.), 1,2,3,4-butanetetra Bis (tridecyl) ester bis (tridecyl) ester (Adecastab LA-62 Asahi Denka Kogyo Co., Ltd.) (N-methyl-2,2,6,6-tetramethyl-4-piperidyl)

Bis (tetramethylpiperidyl)

- bis (tri C ₈ _ ₂₀ alkyl) ester], C Bok ₄ alkylene bis (Te tiger alkyl piperazinone) [1, 1, One ethylenebis (3, 3, 3 ', 3', 5, 5, 5 ,, 5'-octamethylpiperazine-1,2, dione) (Goodrite UV-3034 manufactured by Goodrich Co., Ltd.), etc., ₄ alkylenebis (tetramethylpiperazinone), etc.] S [For example, Chimassorb 944LD (Chipa Specialty Chemicals Co., Ltd.), Tinuvin 622LD (Chiba Specialty Chemicals Co., Ltd.), ADK STAB LA-63 (Asahi Denka Kogyo Co., Ltd.), ADK STAB LA- 68 (manufactured by Asahi Denka Kogyo Co., Ltd.).

Quenchers include nickel bis (octylphenol) sulphide, [2,2,1-chobis (4,1 t, 1 year old octylphenol)] — n-butylamine nickel, nickel complex 1,3,5- Di-t-butyl-4-hydroxybenzyl-monoethyl phosphate. Organic nickel complexes such as nickel dibutyl thiocarbamate and 1-phenyl-3-methyl-4-decanoylpyrazolate nickel; cobalt dicyclohexyldithio. Examples thereof include organic cobalt complexes such as phosphate.

These stabilizers may be used alone or in combination of two or more. Preferred stabilizers include phenolic antioxidants and stabilizers having radical scavenging ability, such as HALS. Further, a stabilizer having such a radical scavenging ability and another stabilizer may be used in combination. Such a combination includes, for example, a phenol-based antioxidant and a zeolite-based antioxidant. Combinations, combinations of phenolic antioxidants and phosphorus antioxidants, etc. are included.

The amount of the stabilizer used is, for example, 0.01 to 15 parts by weight (for example, 0.01 to 10 parts by weight), preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the resin or rubber. It may be about 10 to 10 parts by weight (for example, 0.05 to 8 parts by weight), more preferably about 0.1 to 7 parts by weight (for example, 0.1 to 5 parts by weight).

When a stabilizer having a radical scavenging ability (phenolic antioxidant, HALS, etc.) is used in combination with another stabilizer (phosphorous antioxidant, sulfur-based antioxidant, etc.), The ratio of the stabilizer may be about the former (the weight ratio) = 99Z1 to 20/80 (for example, 9555 to 40Z60).

The ratio between the vulcanizing activator and the stabilizer can be selected according to the type of the vulcanizing activator or the stabilizer, the mixing and kneading temperature, and the like. The former Z The latter (weight ratio) = 99/1 to 2557 5, preferably 9 8 / ^/ 2-3 5 6 5, preferably a further 9 7 Bruno 3-4 5/5 5 (e.g., 9 7 Bruno 3-6 0/4 0) may be about.

[Combination of resin member and vulcanized rubber member]

In the present invention, the vulcanized rubber layer is provided between the resin member and the vulcanized rubber member. Because of the interposition, even when the resin member and the vulcanized rubber member are combined in a wide range, the composite can be reliably and firmly joined, and a highly integrated composite can be obtained. Also, whether the vulcanization system is a sulfur vulcanization system or a non-sulfur vulcanization system, the bonding strength between the resin member and the vulcanized rubber member can be improved. Therefore, the combination of the resin member and the vulcanized rubber member is not particularly limited, and the resin and the rubber can be appropriately combined.

In order to increase the bonding strength when joining the resin member and the vulcanized rubber member, at least one of the vulcanized rubber layer, the vulcanized rubber member and the resin member is formed of a composition containing a vulcanizing activator. Advantageously. For example, the vulcanized rubber layer is formed of an unvulcanized rubber composition containing a vulcanizing agent and a vulcanizing activator, and at least one of the vulcanized rubber member and the resin member (particularly at least the resin member) is vulcanized. When formed from a composition containing a sulfur activator, the resin member and the vulcanized rubber member can be joined with extremely high joining strength.

The thermoplastic resin of the resin member or the composition thereof is composed of a polyphenylene-based resin, and the unvulcanized rubber of the vulcanized rubber layer or the composition thereof is composed of a styrene-gen copolymer rubber. In this case, the vulcanized rubber layer can be bonded to the vulcanized rubber member with a high bonding strength regardless of whether it is vulcanized with a radical generator (such as an organic peroxide) or a sulfur-based vulcanizing agent. In this case, the polyphenylene ether-based resin may be modified or modified with a styrene-based resin.

When vulcanizing a styrene-gen copolymer rubber with a sulfur vulcanizing agent, the amount of the sulfur vulcanizing agent to be used is preferably 1 to 10 parts by weight, more preferably 100 to 100 parts by weight of the rubber component. Is about 2 to 7 parts by weight, more preferably about 3 to 5 parts by weight.

[Method for producing composite]

In the present invention, the rubber element and the resin element are brought into contact with each other via an unvulcanized rubber layer containing a vulcanizing agent, and the unvulcanized rubber or semi-vulcanized rubber is vulcanized. Mold Thereby, the resin Z rubber in which the vulcanized rubber member of the rubber element and the resin member of the resin element are joined via the composite (that is, the vulcanized rubber layer obtained by vulcanizing the unvulcanized rubber layer) Complex). Typically, a vulcanized rubber member is brought into contact with a resin member via an unvulcanized rubber layer containing a vulcanizing agent, and the unvulcanized rubber layer is vulcanized by heating or other means. A composite in which the vulcanized rubber member and the resin member are joined can be obtained.

The rubber element (rubber material) constituting the vulcanized rubber member may be a rubber material which has been vulcanized, and may be an unvulcanized rubber material (unvulcanized rubber composition) or a semi-vulcanized rubber material (half) (Vulcanized rubber member). When the rubber element (rubber material) is an unvulcanized rubber composition or a semi-vulcanized rubber member, both are vulcanized in the vulcanizing step of the unvulcanized rubber layer. Further, the resin element (resin material) constituting the resin member may be an unformed resin composition, a semi-molded resin member, or a molded resin member.

The terms “vulcanized rubber member”, “rubber member” and “resin member” mean a member formed into a predetermined shape as a final component, and include “unvulcanized rubber composition” and “unformed resin composition”. By means a composition that does not have a particular shape. Furthermore, “semi-vulcanized rubber material”, “semi-vulcanized rubber member”, and “semi-formed resin member” refer to a member that has been processed but does not have the shape and Z or component of the form of the final member. It means unvulcanized rubber, active vulcanizing agents, and preforms which may contain vulcanizing activators and uncrosslinked resins.

As described above, the rubber element (particularly, the unvulcanized composition and the semi-vulcanized rubber member) contains at least a vulcanizing agent (particularly, a radical generator-based vulcanizing agent). Further, in order to increase the bonding strength with the intermediate layer, the rubber element (particularly, the unvulcanized composition and the semi-vulcanized rubber member) is made of a vulcanization activator (a polyfunctional polymer having a plurality of polymerizable unsaturated bonds). Compound). The proportion of each component is as described above.

As described above, the resin element (particularly, a resin having a crosslinkable group) A crosslinking accelerator may be included. Further, the resin element (a thermoplastic resin or a resin having a crosslinkable group) may contain a vulcanization activator (a polymerizable compound having a plurality of polymerizable unsaturated bonds) as described above. In order to increase the bonding strength between the vulcanized rubber member and the resin member, the polyfunctional polymerizable compound having a plurality of polymerizable groups is preferably contained in at least one of the rubber element and the resin element, and is contained in both. You may let it. The proportions of these components are also as described above. The unvulcanized rubber composition for forming the unvulcanized rubber layer may contain at least a vulcanizing agent (particularly a radical generator-based vulcanizing agent such as an organic peroxide). In addition, it contains a vulcanizing activator (a polyfunctional polymerizable compound having a plurality of polymerizable groups). In the unvulcanized rubber composition, the contents of the vulcanizing agent and the vulcanizing activator are as described above.

In a preferred embodiment, (i) the resin constituting the resin member is a resin having the specific active atom (active hydrogen atom and hydrogen or active sulfur atom). (Ii) At least one of the unvulcanized rubber composition and the resin member contains a polyfunctional polymerizable compound having a plurality of polymerizable groups. Further, (iii) the resin member is composed of a thermosetting resin or a resin having an unsaturated bond in a molecule, and the unvulcanized rubber composition contains a polyfunctional polymerizable compound having a plurality of polymerizable groups. .

The unvulcanized rubber layer may be formed on at least one of the bonding surfaces of the rubber element and the resin element. Although the unvulcanized rubber layer is often a substantially uniform layer, it is not necessary that the unvulcanized rubber layer be substantially uniform unless the bonding between the vulcanized rubber member and the resin member is impaired. For example, the unvulcanized rubber layer may be a layer having an uneven thickness (for example, an uneven layer or a dotted layer).

Vulcanization molding is usually performed by irradiating light, in particular, heating the rubber element and the resin element through the unvulcanized rubber layer under pressure contact. In this process, the rubber composition for the vulcanized rubber member and the semi-vulcanized rubber member are vulcanized together with the vulcanization of the unvulcanized rubber composition. In addition, With the heat, the unformed resin composition and the semi-formed resin member are also formed, and the resin having a crosslinkable group can be crosslinked and cured. .

The unvulcanized rubber layer is not limited to a film (sheet) of the unvulcanized rubber composition interposed on the bonding surface of the rubber element and / or the resin element, and may be a coating layer formed by a coating agent. For example, a liquid unvulcanized rubber composition (for example, a solution or dispersion of an unvulcanized rubber composition (emulsion, suspension), etc.) as a coating agent is applied to the bonding surface of the rubber element and the Z or resin element. An unvulcanized rubber layer can be formed by drying if necessary. In addition, the film or sheet of the unvulcanized rubber composition may be formed in advance according to the molding method as described above, and together with the composition for the vulcanized rubber member or the composition for the resin member, It may be formed by co-extrusion of an unvulcanized rubber composition.

More specifically, the method of the present invention includes the steps of molding a resin composition, an unvulcanized rubber composition of an intermediate layer, and an unvulcanized rubber composition of a vulcanized rubber member, respectively. Contacting or merging a material, an intermediate layer and an unvulcanized rubber composition, and joining or bonding the resin member and the vulcanized rubber member via the intermediate layer (one-step method); One of the elements is molded (for example, one of the resin member and the vulcanized rubber member is preliminarily molded or formed into a final member), and the other molded element and the intermediate layer are unformed. The vulcanized rubber composition is brought into contact with the other unmolded element (unmolded resin composition or unvulcanized rubber composition), and the uncured rubber composition is bridged or vulcanized while being molded. Resin member and vulcanized rubber via intermediate layer A method of joining or adhering to a member (two-stage method), a molding resin element (a molded resin member previously formed into a preformed or final member form) with an unvulcanized rubber composition for an intermediate layer interposed therebetween. ) And a molded rubber element (a molded rubber member preliminarily molded or formed into a final member form), cross-linked or vulcanized to form a resin member and a vulcanized rubber member via an intermediate layer. And a method of joining or bonding them (three-step method).

More specifically, in the one-step method, for example, a conventional multicolor molding machine (multicolor injection molding machine, multilayer extruder, etc.) is used, and the resin composition and the unvulcanized rubber composition of the intermediate layer are vulcanized. Injecting or extruding the unvulcanized rubber composition of the vulcanized rubber member into a mold having a predetermined shape while melt-kneading the resin composition and crosslinking or vulcanizing the resin composition and the unvulcanized rubber after or during the molding process. A more composite molded article can be obtained. In the contact interface region between the resin composition and the unvulcanized rubber composition, the resin composition and the unvulcanized rubber composition may be mixed.

In the two-step method, a conventional molding machine (such as an injection molding machine, an extrusion molding machine, or a hot press molding machine) can be used for molding the molded resin element, and a conventional molding machine can be used for molding the molded rubber element. (Injection molding machine, press molding machine, transfer molding machine, extrusion molding machine, etc.) can be used. For example, a molded resin element is accommodated in a mold (or capty) corresponding to the shape of the composite, and the unvulcanized rubber composition for the intermediate layer and the unvulcanized rubber composition for the vulcanized rubber member are placed on the resin element. The vulcanized rubber member and the resin member may be bonded via an intermediate layer by injecting or extruding the vulcanized rubber composition and crosslinking or vulcanizing the unvulcanized rubber composition. Further, when the composite is a plate-like or sheet-like member having a two-dimensional spread, the unvulcanized rubber for the intermediate layer can be formed on the molded resin element without using the mold (or the cavity). A composite may be produced by laminating a film or sheet of the composition and a plate-shaped or sheet-shaped unvulcanized rubber composition for forming a vulcanized rubber member, followed by crosslinking or vulcanization. When the molded resin element is brought into contact with the unvulcanized rubber composition (such as close contact), hot press molding or injection molding is used to remove volatile components and gas components in the unvulcanized rubber composition. Then, pressure may be appropriately applied, or pressure molding may be performed in a reduced-pressure atmosphere.

In the three-step method, a molded resin element and a molded rubber element are brought into contact with each other via a film (sheet) of an unvulcanized rubber composition, and the crosslinked or A composite may be obtained by vulcanization, and an unvulcanized rubber layer is formed by applying a coating liquid of an unvulcanized rubber composition to a bonding surface of at least one of a molded resin element and a molded rubber element. Then, the composite may be obtained by pressurizing and molding the molded resin element and the molded rubber element via the unvulcanized rubber layer.

The thickness of the film (sheet) of the unvulcanized rubber composition is not particularly limited, and is, for example, about 0.1 to 10 mm, preferably about 0.5 to 5 mm, and more preferably about 0.5 to 3 mm. There may be. The coating amount (in terms of solid content) of the coating agent on the contact surface or the bonding surface is, for example, about 0.1 to 500 gZm ² , preferably about 10 to 300 gZm ² , particularly about 50 gZm ^2. It may be about 100 gZm ² .

The crosslinking (or vulcanization) temperature (or the joining temperature between the rubber member and the resin member) of the molded resin material and the molded rubber material is, for example, 70 to 250, preferably 100 to 230 °. C, more preferably in the range of about 150 to 200 ° C. The pressure acting between the rubber Z resins can be selected, for example, from the range of about 0.1 to 350 MPa, preferably 1 to 150 MPa, and more preferably about 2 to 10 OMPa.

The solvent of the coating agent is not always necessary when a low molecular weight rubber (for example, liquid rubber) is used, but the solvent may be a hydrocarbon (aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon). Hydrogen), alcohols, esters, ketones, ethers, sulfoxides, amides, and the like.

In the present invention, since a vulcanized layer of an unvulcanized rubber composition containing a vulcanizing agent is interposed between the resin member and the vulcanized rubber member, the resin molded body and the vulcanized rubber molded body can be used in a wide range of combinations. Thus, a complex can be obtained in which the and are firmly joined. Further, the resin molded article and the vulcanized rubber molded article can be firmly joined without subjecting the surface of the resin molded article to an easy adhesion treatment. Furthermore, it is possible to strongly bond a sulfur-vulcanized rubber member with a resin member without changing the rubber formulation. In addition, a space between the resin member and the vulcanized rubber member is provided. Since the vulcanized layer of the unvulcanized rubber composition is interposed, the resin member and the vulcanized rubber member can be firmly joined even in a three-dimensional structure. Industrial applicability

In the composite thus obtained, the rubber member and the resin member are bonded with extremely high strength by vulcanization. As a result, the properties of resin and rubber can be effectively expressed, and used in various applications, such as automotive parts (vibration absorbing bushes, spring plates, door lock members, radiator mounts, etc.), anti-vibration rubber, valves It can be advantageously used as various members such as electric plugs. Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Composition of resin member]

PA 6 12 (A 1): Polyamide 6 12 (NH ₂ terminal ZCOOH terminal = 1 1 (molar ratio))

PA 6 1 2 Preparation of (A 1): hexamethylene di § Min and pressurizing the salt 8 0% by weight aqueous solution in Otokurebu purged with nitrogen dodecanoic dicarboxylic acid ^{(1 7. 5 kg / cm 2} ) heating under (220 T), and the water in the system was discharged to the outside of the system along with the nitrogen gas in 4 hours. After one hour, the temperature was gradually raised (275) to remove water out of the system, and then the internal pressure of the autoclave was returned to normal pressure, followed by cooling to obtain polyamide 612. . The obtained polymer had a number average molecular weight (Δη) of 2000 to 2500 and a ratio of an amino group terminal to a lipoxyl group terminal = 1/1 (molar ratio). This polymer was used alone as a resin composition PA612 (A1). When the vulcanizing agent is an organic peroxide, the number of active hydrogens in PA612 (A1) is four per molecule.

PA 6 12 (A 2): polyamide 6 1 2 (NH ₂ terminal C〇OH powder Edge = 3Z7 (molar ratio) alone

Preparation of PA 6 12 (A 2): The above resin composition PA 6 12 (A 1) and the following resin composition (A 3) were kneaded at a weight ratio of 1 Z 1 using a twin screw extruder. . This was used alone as the resin composition PA 612 (A 2). The number of active hydrogen atoms in P A612 (A2) is 2.4 per molecule.

PA 6 12 (A 3): Polyamide 6 12 (NH ₂ terminal COOH terminal = 1 Z 9 (molar ratio)) alone

Preparation of PA612 (A3): A predetermined amount of dodecanedicarboxylic acid was added to an 80% by weight aqueous solution of hexamethylenediamine and dodecanedicarboxylic acid, and the mixture was pressurized in a nitrogen-purged autoclave (17). The system was heated under a pressure of 5 kZcm ² ), and the water in the system was discharged together with nitrogen gas to the outside of the system in 4 hours. After one hour, the temperature was gradually increased (275 ° C) to remove water from the system, and the internal pressure of the autoclave was returned to normal pressure. After cooling, polyamide 612 was obtained. The obtained polymer had a number average molecular weight (Mn) of about 20000, and the ratio of amino terminal to carboxyl terminal = 19. This polymer was used alone as the resin composition PA612 (A3). The number of active hydrogens in PA612 (A3) is 0.8 per molecule.

P P E (B 1): Polyphenylene ether resin

Vestorannl900 manufactured by Degussa (Degusa) was used. The number of active hydrogens per molecule is 6 or more.

P P S (C 1): Polyphenylene sulfide resin

Fortron 0220 A9 manufactured by Polyplastics Co., Ltd. was used. The number of active sulfur per molecule is 6 or more.

m— P B T (0 1): Denatured? 8 resin

m—Preparation of PBT (D 1): 883 g of distilled and purified dimethyl terephthalate, 74.7 g of butanediol and 70.4 g of butylenediol, 1.82 g of calcium acetate, 30.0 g of antimony oxide Add 64 g The mixture was placed in a polymerization tube having a stirrer, a nitrogen gas introduction tube, a distillation side tube, and connected to a vacuum system. The polymerization tube was heated to 180 in an oil bath, and while slowly passing nitrogen gas, stirring was started when the amount of methanol distilled out reached the theoretical value, and the temperature of the system was gradually increased to 250 to 260. ° C and the degree of vacuum was gradually increased to reach 100 Pa or less. The condensation reaction takes 2 to 3 hours to proceed while distilling a small amount of butanediol to be formed, and the relative viscosity in a mixed solvent of tetrachloroethane Z phenol = 40Z60 is measured as appropriate. The reaction was stopped when the volume reached 10,000. The concentration of unsaturated bonds in the polymer obtained was an average of 4 per polymer molecule, 0.4 mol Zkg. This polymer was used alone as the modified PBT resin composition (D1).

Unsaturated PES (E 1): unsaturated polyester resin

Preparation of unsaturated PE S (El): 604 g of maleic anhydride, 507 g of propylene blend, and 0.22 g of hydroquinone monomethyl ether and 0.6 g of esterification catalyst dibutyltin oxide in a nitrogen stream at normal pressure The resulting mixture was dehydrated and condensed at 180 to 190 ° C. to obtain an unsaturated polyester having a weight average molecular weight of 5,800. 3.4 g of cobalt naphthenate was added to this unsaturated polyester, and dissolved and diluted with 600 g of ethyl methacrylate and 100 g of styrene. To 100 parts by weight of the diluted solution, 3 parts by weight of an organic peroxide (Nippon Oil & Fats Co., Ltd., Perbutyl O) was added, stirred, and then cured under 80 conditions to obtain a flat plate having a thickness of 3 mm. This was used as a sample of the unsaturated polyester resin composition (E1).

Melamine (F 1): Melamine resin

A flat plate having a thickness of 4 mm was prepared using "Sumicon MMC-50" (black colored product) manufactured by Sumitomo Bakelite Co., Ltd. and used as a sample of the melamine resin composition (F1).

TR IM: Trimethylolpropane trimethacrylate [Composition of vulcanized rubber layer]

SBR: "JSR0202" (styrene content 46) manufactured by JSR Corporation

E PDM: D SM Company `` Keltan 509 X100 ''

NR: Thai domestic # 3

NBR: “Nipo 1 1 0 4 2” manufactured by Zeon Corporation

VMQ-1

(A) dimethylchlorosilane _{_{(CH 3) 2 S i C}} 12 (B) and methyl vinyl chlorosilane _{_{(CH 3) CH 2 = CH-}} S i C 1 2 and the molar ratio 9 9.9 8: 0.0 2 Using this, a (CI) cyclic dimethylsiloxane-methylvinylsiloxane tetramer was obtained. To 100 moles of this (C 1) tetramer, 0.0011 moles of lithium hydroxide was added, and the polymerization was carried out at a temperature of 150 ° (: nitrogen atmosphere. The intrinsic viscosity of the polymer (siloxane A) [7]] (25 ° C, c St) is log? 7 = 7.7. From the value of the intrinsic viscosity, the average molecular weight is 290,000, It was determined to be a polysiloxane having a degree of polymerization of about 400. The amount of vinyl in the obtained polymer was determined by —NMR, and it was determined that the average of 100 repeating units was 0.1%. It had 0.2 vinyl groups, ie, 0.8 double bonds per molecule on average.

The molar ratio of (A) dimethylchlorosilane to (B) methylvinylchlorosilane was 50:50 to obtain (C 2) cyclic dimethylsiloxane-methylvinylsiloxane tetramer. To 100 mol of the (C 2) tetramer, 0.445 mol of potassium hydroxide was added and polymerized. The obtained polymer (siloxane B) was subjected to gas chromatography (Capillary column: DURABONDDB_1701 from J & W, injection temperature: Cool-on column method) The temperature was raised to 270 ° C in 50 ° C / 30 seconds, and the carrier gas was: Analysis by helium (30 ml / in, detector: FID) revealed a degree of polymerization of about 10. — NMR analysis showed that an average of 50 vinyl groups out of 100 repeating units, And Had 5 double bonds per molecule.

Siloxane A and Siloxane B were mixed at a molar ratio of 47:53, and used as VMQ-1 having an average of three double bonds per molecule.

FKM: Fluororubber Daikin G Daikin Co., Ltd. Dai EL G902 DCP: Dicumylvanoxide Nippon Yushi Co., Ltd. “Parkmill D”

S: Sulfur powder “# 32 5” manufactured by Tsurumi Chemical Industry Co., Ltd.

[Composition of rubber member]

EP DM: 100 parts by weight of EP DM, 3 parts by weight of Ves tenamer8012 (manufactured by Degussa), 3 parts by weight of carbon black [N582] (manufactured by Asahi Rikibon Co., Ltd.), 3 parts by weight of magnesium silicate One part "(manufactured by Nippon Mistron Co., Ltd.) 25 parts by weight, naphthenic oil" Diana Process Oil NS100 "(manufactured by Idemitsu Kosan Co., Ltd.) 5 parts by weight, paraffin oil" Diana Process Oil PW 3 " 800 ”(manufactured by Idemitsu Kosan Co., Ltd.) 14 parts by weight, 1 part by weight of polyethylene diol (400), 0.5 part by weight of stearic acid, 3 parts by weight of zinc oxide.

SBR 60 / NBR 40: 60 parts by weight of the above SBR, 40 parts by weight of the above NBR, 50 parts by weight of Ribon Bon Black "N582" (manufactured by Asahi Carbon Co., Ltd.), Diana Process Naphthenic oil Oil NS 100 "(manufactured by Idemitsu Kosan Co., Ltd.) 10 parts by weight, stearic acid 1 part by weight, zinc oxide 5 parts by weight, stabilizer" Nonflex RD "(manufactured by Seikagaku Co., Ltd.) 1 weight 1 part by weight, Stabilizer "Santite 2" (manufactured by Seikagaku Co., Ltd.) 0.2 part by weight of stabilizer "Santogard PV I" (manufactured by Flexis Co., Ltd.), Noxeller vulcanization accelerator C Zj (Ouchi Shinko Chemical Co., Ltd.) 1 part by weight, vulcanization accelerator "Noxera-TS" (Ouchi Shinko Chemical Co., Ltd.) 0.3 part by weight.

SBR 60 ZNR40: SBR 60 parts by weight above, NR 40 parts by weight above, Ribon Bon Black "Asahi # 70" (made by Asahi Carbon Co., Ltd.) 4 5 layers Amount, naphthenic oil "Diana Process Oil NS 100" (made by Idemitsu Kosan Co., Ltd.) 10 parts by weight, stabilizer "Nocrack ODA" (made by Ouchi Shinko Chemical Co., Ltd.) 1.5 weight Parts, stabilizer “Nocrack 224” (Ouchi Shinko Chemical Co., Ltd.) 1.5 parts by weight, vulcanization accelerator “Noxeller DM” (Ouchi Shinko Chemical Co., Ltd.) 0.6 parts by weight 0.3 parts by weight of vulcanization accelerator "NOXELLA CZ" (manufactured by Ouchi Shinko Chemical Co., Ltd.) 0.3 parts by weight of stearic acid 1.5 parts by weight, zinc oxide 5 parts by weight.

VMQ-2: "Silicone rubber SH851" manufactured by Toray Dow Corning Co., Ltd.

FKM: Fluoro rubber “DaiELG902” (manufactured by Daikin Industries, Ltd.) 100 parts by weight, power pump rack “Thermax x N990” Cancarb 10 parts by weight

BR: Butadiene rubber “BUNA CB 100” (manufactured by Bayer) 100 parts by weight, naphthenic oil “Diana Process Oil NS-24” (manufactured by Idemitsu Kosan Co., Ltd.) 100 parts by weight, power pump rack Shaw Black N330T (manufactured by Showa Kyapot Co., Ltd.) 50 parts by weight, Stabilizer "Vu1 kaηοX4010 Ν Α" (manufactured by Bayer AG) 1.5 parts by weight Sulfur accelerator Accelerator Noxeller CZ (Ouchi Shinko Chemical Co., Ltd.) 1 part by weight, stearic acid 2 parts by weight, zinc oxide 5 parts by weight.

DCP: Jikmil Parkside Nippon Resin Co., Ltd. “Parkmill DJ”

TA I C: Triaryl isocyanurate

[Test method]

Each of the above resin compositions was molded by an injection molding method or a compression molding method to obtain a flat plate having a thickness of 4 mm.

A rubber solution prepared by the following method was applied to one surface of the flat plate to a thickness of 100 using Barco overnight. Rubber solution applied Thereafter, the mixture was left for 1 hour, and the solvent was air-dried to form an unvulcanized rubber layer. The resin flat plate having the unvulcanized rubber layer is placed in a mold whose temperature is controlled at 170 with the unvulcanized rubber layer as an upper surface, and the unvulcanized rubber constituting the rubber member is placed on the unvulcanized rubber layer. The unvulcanized rubber layer and the unvulcanized rubber member were bonded by vulcanization while a predetermined amount of the vulcanized rubber composition was loaded and compression-molded so that the thickness of the rubber member became 3 mm. The heating time was approximately 15 minutes.

Table 1 shows the combinations of the resin flat plate, the unvulcanized rubber layer, and the vulcanized rubber member. In the table, in Examples 2, 3 and Examples 10 and 11, "* J indicates that after forming an unvulcanized rubber layer on a resin plate, and then vulcanizing this unvulcanized rubber layer, This shows that the unvulcanized rubber composition for a rubber member was put on the vulcanized rubber layer and vulcanized at 170 ° C.

[Preparation of rubber solution]

100 parts by weight of the rubber for the rubber layer having the component ratio (parts by weight) shown in the table was dissolved in 400 parts by weight of a mixed solvent containing ethyl acetate, MEK, and toluene in a ratio of 1: 1: 1. To this solution, a vulcanizing agent and trimethylolpropane trimethacrylate (TRIM) were added in the proportions shown in the table to prepare a rubber solution.

[Evaluation of adhesiveness]

The resin / rubber layer obtained by the above method, the flat composite of the Z rubber member was cut into a width of 3 Om m, and the obtained test piece was subjected to a 180 ° peel test. In this peel test, the adhesiveness was evaluated according to the following criteria.

"A": A peeling interface occurs in the rubber layer or the rubber member (cohesive failure), and the destruction is 100% cohesive failure.

"B J: 50% or more is cohesive failure

"C": Sufficient tackiness is observed. 50% or more of peeling occurs at the interface of resin Z rubber layer or rubber layer rubber member.

"D": easily peels off at the interface between the resin Z rubber layer and the rubber layer

Table 1 shows the results. In the table, the ratio of each component is part by weight. As is clear from Table 1, the composites obtained in the examples show high bonding strength.

table 1

Resin component composition Vulcanized rubber layer fiber rubber component composition

Resin Number of active atoms VA rubber Vulcanizing agent VA rubber Vulcanizing agent Others Adhesive Example 1 PA612 (A1) 4 TRIM 5 EPDM DCP2 0 EPDM DCP 2.5 1 A Example 2 PA612 (A1) 4 TRIM 5 SBR DCP 0.2 * 0 SBR60 / NBR40 S 2 ― B Example 3 PA612 (A1) 4 TRIM 5 SBR DCP 0.2 * 0 SBR60 / NR40 S 2-1B Example 4 PA612 (A1) 4 0 VMQ-1 DCP 2 TRIM 0.5 Job-2 DCP 2.5 ― A Example 5 PA612 (A1) 4 0 EPDM DCP 2 TRIM 3 FKM DCP 2.5 TAIC 4 A Example 6 PA612 (A1) 4 0 EPDM DCP 2 TRIM 3 EPDM DCP 2.5 ― A Example 7 PA612CA1) 4 0 EPDM DCP 2 0 EPDM DCP 2.5 ― B Comparative Example 1 PA612 (A1) 4 TRIM 5 EPDM DCP 2.5 1D Example 8 PA612 (A2) 2.4 0 EPDM DCP 2 0 EPDM DCP 2.5 ― C Example 9 PA612 (A2) 2.4 TRIM 5 EPDM DCP 2 0 EPDM DCP 2.5-A Comparative Example 2 PA612 (A2) 2.4 TRIM 5 EPDM DCP 2.5 D Comparative Example 3 PA612 (A3) 0.8 0 EPDM DCP 2 0 EPDM DCP 2.5 D Comparative Example 4 PA612CA3) 0.8 TRIM 5 EPDM DCP 2.5 D Example 10 PPE (Bl)> 6 0 EPDM DCP 2 * TRIM 3 EPDM S 2 A Example 11 PPE (Bl)> 6 0 SBR DCP 0.2 * 0 SBR60 / NBR40 S 2 A Example 12 PPE (Bl) > 6 0 SBR S 2 0 SBR60 / NR40 S 2 A Example 13 PPE (Bl)> 6 0 SBR / EPDM S 2 0 EPDM S 2 A Example 14 PPE (Bl)> 6 0 SBR S 2 0 BR S 2 A Example 15 PPS (Cl)> 6 0 VMQ-1 DCP 2 TRIM 0.5 VMQ-2 DCP 2.5 A Example 16 m-PBT (Dl), Ichiko Itoguchi EPDM DCP 2 TRIM 3 EPDM DCP 2.5 A Example 17 Unsaturated PES (El) FKM DCP 2 TRIM 3 FKM DCP 2.5 TAIC 4 A Example 18 Min (Fl) VMQ-1 DCP 2 TRIM 0.5 VMQ-2 DCP 2.5 B

Claims

The scope of the claims

1. A resin-rubber composite in which a vulcanized rubber member and a resin member are joined via a vulcanized rubber layer vulcanized with a vulcanizing agent.

2. The composite according to claim 1, wherein the vulcanizing agent is a sulfur vulcanizing agent or a peroxide vulcanizing agent.

3. The composite according to claim 1, wherein the vulcanizing agent is an organic peroxide.

4. The composite according to claim 1, wherein the resin member is composed of at least one selected from a thermoplastic resin and a resin having a crosslinkable group.

5. The composite according to claim 4, wherein the resin having a crosslinkable group is at least one selected from a thermosetting resin and a thermoplastic resin having an unsaturated bond.

6. The composite according to claim 1, wherein the unvulcanized rubber composition and the resin member for forming the vulcanized rubber layer satisfy at least one of the following conditions (i) to (iii).

(i) The resin member has an orbital interaction energy coefficient S represented by the following formula (1) of not less than 0.006 and at least one active atom selected from a hydrogen atom and a sulfur atom. Consists of a thermoplastic resin with at least two in one molecule

° ⁼ , then HOMO, n) / I ^E C "~ ^E H0M0, n I + ( ^C LUM0, n) / IE _c — E LUMO, n I ( ¹ )

_{_{(Wherein, E c, C H 0M0,}} n, E H0M0, n, C LUM0, n, E LUM0, n is either also calculated by a semiempirical molecular orbital method M_〇 P AC PM 3 values hand,

E _c indicates the orbital energy (e V) of the radical of the radical generator as a vulcanizing agent. ^ ^ Indicates the molecular orbital coefficient of the highest occupied molecular orbital (HOMO) of the nth active atom constituting the basic unit of the thermoplastic resin, and E _H0M0 , _n indicates the orbital energy (e V) of the HOMO. , C LUM0, n is the molecule of the lowest unoccupied molecular orbital (LUMO) of the nth active atom Orbital coefficient, and E _LUM0 , _n indicate the orbital energy (eV) of the L UMO

(ii) at least one of the unvulcanized rubber composition and the resin member contains a polyfunctional polymerizable compound having a plurality of polymerizable groups.

(iii) The resin member is composed of a thermosetting resin or a resin having an unsaturated bond in a molecule, and the unvulcanized rubber composition contains a polyfunctional polymerizable compound having a plurality of polymerizable groups.

7. The composite according to claim 1, wherein at least one of the vulcanized rubber layer, the vulcanized rubber member and the resin member is formed of a composition containing a vulcanization activator.

8. The composite according to claim 7, wherein the vulcanization activator comprises a polyfunctional polymerizable compound having a plurality of polymerizable groups.

9. The vulcanized rubber layer is formed of an unvulcanized rubber composition containing a vulcanizing agent and a vulcanizing activator, and at least one of the vulcanized rubber member and the resin member contains the vulcanizing activator The composite according to claim 1, wherein the composite is formed of a composition.

10. The composite according to claim 7, wherein the resin member is formed of a composition containing a vulcanization activator.

11. The composite according to claim 7, wherein the amount of the vulcanization activator is 0.1 to 10 parts by weight based on 100 parts by weight of at least one component selected from resin and rubber.

12. The composite according to claim 7, wherein the amount of the vulcanizing activator is 2 parts by weight or less based on 100 parts by weight of the rubber.

10. The resin member according to claim 10, wherein the resin member further comprises a stabilizer for the vulcanization activator, and the stabilizer is at least one selected from an antioxidant, a light stabilizer and a thermal polymerization inhibitor. Complex.

14. The composite according to claim 13, wherein the ratio between the vulcanizing activator and the stabilizer is former / latter (weight ratio) = 991 to 25 to 75.

1 5. The resin member is made of polyamide resin, polyester resin, Riacetal resin, Polyphenylene ether resin, Polysulfide resin, Polyetherketone resin, Polycarbonate resin, Polyimide resin, Polysulfone resin, Polyurethane resin, Polyolefin resin, Halogen-containing Vinyl resin, styrene resin, (meth) acrylic resin, thermoplastic elastomer, phenol resin, amino resin, epoxy resin, thermosetting polyimide resin, thermosetting polyurethane resin, silicone resin, unsaturated 2. The composite according to claim 1, wherein the composite is composed of at least one resin selected from a polyester resin, a vinyl ester resin, a diaryl phthalate resin, and a thermosetting (meth) acrylic resin.

16. The composite according to claim 1, wherein the vulcanized rubber layer is vulcanized with a sulfur-based vulcanizing agent.

17. The composite according to claim 1, wherein the vulcanized rubber layer is composed of a gen-based rubber.

18. The composite according to claim 1, wherein the vulcanized rubber layer is composed of a styrene-gen-based rubber vulcanized with a sulfur-based vulcanizing agent, and the resin member is composed of a polyphenylene ether-based resin.

1 9. A rubber element selected from an unvulcanized rubber composition, a semi-vulcanized rubber member and a vulcanized rubber member via an unvulcanized rubber composition layer containing a vulcanizing agent, and an unformed resin composition Object, a semi-molded resin member and a resin element selected from a molded resin member, and vulcanizes the unvulcanized rubber or semi-vulcanized rubber. A method for producing a resin Z rubber composite in which a resin member is joined.

20. An unvulcanized rubber composition layer containing a vulcanizing agent is formed on at least one of the bonding surfaces of the rubber element and the resin element, and this unvulcanized rubber composition layer is formed. 10. The method according to claim 19, wherein the rubber element and the resin element are heated under pressure contact via the rubber element.

21. The method according to claim 20, wherein the unvulcanized rubber composition layer containing the vulcanizing agent is formed of a film or coating agent of the unvulcanized rubber composition.

2 2. The unvulcanized rubber composition of the intermediate layer is interposed between the molded resin member and a rubber element selected from the unvulcanized rubber composition and the semi-vulcanized rubber member, and the unvulcanized rubber and Z 10. The method according to claim 19, wherein the crosslinking or vulcanization is performed while molding the semi-vulcanized rubber.

23. The method according to claim 19, wherein at least one of the unvulcanized rubber composition layer, the rubber element and the resin element contains a vulcanization activator.

24. A layer of an unvulcanized rubber composition containing an organic peroxide and a polyfunctional polymerizable compound having a plurality of polymerizable groups is interposed between the rubber element and the resin element, under pressure. 10. The method according to claim 19, wherein the molding is carried out by heating.

25. The method according to claim 24, wherein at least one of the rubber element and the resin element contains a polyfunctional polymerizable compound having a plurality of polymerizable groups.

26. The method according to claim 19, wherein the resin element contains a vulcanization activator, and the amount of the vulcanization activator is 0.1 to 5 parts by weight based on 100 parts by weight of the resin element.