WO2004007194A1 - Composite et son procede de production - Google Patents

Composite et son procede de production Download PDF

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Publication number
WO2004007194A1
WO2004007194A1 PCT/JP2003/008569 JP0308569W WO2004007194A1 WO 2004007194 A1 WO2004007194 A1 WO 2004007194A1 JP 0308569 W JP0308569 W JP 0308569W WO 2004007194 A1 WO2004007194 A1 WO 2004007194A1
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WO
WIPO (PCT)
Prior art keywords
resin
rubber
group
weight
vulcanized
Prior art date
Application number
PCT/JP2003/008569
Other languages
English (en)
Japanese (ja)
Inventor
Toru Ikuta
Mitsuteru Mutsuda
Yasumasa Negoro
Original Assignee
Daicel-Degussa Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daicel-Degussa Ltd. filed Critical Daicel-Degussa Ltd.
Priority to AU2003252471A priority Critical patent/AU2003252471A1/en
Publication of WO2004007194A1 publication Critical patent/WO2004007194A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2319/00—Synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2398/00—Unspecified macromolecular compounds

Definitions

  • 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 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.
  • thermoplastic component such as a polyformaldehyde olefin polymer and a vulcanized rubber component compatible with the thermoplastic component are disclosed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • thermoplastic resin and rubber are limited in order to obtain high adhesive strength.
  • 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.
  • 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.
  • 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.
  • 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.
  • changing rubber formulations is often difficult in practice.
  • 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
  • the inventors of the present invention have conducted intensive studies in order to achieve the above-mentioned object.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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
  • 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 ⁇ P AC PM 3. hand,
  • E c indicates the orbital energy (e V) of the radical generator as a vulcanizing agent
  • 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 ⁇ M ⁇
  • C LUM0, n indicates the lowest unoccupied molecular orbital (LUMO) of the nth hydrogen atom. It indicates the molecular orbital coefficient
  • E LUM0 , n indicates the orbital energy (e V) of the LUMO.
  • At least one of the unvulcanized rubber composition and the resin member Contains a polyfunctional polymerizable compound having a plurality of polymerizable groups
  • 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 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.
  • 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.
  • the resin member examples 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.
  • the vulcanized rubber layer may be vulcanized with a sulfur-based vulcanizing agent.
  • 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.
  • 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.
  • 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.
  • the unvulcanized rubber or the semi-vulcanized rubber may be vulcanized, and the rubber element and the resin element may be molded if necessary.
  • 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.
  • the unvulcanized rubber composition layer containing the vulcanizing agent may be formed of a film or a coating material of the unvulcanized rubber composition.
  • 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.
  • 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.
  • 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.
  • at least one of the rubber element and the resin element may include a polyfunctional polymerizable compound having a plurality of polymerizable groups.
  • rubber means a vulcanized rubber layer Rubber or a rubber for forming a vulcanized rubber member (the rubber element).
  • resin is used to include a resin (the resin element) for forming a resin member.
  • 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 (Thermoplastic resin)
  • thermoplastic resin examples 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
  • thermoplastic resin examples 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.
  • polyamide resin examples include an aliphatic polyamide resin, an alicyclic polyamide resin, and an aromatic polyamide resin.
  • the alicyclic polyamide-based resin examples 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
  • 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).
  • a polyamide in which the diamine component is an aromatic component Condensates of aromatic diamines such as MXD-6 (such as meta-xylylenedi
  • dimer monoacid is further added to the dicarboxylic acid component.
  • 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.
  • a high-impact polyamide which has been subjected to high impact.
  • the ratio between the terminal NH 2 group and the terminal CO OH group is not particularly limited.
  • 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).
  • 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.
  • aromatic polyester resins polyalkylene ⁇ Relay preparative resin (e.g., polyethylene terephthalate ( ⁇ ⁇ ), polybutylene terephthalate evening rate ( ⁇ ⁇ ) 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
  • polyarylate resin for example, polyarylate resin obtained by polycondensation of bisphenols (such as bisphenol ⁇ ) 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.
  • 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 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)
  • 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.
  • 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.
  • 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.
  • the poly (thio) ether resins include polyoxyalkylene resins, polyphenylene ether resins, polysulfide resins (polythioether resins), and polyetherketone resins.
  • Preferred polyether resins include polyacetal resins, polyphenylene ether resins, polysulfide resins, and polyetherketone resins.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polysulfide resin is not particularly limited as long as it has a thio group (—S—) in a polymer chain.
  • a resin include a polyphenylene sulfide resin, a polydisulfide resin, a polyphenylene sulfide resin, a polyketone sulfide resin, and a polythioether sulfone resin.
  • 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.
  • Dihalogenobenzophenone 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.
  • 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).
  • aromatic polycarbonates obtained by the reaction of phosgene or carbonic acid diester (dialkyl carbonate such as diphenyl carbonate, dialkyl carbonate such as dimethyl carbonate).
  • 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.
  • 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).
  • dihalogenodiphenylsulfone such as dichlorophenylsulfone
  • bisphenols such as bisphenol A or a metal salt thereof.
  • An example is a sulfone resin (trade name: RADEL).
  • the polyurethane resin can be obtained by reacting a diisocyanate, a polyol (particularly, a diol) and, if necessary, a chain extender.
  • a diisocyanate as a diisocyanate
  • Aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate
  • alicyclic diisocyanates such as 1,4-cyclohexanediisocyanate and isophorone diisocyanate
  • phene Examples thereof include aromatic diisocyanates such as range isocyanate, tolylene diisocyanate, diphenylmethane-1,4'-diisocyanate, and aromatic aliphatic diisocyanates such as xylylene diisocyanate.
  • 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.
  • 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
  • Jiamin acids can also be used.
  • 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.
  • 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.
  • olefins such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (methylpentene-11), and copolymers of olefins and copolymerizable monomers.
  • ethylene-vinyl acetate copolymer ethylene- (meth) acrylic acid copolymer
  • ethylene- (meth) acrylate copolymer ethylene- (meth) acrylate copolymer
  • 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.
  • 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.
  • 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.).
  • Styrene resin examples include homo- or copolymers of styrene-based monomers (such as polystyrene, styrene-vinyltoluene copolymer, and styrene- ⁇ -methylstyrene copolymer), and copolymerizable monomers with styrene-based monomers.
  • styrene-based monomers such as polystyrene, styrene-vinyltoluene copolymer, and styrene- ⁇ -methylstyrene copolymer
  • 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
  • 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.
  • the compatible monomer include vinyl monomers such as vinyl acetate and vinyl chloride, and styrene monomers such as styrene and -methylstyrene.
  • 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)
  • 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
  • aliphatic polyether examples 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.
  • 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.
  • the block structure is not particularly limited, and the triblock structure, the multiblock structure, A star block structure or the like may be used.
  • thermoplastic elastomers include polyamide-based elastomers, polyester-based elastomers, polyurethane-based elastomers, polystyrene-based elastomers, and polyolefin-based elastomers.
  • 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 (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).
  • 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, ethylvin
  • 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;
  • thermoplastic resin having an unsaturated bond examples 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).
  • thermoplastic resin with unsaturated bond introduced by copolymerization or co-condensation
  • resin with unsaturated bond and resin Polymer blends examples 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).
  • 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
  • Preferred resins are the above-menti
  • 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.
  • 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
  • the following combinations can be exemplified.
  • the form in parentheses indicates the bonding form between the reactive group (A) and the reactive group (B).
  • 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).
  • 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.
  • 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).
  • the reactive group (B) may be used as the reactive group (B).
  • the monomer having the reactive group (B) is used as a copolymerization component to thereby form the reactive group (B). ) Can be introduced.
  • 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 [, (
  • 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.
  • epoxy group-containing compound For example, aryl glycidyl ether, glycidyl (meth) acrylate, and the like
  • isocyanate group compounds for example, vinyl isocyanate
  • the reactive group (B) may be introduced. May be used to modify or modify the resin.
  • 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.
  • the monomer having the reactive group (B) is usually used as a copolymer component to introduce the reactive group (B) in many cases.
  • the reactive group (B) can be easily introduced by a graft reaction of the polymerizable compound having the reactive group.
  • 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 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)
  • a method of co-condensing (or copolymerizing) unsaturated polyhydric alcohols such as
  • a monomer having a conjugated unsaturated bond eg, -1,3-butadiene, 2-methyl
  • — Copolymerization of optionally substituted conjugated C 4 _ 1 () alkadiene such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene and chloroprene).
  • 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].
  • thermoplastic resin (A) May be a saturated resin having no unsaturated bond or a resin having an unsaturated bond.
  • 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).
  • 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
  • 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
  • Resin (B) (weight ratio) 595-95 / 5, preferably 30Z70-95Z5, more preferably about 50Z50-95 / 5.
  • an unsaturated bond-containing rubber for example, polyoctenylene
  • 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.
  • (B) may form a polymer alloy (eg, a polymer alloy having a sea-island structure).
  • a polymer alloy eg, a polymer alloy having a sea-island structure
  • thermoplastic resin examples 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.
  • 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).
  • 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 (Thermosetting resin having a crosslinkable functional group)
  • thermosetting resin examples 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).
  • a functional group eg, a methylol group, an alkoxymethyl group, an epoxy group, an isocyanate group, etc.
  • thermosetting resins include polycondensation or addition condensation resins (phenolic resins, amino resins, epoxy resins, thermosetting polyimide resins, thermosetting polyurethane resins, silicone resins).
  • 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.
  • 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.
  • 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.
  • aldehydes examples 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.
  • 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).
  • 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).
  • 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.
  • 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).
  • thermosetting polyurethane resin examples 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).
  • 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.
  • 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.
  • 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.
  • an 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.
  • vinyl ester resin examples 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.
  • diaryl phthalate resin examples include resins obtained from diaryl phthalate monomers such as diaryl orthophthalate and diaryl isophthalate.
  • 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.
  • 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)].
  • 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 basic unit in the formula (1) means a model molecular structure formed by a polymer terminal and about 1 to 3 repeating units.
  • 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.
  • PBT polybutylene terephthalate evening rate
  • 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.
  • the radical generator 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,
  • 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
  • radical generation is considered.
  • 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.
  • thio group -S-
  • mercapto '(-SH) group alkylthio group
  • alkylthio group alkylthio group such as methylthio group, ethylthio group, etc.
  • sulfiel group sulfiel group
  • 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.
  • methylidyne group examples 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.
  • 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
  • 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).
  • the terminal NH 2 group Z terminal COOH group 1 1 (molar ratio)
  • 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.
  • 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.
  • 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.
  • a hydrogen atom at the terminal amino group for example, a hydrogen atom at the terminal amino group, a hydrogen atom bonded to a carbon atom at the ⁇ -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 ⁇ a hydrogen atom of a methylidine group
  • a hydrogen atom of a terminal amino group constitutes an active hydrogen atom.
  • polyester-based resins usually, (poly) oxyalkylene units
  • the hydrogen atom of the methylene group adjacent to the oxygen atom constitutes an active hydrogen atom.
  • 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 ⁇ ⁇ a hydrogen atom of a methylidyne group), particularly a hydrogen atom of a terminal amino group, constitutes an active hydrogen atom.
  • 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,
  • a hydrogen atom of a methyl group bonded to a benzene ring forms an active hydrogen atom
  • a polysulfide resin for example, a thio group in a main chain forms an active atom.
  • 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.
  • 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.
  • a hydrogen atom of an oxyalkylene unit constituting the soft phase may constitute an active hydrogen atom.
  • an amino group for example, an amino group constituting melamine, guanamine, etc.
  • an active hydrogen atom for example, an amino group constituting melamine, guanamine, etc.
  • 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 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).
  • cross-linking accelerator examples 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).
  • radical generators radiation 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.
  • 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.
  • 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.
  • the rubber member is obtained by molding (vulcanizing) a rubber composition containing a vulcanizing agent and rubber.
  • the type of the rubber is not particularly limited.
  • 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, fluoro rubber, silicone rubber, urethane rubber, epichlorohydrin
  • 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).
  • NR natural rubber
  • IIR isobutylene isoprene rubber
  • BR bush gen rubber
  • CR chloroprene rubber
  • NBR Acrylonitrile-butadiene rubber
  • NCR nitrile chloroprene rubber
  • NIR nitrile isoprene rubber
  • SBR styrene butadiene rubber
  • SB Block copolymers composed of styrene and butadiene blocks, etc.
  • SCR styrene chloroprene rubber
  • SIR styrene isoprene rubber
  • Gen-based rubber also includes hydrogenated rubber, for example, hydrogenated nitrile rubber (HNBR).
  • HNBR hydrogenated nitrile rubber
  • 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). %).
  • olefin rubber examples include, for example, ethylene propylene rubber (EPM), ethylene-propylene-gen rubber (such as EPDM), and polypropylene rubber.
  • EPM ethylene propylene rubber
  • EPDM ethylene-propylene-gen rubber
  • polypropylene rubber examples include, for example, 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.
  • fluorine rubber examples 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.
  • 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_ ⁇ (4- a) / 2 organopolysiloxane composed of units represented by.
  • 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.
  • 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
  • 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.
  • 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.
  • urethane rubber (U) examples include a polyester type urethane elastomer and a polyether type urethane elastomer.
  • modified rubber examples 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.
  • X-SBR carboxylated styrene butadiene rubber
  • X-NBR carboxylated nitrile rubber
  • X-EP (D) Rubbers having a carboxylic group or an acid anhydride group such as M) are included.
  • the rubber can be vulcanized with various vulcanizing agents, and the type of the vulcanizing agent is not particularly limited.
  • 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.
  • sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.
  • 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
  • thiurams tetramethylthiuram monosulfuric acid
  • T MTD tetramethylthiuram disulfide
  • TETD tetraethylthiuram disulfide
  • TB TD tetrabutylthiuram disulfide
  • DP TT dipentamethylenethiuram tetrasulfide
  • 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.), Period
  • 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.
  • 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,
  • 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.
  • a photopolymerization initiator can also be used as a radical generator.
  • 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).
  • 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, poly ⁇ -dinitrobenzene, modified phenolic resin (alkylphenol formaldehyde resin, brominated alkylphenol formaldehyde resin, etc.).
  • 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.
  • 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.
  • 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.
  • 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.
  • a vulcanizing agent of the same type (particularly the same type) as the vulcanizing agent used for vulcanizing the vulcanized rubber member.
  • 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). .
  • 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.
  • the vulcanization activator 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.
  • the resin is a polyamide resin
  • a radical generator and a vulcanization activator when 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.
  • the vulcanization activator examples 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
  • 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, ⁇ , ⁇ '— 3 —Methyl-1,4-phenylenedimaleimide, 4, 4' —Bis ( ⁇ , ⁇ , maleimide) diphenylmethane, 4, 4 ' 1-bis (N, N, 1-maleimide) diphenylsulfone, 4,4, -bis (N, ⁇ '-maleimide) diphenyl ether, etc.), aliphatic bismale-imide ( ⁇ , ⁇ '), 1, 2 — Ethylene bismaleimide, ⁇ , ⁇ '— 1, 3 — propylene bismaleimide, ⁇ , ⁇ ' — 1, 4-tetramethylene bismaleimide, etc.).
  • aromatic bismaleimides N, N'-1,3-phenylenediimide, N, N'-1,4
  • 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.
  • 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.
  • 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.
  • 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 ⁇ 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)]
  • 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.
  • the amount of the vulcanization activator is 0.1 per 100 parts by weight of at least one component selected from rubber and 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 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.
  • 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.
  • a vulcanization aid may be further used in order to increase the efficiency of adhesion.
  • 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.
  • 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.
  • 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.
  • the oligomer when used as a vulcanization aid, 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.
  • 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 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.
  • the rubber is silicone rubber
  • the most common filler added as a reinforcing agent is silica powder.
  • 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.
  • wet silica 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.
  • plasticizers phthalate esters, aliphatic dicarbonate esters, sulfur-containing plasticizers, polyester polymer plasticizers, etc.
  • 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.
  • 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.
  • 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)
  • 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.
  • 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.
  • the stabilizer may stabilize the resin or rubber. It is preferred to stabilize the sulfur activator.
  • an antioxidant including a heat-resistant processing stabilizer and a light stabilizer
  • a thermal polymerization inhibitor hydroquinones such as hydroquinone and methylhydroquinone
  • 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.
  • 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- Echir
  • 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,
  • 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-
  • 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
  • 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 (nonylphen
  • zwitterion-based antioxidants examples 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
  • 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).
  • 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.
  • 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.
  • 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).
  • 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 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.
  • 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.
  • 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.
  • the resin member and the vulcanized rubber member can be joined with extremely high joining strength.
  • thermoplastic resin of the resin member or the composition thereof is composed of a polyphenylene-based resin
  • the unvulcanized rubber of the vulcanized rubber layer or the composition thereof is composed of a styrene-gen copolymer rubber.
  • 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.
  • the polyphenylene ether-based resin may be modified or modified with a styrene-based resin.
  • 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.
  • 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.
  • 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
  • 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).
  • 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.
  • 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.
  • vulcanized rubber member means 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.
  • unsemi-vulcanized rubber material refers 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.
  • the rubber element 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.
  • 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).
  • a vulcanizing activator a polyfunctional polymerizable compound having a plurality of polymerizable groups.
  • the contents of the vulcanizing agent and the vulcanizing activator are as described above.
  • the resin constituting the resin member is a resin having the specific active atom (active hydrogen atom and hydrogen or active sulfur atom).
  • At least one of the unvulcanized rubber composition and the resin member contains a polyfunctional polymerizable compound having a plurality of polymerizable groups.
  • 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.
  • 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.
  • 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.
  • 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.
  • a liquid unvulcanized rubber composition for example, a solution or dispersion of an unvulcanized rubber composition (emulsion, suspension), etc.
  • An unvulcanized rubber layer can be formed by drying if necessary.
  • 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.
  • 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.
  • a resin composition 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).
  • a conventional multicolor molding machine multicolor injection molding machine, multilayer extruder, etc.
  • the resin composition and the unvulcanized rubber composition of the intermediate layer are vulcanized.
  • a more composite molded article can be obtained.
  • the resin composition and the unvulcanized rubber composition may be mixed.
  • a conventional molding machine such as an injection molding machine, an extrusion molding machine, or a hot press molding machine
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the resin molded body and the vulcanized rubber molded body can be used in a wide range of combinations.
  • a complex can be obtained in which the and are firmly joined.
  • 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.
  • 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.
  • the rubber member and the resin member are bonded with extremely high strength by vulcanization.
  • 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.
  • 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. .
  • 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.
  • 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 number of active hydrogens in PA612 (A3) is 0.8 per molecule.
  • Vestorannl900 manufactured by Degussa (Degusa) was used.
  • the number of active hydrogens per molecule is 6 or more.
  • Fortron 0220 A9 manufactured by Polyplastics Co., Ltd. was used.
  • the number of active sulfur per molecule is 6 or more.
  • 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]
  • NBR “Nipo 1 1 0 4 2” manufactured by Zeon Corporation
  • 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.
  • 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.
  • 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
  • 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 ka ⁇ X4010 ⁇ ⁇ " (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.
  • 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.
  • “* 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.
  • the resin / rubber layer obtained by the above method was cut into a width of 3 Om m, and the obtained test piece was subjected to a 180 ° peel test.
  • the adhesiveness was evaluated according to the following criteria.
  • a peeling interface occurs in the rubber layer or the rubber member (cohesive failure), and the destruction is 100% cohesive failure.
  • 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.

Abstract

Cette invention porte sur un composite résine/caoutchouc comprenant un élément caoutchouc vulcanisé et un élément résine, lesquels éléments sont liés l'un à l'autre par une couche de caoutchouc vulcanisé. Ce composite est produit selon un procédé consistant à mettre un élément caoutchouc et un élément résine en contact mutuel et sous pression au moyen d'une couche de caoutchouc non vulcanisé, laquelle couche de caoutchouc non vulcanisé contient un agent de vulcanisation ; puis à chauffer et à mouler ces éléments tout en maintenant le contact sous pression. L'élément résine peut comprendre une résine thermoplastique ou une résine renfermant un groupe réticulable, et peut comprendre une résine comprenant un atome actif. Les composants d'au moins une composition de caoutchouc non vulcanisé permettant de former la couche de caoutchouc vulcanisé et l'élément résine peuvent renfermer un composé polymérisable polyfonctionnel comportant de multiples groupes polymérisables. Cette invention permet ainsi d'obtenir un composite dans lequel l'élément résine et l'élément caoutchouc vulcanisé sont fortement liés l'un à l'autre dans une large gamme de combinaisons.
PCT/JP2003/008569 2002-07-12 2003-07-04 Composite et son procede de production WO2004007194A1 (fr)

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JP2002204295A JP2004042486A (ja) 2002-07-12 2002-07-12 複合体及びその製造方法
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US7875975B2 (en) 2000-08-18 2011-01-25 Polyic Gmbh & Co. Kg Organic integrated circuit completely encapsulated by multi-layered barrier and included in RFID tag
CN103525349A (zh) * 2013-09-23 2014-01-22 株洲时代新材料科技股份有限公司 一种热硫化胶粘剂及其制备方法
EP2915664A4 (fr) * 2012-11-01 2016-07-13 Nok Corp Composite résine-caoutchouc
CN106641482A (zh) * 2016-09-26 2017-05-10 中国科学院兰州化学物理研究所 复合管道及其制备工艺

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JP3839015B2 (ja) * 2003-10-10 2006-11-01 電気化学工業株式会社 クロロプレン系ゴム組成物とナイロンとの加硫接着体
JP3839014B2 (ja) * 2003-10-10 2006-11-01 電気化学工業株式会社 クロロプレン系ゴム組成物とナイロンとの加硫接着体
JP4754341B2 (ja) * 2005-12-06 2011-08-24 株式会社クラレ ジエン系ゴム接着用水添スチレン系エラストマー成形体
KR100662539B1 (ko) * 2005-12-30 2006-12-28 제일모직주식회사 연료전지 바이폴라 플레이트용 조성물
JP4978425B2 (ja) * 2007-10-29 2012-07-18 宇部興産株式会社 ポリアミド積層体
CN102610353A (zh) * 2011-01-24 2012-07-25 北京中科三环高技术股份有限公司 一种高取向度高性能各向异性柔性磁体的制备方法
CN102673056B (zh) * 2012-05-24 2014-07-09 北京化工大学 一种叠层网状热塑性弹性体及制备方法
CN105269899B (zh) * 2014-12-17 2018-03-30 刘瑾 一种饮料机缓冲垫及制备该饮料机缓冲垫的方法
CN105684725A (zh) * 2016-01-23 2016-06-22 中山安荞生物科技有限公司 一种优质牛樟芝菌种扩培装置
DE102016211368A1 (de) * 2016-06-24 2017-12-28 Continental Reifen Deutschland Gmbh Schwefelvernetzbare Kautschukmischung und Fahrzeugreifen
JP7181727B2 (ja) 2018-08-10 2022-12-01 ポリプラ・エボニック株式会社 複合成形体、及びその製造方法
CN110067293A (zh) * 2019-04-25 2019-07-30 广东景源建设工程有限公司 污水管道工程施工工艺
CN111923529A (zh) * 2020-09-23 2020-11-13 歌尔股份有限公司 一种复合振膜及其制备方法、以及发声装置
CN113214524B (zh) * 2021-06-11 2022-06-07 四川大学 耐摩擦高抗剪复合橡胶密封材料
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Publication number Priority date Publication date Assignee Title
US7875975B2 (en) 2000-08-18 2011-01-25 Polyic Gmbh & Co. Kg Organic integrated circuit completely encapsulated by multi-layered barrier and included in RFID tag
EP2915664A4 (fr) * 2012-11-01 2016-07-13 Nok Corp Composite résine-caoutchouc
CN103525349A (zh) * 2013-09-23 2014-01-22 株洲时代新材料科技股份有限公司 一种热硫化胶粘剂及其制备方法
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