WO2002098985A1

WO2002098985A1 - Composite dispersion and process for production thereof

Info

Publication number: WO2002098985A1
Application number: PCT/JP2002/004829
Authority: WO
Inventors: Toru Ikuta; Hajime Komada; Mitsuteru Mutsuda
Original assignee: Daicel-Degussa Ltd.
Priority date: 2001-05-30
Filing date: 2002-05-17
Publication date: 2002-12-12
Also published as: KR20030022329A; CN1464899A

Abstract

A composite dispersion essentially constituted of a continuous phase of a vulcanized rubber and a disperse phase of a resin can be produced by melt-kneading a resin and a green rubber (particularly a rubber composition containing a radical generator and a vulcanization promoter) together and molding the resulting compound while vulcanizing or cosslinking the green rubber. The above resin is one having active atoms (e.g., a thermoplastic resin such as polyamide resin, a thermosetting resin, or a crosslinked or cured resin). In the above composite dispersion, a rubber constitutes the matrix phase and a part of the dispersed resin particles come out to the surface. Therefore, the composite dispersion exhibits on the surface sliding properties or other characteristics inherent in resin, while keeping the characteristics inherent in rubber.

Description

Description Composite dispersion and method for producing the same

TECHNICAL FIELD The present invention relates to a composite dispersion (or composite dispersion member) composed of resin and rubber, which is useful as a machine component, an automobile component, and the like, and a method for producing the same. Background art

As the required quality of polymer materials increases, several properties (for example, tensile strength, tensile elasticity, hardness, abrasion resistance, heat resistance, cold resistance, oil resistance, chemical resistance, weather resistance, Materials with high formability) are expected. For example, there is a demand for a material having characteristics of rubber and characteristics different from those of rubber (for example, a low coefficient of friction, which is a characteristic of resin). Therefore, a composite having the characteristics of resin and rubber has been proposed by joining and integrating a resin molded member and a rubber molded member.

As a method of obtaining a composite, for example, a method of bonding a resin molded part and a rubber molded part using an adhesive is known.

Further, a method of directly joining a resin molded member and a rubber molded member has been proposed. For example, Japanese Patent Application Laid-Open No. 50-25682 discloses that a thermoplastic plastic and a vulcanized rubber compatible with the thermoplastic plastic are brought into frictional contact on a contact surface, and the plastic surface is melted and contacted. It has been proposed to obtain a composite by solidifying a thermoplastic resin component and a rubber component in this state. However, with this method, it is difficult to obtain a complex-shaped complex with high productivity.

Japanese Patent Application Laid-Open No. 9-124803 discloses an acrylonitrile-containing thermoplastic resin (such as AS or ABS resin) and an acrylonitrile-containing rubber. It has been proposed that a composite member is obtained by heating and contacting these components by utilizing the compatibility between a thermoplastic resin and rubber. However, this method is limited to resins and rubbers containing acrylonitrile, and the practicality is considerably narrowed.

Japanese Patent Application Laid-Open No. 8-156628 / 88 discloses that a resin composition containing an epoxy group is brought into contact with a vulcanized elastic rubber having a propyloxyl group or an acid anhydride group and vulcanized. There has been proposed a method of obtaining a composite member to be joined at a contact surface between a resin and a rubber by utilizing a chemical reaction between an epoxy group and a carboxyl group. However, in this method, since a chemical reaction between an epoxy group and a lipoxyl group is used, the types of resin and rubber are greatly restricted, and it is difficult to obtain a composite in a wide range.

Japanese Unexamined Patent Publications Nos. 2-154039, 3-133631 and 3-1318114 disclose a polyamide resin and a rubber component. In a method for producing a composite by vulcanizing in the presence of a vulcanizing system, a rubber containing a carboxyl group or an acid anhydride, a peroxide and a vulcanizing activator (ethylene glycol dimethacrylate, tri It has been proposed to use a rubber component containing an aryl silane compound and an alkoxysilane compound. In these documents, a polyamide type resin having more terminal amino groups than terminal carboxyl groups is mainly used as an aliphatic polyamide resin. That is, the reaction between an amino group and a carboxyl group or an acid anhydride group is utilized. For this reason, the types of resin and rubber are greatly restricted, and it is difficult to obtain a composite of resin and rubber in a wide range.

Japanese Patent Application Laid-Open No. Hei 7-11013 discloses a polyamide molding by contacting a boriamid molded body, rubber, and a rubber band containing a peroxide vulcanizing agent and a silane compound to vulcanize. A method for obtaining a composite member of a body and a vulcanized rubber has been proposed.

However, the composite obtained by these methods is composed of a resin member and a rubber member. And the contact surface. Therefore, the surface of the composite shows only one property of resin and rubber, and cannot show both properties of resin and rubber.

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

Another object of the present invention is to provide a composite dispersion capable of effectively exhibiting characteristics of both a resin and a rubber, and a method for producing the same.

It is still another object of the present invention to provide a composite dispersion having the properties of a rubber and exhibiting the properties of a resin effectively on the surface, and a method for producing the same. Disclosure of the invention

The present inventors have conducted intensive studies to achieve the above object, and as a result, by kneading and molding a rubber and a resin, a vulcanized or crosslinked vulcanized rubber phase and a resin phase are strongly joined, The present inventors have found that the properties of both resin and rubber are effectively exhibited, and completed the present invention.

That is, in the composite dispersion of the present invention, the vulcanized rubber phase constitutes a continuous phase and the resin phase constitutes a dispersed phase, and the vulcanized rubber phase and the resin phase are directly joined. In addition, "direct bonding" means "the vulcanized rubber phase and the resin phase are adhered to each other without using an adhesive, and when both sheet-like phases are mechanically separated, the rubber phase A state in which peeling proceeds with cohesive failure ”.

The composite dispersion may form a sea-island structure with the vulcanized rubber phase and the resin phase. Further, the dispersed phase particles may be partially exposed on the surface.

Further, the resin phase may be composed of at least one of a thermoplastic resin and a thermosetting resin. The resin phase includes various resins, for example, a polyamide resin, a polyester resin, and a poly (thio) ether. Resin, polycarbonate resin, polyimide resin, polysulfone resin, polyurethane resin, polyolefin resin, halogen-containing resin, styrene resin, (meth) acrylic resin, thermoplastic elastomer, phenol Resin, amino resin, epoxy resin, silicone resin, thermosetting polyimide resin, thermosetting polyurethane resin, thermosetting acrylic resin, vinyl ester resin, unsaturated polyester resin, diaryl It can be composed of a phthalate resin or the like. The rubber phase can be used in a wide range, and can be composed of, for example, a diene rubber, an olefin rubber, an acrylic rubber, a fluorine rubber, a silicone rubber, a urethane rubber, or the like. In the composite dispersion, at least one of the vulcanized rubber phase and the resin phase may be formed of a composition containing a vulcanizing agent, and the vulcanizing agent may be a radical generator, sulfur, or the like.

The resin phase has a high activity with respect to a radical generator, a hydrogen atom and a specific orbital interaction energy coefficient S by the molecular orbital method represented by the following formula (1) of not less than 0.006 and Z Alternatively, it may be composed of a resin having at least two sulfur atoms per molecule on average.

° ⁼ H0M0.il) z I ^ c ™-^ HOMO, n I +, CajM0, n IL _c- L _LUMOll | (1)

(Where E _e , C war _n , E sleep, „, C stroke, 画, and E occupation _n are all values calculated by the semi-empirical molecular orbital method MO PACPM 3, and E _e is Indicates the orbital energy (eV) of the radical of the radical generator, and C Sub. _N is the number of the highest occupied molecular orbital (HOMO) of the nth hydrogen atom and Z or sulfur atom constituting the basic unit of the resin. a molecular orbital coefficient, E picture .. _n molecular orbital coefficients of indicate the orbital energy (e V) of the HOMO, C _n is the lowest unoccupied molecular orbital of the n-th hydrogen atom and / or sulfur atom (LUMO) 、 _Ωι „.„ Indicates the orbital energy (eV) of the L UMO)

Further, the resin phase is at least one kind selected from a thermoplastic resin having an unsaturated bond and a thermosetting resin having a bridging functional group. It may be composed of a crosslinkable resin. The thermoplastic resin having an unsaturated bond may have any one of the following aspects (1) to (3), wherein the concentration of the unsaturated bond is 0.01 to 6 with respect to 1 kg of the resin. It may be about 6 moles.

(1) Formed by the reaction between a polymerizable compound having a reactive group (A) and an unsaturated bond and a thermoplastic resin having a reactive group (B) reactive with the reactive group (A). Resin

(2) Thermoplastic resin with unsaturated bonds introduced by copolymerization or co-condensation

(3) Polymer blend composed of resin having unsaturated bond and resin

Vulcanizing agents include radical generators such as organic peroxides, azo compounds, sulfur-containing organic compounds, and sulfur. At least one component of the unvulcanized rubber and the resin contains a vulcanization activator, for example, an organic compound having at least two polymerizable unsaturated bonds in one molecule. (Unvulcanized rubber) and a resin are kneaded and molded to produce a composite dispersion composed of a vulcanized rubber phase and a resin phase. In this method, at least one of the rubber and the resin may contain a vulcanizing agent. The resin may be used in the form of a powder.

In the present invention, the resin includes a graft copolymer containing a rubber component (for example, HIPS, ABS resin, etc.). BEST MODE FOR CARRYING OUT THE INVENTION

[Resin]

As the resin, a thermoplastic resin or a thermosetting resin can be used. Examples of the thermoplastic resin include a polyamide resin, a polyester resin, a polyurethane resin, and a poly (thio) ether resin (polyester resin). Condensation of Riacetal resin, Polyphenylene ether resin, Polysulfide resin, Polyetherketone resin), Polycarbonate resin, Polyimide resin, Polysulfone resin, Polyurethane resin -Based thermoplastic resins; vinyl-based thermoplastics such as polyolefin-based resins, (meth) acrylic-based resins, styrene-based resins, octogen-containing resins, and vinyl-based resins (for example, polyvinyl acetate, polyvinyl alcohol, etc.) Resin: thermoplastic elastomers and the like can be exemplified. Examples of the thermosetting resin include a polycondensation or addition condensation type resin such as a phenol resin, an amino resin, an epoxy resin, a silicone resin, a thermosetting polyimide resin, and a thermosetting polyurethane resin; Examples thereof include addition polymerization resins such as acrylic resins, vinyl ester resins, unsaturated polyester resins, and diaryl phthalate resins.

These resins (thermoplastic resins, thermosetting resins) can be used alone or in combination of two or more.

The resin is preferably a resin having a high activity with respect to a vulcanizing agent (particularly, a radical generator). Examples of such a resin include (i) a resin having an active atom, (ii) a resin having a crosslinkable group, and (iii) a resin having an active atom and a crosslinkable group. Simply referred to as resin or active resin). By using the active atom and / or the resin having a crosslinkable group (active resin), even if a wide range of rubber is selected as the rubber component, the rubber phase and the resin phase can be reliably bonded.

(Resin having active atoms)

In the present invention, the term "active atom" refers to an atom having high activity for a radical generator (for example, an active hydrogen atom or an active sulfur atom). Specifically, the resin can be selected according to the type of the radical generator. For example, the orbital interaction energy coefficient S represented by the following formula (1) is a constant value (for example, 0.06, Preferably, it may have 0.08) or more active atoms. Preferred orbital interaction energies of active atoms The coefficient S is about 0.006 to 0.06, preferably about 0.007 to 0.05 (particularly 0.01 to 0.045). The number of active atoms depends on the binding site (terminal, branched chain, main chain, etc.) of the functional group having an active atom. For example, in one molecule of resin, an average of two or more (2 to 100,000) Number), preferably 2.5 or more (about 2.5 to 500) on average, more preferably 3 or more (about 3 to 1000) on average. The number of active atoms in one resin molecule is usually about 2 to 100 (preferably 2.5 to 50, more preferably 3 to 25, particularly 3 to 20).

° ~ (. Occupation, IL _c- l L n τ (C occupation _n ), I — L _L painting, η I (丄)

(Wherein, E _c, C Yue., _N, E image., _N, C _L謹, _n, E _L image, _n is either also calculated by a semiempirical molecular orbital method MO PACPM 3 values Te, E _c representing an orbital radical radical generator Enerugi _{(e V), C H (} mn the highest occupied molecular orbital of the n-th hydrogen atom and Z or sulfur atom constituting the basic unit of the resin (HOMO) indicates the molecular orbital coefficient, E _H瞧, _n indicates the orbital energy (e V) of the HOMO, and CL _L , _n indicates the n-th hydrogen atom and the lowest vacant molecule of Z or sulfur atom. Indicates the molecular orbital coefficient of the orbit (L UM 0),

Indicates the orbital energy of the L UMO-(eV))

MO PAC PM 3 in equation (1) is one of the molecular orbital methods (MO). The molecular orbital method is one of the approximation methods for discussing the electronic state of a molecule, and is an empirical method such as the Huckel method, a semi-empirical method that enhances the approximation of the Huckel method, and a non-empirical method for obtaining the molecular orbital function only by strict calculations There are three main methods. In recent years, with the development of computers, semi-empirical methods and ab initio methods have become the main methods. Molecular orbital method is one of the most powerful ways to relate molecular structure and its chemical reactivity. For example, the number of registrations related to the molecular orbital method in the Japan Science and Technology Literature Information Database (JOIS) is about 530,000 when the keyword is searched as “molecular orbital method” (period: 1980- (May 2000). MO PACPM 3 is one of the semi-empirical methods. This is the core of the DO (Neglect of Diatomic Differential Overlap) method.

MOPAC PM 3 is mainly used for studying the reaction of organic compounds. Many documents and books [Molecular Orbital Method M OP AC Guidebook] (Tsuneo Hirano, Kazutoshi Tanabe, Kaibundo, 1999) 1st year), "Sankei * Introduction to Quantum Chemistry" (Seijiro Yonezawa et al., Chemistry Dojin, 1983), "Computational Chemistry Guidebook" (Translated by Eiji Osawa et al., TimClark, Maruzen, 1980) Year)].

The basic unit in the formula (1) means a model molecular structure formed by a terminal of a polymer and about 1 to 3 repeating units. That is, when calculating with MO PAC PM 3 for a polymer compound, it is difficult to calculate for the molecule itself because the number of atoms constituting the molecule is too large. Therefore, the calculation may be performed on a molecular structure model (basic unit) formed of the terminal of the polymer and about 2 to 3 repeating units. For example, polybutylene terephthalate molecular structure of Ichito (PBT) (repeating unit), in general, the chemical formula one _{_{(CH 2 - CH 2 - CH}} 2 -CH 2 -0-C (= 0) - C 6 H 4 - C (= O) - O ) n - but represented by, in the formula (1), the basic unit, conveniently _{_{_{HO- CH 2 _CH 2 - CH 2}}} - CH 2 -〇- C (= 0 )-C ₆ H ₄ -C (= O) -OH.

The orbital interaction energy coefficient S in equation (1) is sometimes referred to as the reactivity index, is defined and described in various books, etc., and is extremely commonly used when discussing chemical reactivity. It is a parameter. For example, “Introductory Frontier Orbit Theory” (p. 72, Shinichi Yamabe and Toshi Inagaki, Kodansha Sentifik, 1989) states that the orbital interaction energy coefficient S is When interacting, (a) the smaller the energy difference, and (b) the larger the overlap, the stronger the interaction. " The formula (1) is based on the late Nobel Prize winner Hiroshi Fukui Based on the concept of superdelocalozabi 1 ity (S r) published in 1954 by Kato (see "To use the molecular orbital method", page 71, Minoru Imoto, Kagaku Dojin, 1986) ), S r, and similar expressions (1) have been derived in various books and literatures. It is important to note that the molecular orbital method is a widely accepted method for discussing molecular structure and its chemical reactivity ₍ therefore, the orbital interaction energy coefficient S defined by equation (1)) [1 / eV] is not merely a conceptual value, but a value that has the same meaning as the parameters and physical properties (molecular weight, functional groups, etc.) for specifying the material.

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

As the hydrogen atom (active hydrogen atom) having an orbital interaction energy coefficient S of a certain value (eg, 0.06) or more, 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 groups, Ami de binding (-NH-) group, etc.), methyl (-. CH ₃₎ group, methylene (one CH Hydrogen atoms such as _2- ) group (main chain or terminal methylene group) and methylidine (one CH =) group (main chain or terminal methylidine group). As the sulfur atom (active sulfur atom) having an orbital interaction energy coefficient S of a certain value (for example, 0.06) or more, when the radical generator is an organic peroxide, a thio group (1-S -), mercapto (- SH) group, an alkylthio group (methylthio group, C 1 such Echiruchio groups - such as ₄ alkylthio group), a sulfinyl group (- a sulfur atom, such as SO-). 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 of a linear or branched alkylene group forming a main chain or a side chain, and a (poly) oxyalkylene unit such as a (poly) oxymethylene unit and a (poly) oxethylene unit. And a methylene group adjacent to a nitrogen atom such as an amino group or an imino group. Examples of the methylidyne group include an a-position methylidyne group adjacent to an amino group or an imino group, for example, an a-position methylidyne group with respect to the amino group of the aminocycloalkyl group.

The resin having active atoms only needs to have a plurality of (for example, two or more on average) active molecules in one molecule. That is, the resin is generally not a single molecule, but a mixture of a number of molecules that differ somewhat in structure, chain length, and the like. Therefore, it is not necessary that every molecule has a plurality of active atoms, and it is sufficient if the average number of active atoms per molecule is 2 or more when calculated for a plurality of expected main basic units. For example, repeating units - contained in the polymer having the (made of Polyamide 6 6) - (NH- (CH 2) 6-NH-C (= 0) - (CH 2) 4 - (C = 0)) n the number of active hydrogen atoms, the model basic unit _{_{NH 2 - (CH 2) 6}} -NH-C (= O) one _{_{(CH 2) 4 -C (=}} O) can be calculated on the basis of -OH, a radical onset raw When the agent is an organic peroxide, the two hydrogen atoms of the terminal NH ₂ group are active hydrogen atoms' (ie, S≥0.006). In this case, the average number N of active hydrogen atoms in one molecule of the polyamide 66 is determined by the ratio of terminal NH ₂ groups to terminal C〇〇H groups of the polymer (polyamide 66) as an aggregate. It can be calculated based on the following equation (2).

N = 2 X A

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

For example, when the terminal NH ₂ group Z terminal CO OH group = 1/1 (molar ratio), the number of terminal NH ₂ groups in one molecule A = 1, the active hydrogen source in one molecule The number of children is N = 2. When the terminal NH ₂ group / terminal COOH group = 1/2 (molar ratio), the number of terminal NH ₂ groups in one molecule A = 23, the number of active hydrogen atoms in one molecule N = 4 / 3 pieces.

When the resin is a mixed resin composed of a plurality of resins having different numbers of active atoms, the number of active atoms of the mixed resin can be represented by an average value of the number of active atoms of each resin. In other words, the number of active atoms is individually calculated from the basic unit of each resin constituting the mixed resin, and the average of the number of active atoms is calculated based on the weight ratio of each resin. Can be calculated. For example, the mixed resin is composed of the aforementioned N = 2 polyamides 66 (A) and the N = 4/3 polyamides 66 (B), and (A) / (B) When = 1/1 (molar ratio), the number of active atoms in one molecule of the mixed resin can be regarded as N-5Z3. Further, the mixed resin is composed of the N = 2 polyamides 66 (A) and a polyamide 66 (C) having all lipoxyl groups (that is, N = 0) at all terminals, When A) / (C) = 3/1 (molar ratio), the number of active atoms in one mixed resin molecule can be regarded as N = 3Z2.

Examples of the thermoplastic resin having such an active atom include, among the resins exemplified above, 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, and the like.

Further, the resin having no plurality of active atoms may be used as a modified resin into which active atoms (an amino group, an oxyalkylene group, etc.) are introduced. Examples of such thermoplastic resins include pinyl polymer resins [(meth) acrylic resins (polymethyl methacrylate, methyl methacrylate-styrene copolymer (MS resin), polyacrylonitrile, etc.). ), Styrene resin (polystyrene; AS resin, styrene copolymer such as styrene-methyl methacrylate copolymer); H Styrene-based graft copolymers such as IPS and ABS resins, etc., homo- or copolymers of halogen-containing monomers (polyvinyl chloride, vinylidene chloride copolymer, etc.), vinyl-based resins (polyvinyl acetate, Condensed resins (polyphenol A (bisphenol A-type polycarbonate resin, etc.), polyimide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, poly) Arylate resin).

In the vinyl polymer resin, for example, a vinyl monomer is copolymerized with a monomer having a propyloxyl group or an acid anhydride group such as (meth) acrylic acid or maleic anhydride to give a vinyl polymer resin. A sulfoxyl group or an acid anhydride group is introduced and, if necessary, reacted with thionyl chloride to form an acid chloride group. Ammonia, monosubstituted amines (monoalkylamine, monoarylamine, etc.) and the above examples The modified resin may be produced by reacting with a diamine to introduce an amino group. Further, (poly) oxyalkylene glycol mono (methyl) acrylate or (poly) oxyalkylene glycol monoalkyl ether (meth) acrylate may be copolymerized with the above-mentioned vinyl monomer, or may be used as a vinyl polymer-based resin. By graft polymerization, an active hydrogen atom may be introduced for modification.

Further, not only a vinyl polymer resin but also a condensation resin, a carboxyl group or an acid anhydride group-containing monomer is graft-polymerized on the resin to introduce a carboxyl group or an acid anhydride group into the resin. In the same manner as described above, if necessary, it is reacted with thionyl chloride to generate an acid sulfide group, and then modified by introducing an amino group by reacting with ammonia and monosubstituted amines ゃ the diamines exemplified above. Good.

Further, the resin may be composed of a resin composition of a resin (or a modified resin) containing the active atoms at a predetermined concentration and another resin. Other thermoplastic resins include an unmodified thermoplastic resin corresponding to the modified resin, for example, a styrene resin, a (meth) acrylic resin, and a halogen-containing monomer. Homo- or copolymers (such as fluororesins), vinyl resins, polycarbonate resins, polyimide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyarylate resins, liquid crystalline polyester resins And so on.

In the case of thermosetting resins (for example, amino resins such as urea resin, aniline resin, melamine resin and guanamine resin, and condensation resins such as phenol resin and epoxy resin), a curing agent having an active atom is used. Active atoms may be introduced by crosslinking or curing. The hardener can be selected according to the type of the resin. Examples thereof include amine hardeners (for example, aliphatic polyamines such as triethylenetetramine, aromatic polyamines such as metaphenylenediamine and diaminodiphenylmethane), and amines. Hardening agents (for example, polyamide amines).

In addition polymerization resins such as radical polymerization with low active atom concentration (for example, unsaturated polyester, vinyl ester resin, diaryl phthalate resin, etc.), the active atom is copolymerized with a monomer having an active atom. May be introduced. The monomer having an active atom, for example, Okishi C ₂ - ₄ monomer having an alkylene unit ((poly) O · The shea ethylene glycol mono (meth) Akuri rate Bok such as (poly) O alkoxy alkylene glycol mono (Poly) oxyalkylenedaricol monoalkyl ether (methyl) acrylate, such as (meth) acrylate, (poly) oxyethylene glycol monomethyl ether (meth) acrylate, polyfunctional monomer, for example, (Poly) oxyalkylene glycol di (meth) acrylate such as (poly) oxyethylene glycol di (meth) acrylate, di (meth) acrylate of bisphenol A-alkylene oxide adduct) and amide bond Monomer (acrylamide, methylene-bis (meth) Acrylamide, and acrylamides such as 1,1-bisacrylamide dohethane). In the thermosetting acrylic resin, an amino-based resin (for example, melamine resin, guanamine resin, etc.) may be used as a cross-linking agent to crosslink and introduce active atoms. The active atom may be introduced by copolymerizing with a polyfunctional polymerizable monomer having an active atom.

The proportion of the resin having an active atom is about 30 to 100% by weight, preferably about 50 to 100% by weight, and more preferably about 80 to 100% by weight, based on the whole resin component. .

(Resin having crosslinkable group)

A resin having a crosslinkable group (hereinafter sometimes referred to as a crosslinkable resin) includes a thermoplastic resin having an unsaturated bond (polymerizable or crosslinkable unsaturated bond) and a thermosetting resin having a crosslinkable functional group. Can be roughly divided into The crosslinkable resin may have the unsaturated bond and the crosslinkable functional group. When such a crosslinkable resin is used, the crosslinking reaction proceeds at the interface between the rubber component and the resin component in the vulcanization of the rubber component. The rubber phase (or vulcanized rubber phase) and the resin phase can be joined firmly.

In a thermoplastic resin having an unsaturated bond, the unsaturated bond is not particularly limited as long as it can be activated by a vulcanizing agent (such as a radical generator), and exhibits a crosslinkability or a polymerizability upon application of heat or light. Various bonds (particularly, polymerizable unsaturated bonds) can be exemplified. Such an unsaturated bond or a unit having an unsaturated bond includes a linking group (ester bond (-oc (= o)-,-

C (= 0) 0-), amide bond (-NHC0-, -C0NH-), imino bond (-book-), urethane bond (-NHC (= 0) 0-), urea bond, piuret bond ) May be bonded to the thermoplastic resin. Further, the unsaturated bond or the unit thereof may be located at the terminal (main chain terminal) and Z or a side chain of the resin, or may be located at the main chain of the resin, or both of them. May be located.

Examples of the group having an unsaturated bond include a vinyl group, C ₂ _ ₆ alkenyl groups such as benzyl, isopropyl, 1-butenyl, aryl, 2-methyl-2-propenyl and 2-butenyl; 4-vinylphenyl, 4-isopropyl C _2, such as Nirufueniru the group - ₆ alkenyl _ C ₆ - _2. Ariru group; C _6, such as a styryl group - _2. Ariru - C ₂ - ₆ alkenyl group; Echiniru group, 1 one propynyl group,

1-Petinyl group, Propargyl group, 2-Petinyl group, 1-Methyl-

2-propynyl C ₂ such groups - ₆ alkynyl group; a vinylene group, methyl vinylene group, Echirubi two alkylene groups, 1, 2-Jimechirubi two mono- or di-C i-e alkyl vinylene group such as alkylene, click port Robiniren group such as A vinylene group which may have a substituent such as a halovinylene group; a vinylidene group; an ethynylene group;

Specific embodiments of the thermoplastic resin having an unsaturated bond include, for example, the following embodiments (1) to (4).

(3) Polymer blend composed of resin having unsaturated bond and resin

(4) Various organic reactions (for example, introduction of Bier group by Leppe reaction using acetylene, introduction of unsaturated bond using organometallic reagent such as vinyl lithium, introduction of unsaturated bond by coupling reaction, etc. ) Thermoplastic resin with unsaturated bond introduced

Among these resins, preferred resins are the resins (1), (2), and (3).

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

(A1) hydroxyl group:

(B) carbonyl group or its acid anhydride group (ester bond), isocyanate group (ester bond)

(A2) Carboxyl group or its anhydride group:

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

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

(A4) Epoxy group:

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

(A5) Isocyanate group:

(B) Hydroxyl group (ester bond), carboxyl group or its anhydride group (amide bond), amino group (amide bond)

As the polymerizable compound, arsenate Dorokishiru group-containing compound [for example, § Lil alcohol, 2 - butene - 1 - ol, 3-buten - such as 2-Saiichi Le C ₃ - _e alkenol, C 3, such as propargyl alcohol - ₆ alkyno Ichiru, 2- arsenide Dorokishechiru (meth) Akuri rate Bok, 2-hydroxycarboxylic propyl (meth) Akuri, single Bok, C _2, such as butanediol mono (meth) § click Li rate - ₆ alkylene glycol mono ( Acrylate, diethylene glycol mono (meth) acrylate Polyoxy C ₂ such bets - ₆ alkylene glycol mono (meth) § click relays Bok, 4-hydroxystyrene, 4-hydroxy-alpha - C _2, such as methyl styrene - ₆ alkenyl phenol, dihydroxy styrene Ren, vinylnaphthol etc.], the force Rupokishiru group or acid anhydride group-containing compound [e.g., (meth) acrylic acid, black Tonsan, 3-butenoic acid of any C ₃ _ ₆ alkene Cal Pont acid, Itakon acid, maleic acid, C such as anhydrous Ma maleic acid ₄ _ ₈ alkene dicarboxylic acid or anhydride thereof, unsaturated aromatic carboxylic acid such as vinyl Le benzoate, Kei cinnamic acid, Amino group-containing compound (e.g., C _3, such as Ariruamin - ₆ Arukeniruami down, 4 one Aminostyrene, diaminostyrene, etc.), epoxy group-containing compounds (for example, aryl glycidyl ether, Examples thereof include ricidyl (meth) acrylate and the like, and isocyanate group compounds (eg, vinyl isocyanate and the like).

The resin (1) may be modified by introducing a reactive group (B). The method for introducing the reactive group (B) into the resin includes: (i) a monomer having the reactive group (B) in the production of the resin (for example, the polymerizable compound described above); (Or monomers or oligomers that are the raw materials for the resin), and (ii) various organic reactions such as introduction of carboxyl groups by oxidation, halogenation, and grafting of polymerizable monomers. Available. In the case of a pinyl polymer resin, the reactive group (B) is often introduced by using a monomer having the reactive group (B) as a copolymerization component in many cases. In any resin including the above, the reactive group (B) can be easily introduced by a graft reaction of the polymerizable compound having the reactive group.

In the resin (2), as a method for introducing an unsaturated bond, for example, in the preparation of a condensation resin (for example, a polyamide resin, a polyester resin, or the like), as a part of the reaction component (comonomer), Compounds having a functional unsaturated bond [e.g., aliphatic unsaturated dicals Unsaturated polyvalents such as boric acid (maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous itaconic acid, citraconic acid, citraconic anhydride, mesaconic acid, etc .; aliphatic unsaturated dicarboxylic acid, etc.) Carboxylic acid; unsaturated polyhydric alcohols such as aliphatic unsaturated diols (eg, C 4-such as 2-butene-1,4-diol; aliphatic unsaturated diols)] ) Can be exemplified. In addition-polymerized resins (for example, olefin resins), a monomer having a conjugated unsaturated bond (for example, 1,3-butadiene, 2- Methacrylates such as methyl-1,3-butanediene, 2,3-dimethyl-1,3-butadiene, and conjugated C ₄ —i, which may have substituents such as alkadiene). Can be illustrated.

In the resin (3), the thermoplastic resin (A) and the resin (B) having an unsaturated bond are mixed to form a polymer blend (or a resin composition), so that 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). Further, the thermoplastic resin (A) may be a resin having no unsaturated bond or a resin having an unsaturated bond.

Examples of the resin (B) having an unsaturated bond include a thermoplastic resin having an unsaturated bond introduced therein, such as the above-mentioned embodiments (1), (2) and (4), and a rubber containing an unsaturated bond (for example, polybutadiene, isoprene, polygonal pen Tenama, Poriheputenama one, polyoctenamer, poly (3-methylation old Kutenama), Poridesenama, poly (three to Mechirudesenama one), poly C ₄ _ E ₅ Aruke two lens such as polymethyl Dodesenama, butadiene one Isopuren copolymer Copolymers of C ₄ —e ₅ alkadiene, rubber-modified polyolefins such as butadiene-modified polyethylene, etc.). Incidentally, the poly-C ₄ - i ₅ Aruke two Ren, Shikuroo Refuin compounds (e.g., cyclopentene, consequent opening heptene, Shikuroo period, cyclodecene, etc. Good C ₅ _ _2. Shikuroorefi emission may have a substituent such as cyclododecene) metathesis polymerization, Poria Luque two lens (e.g., polybutadiene, etc. ) May be obtained by partial hydrogenation.

In the resin (4), the ratio of the resin (B) is within a range where unsaturated bonds can be introduced into the polymer blend at a predetermined concentration, for example, resin (A) / resin (B) (weight ratio) = 5 95 to 95/5, preferably 30/70 to 95Z5, more preferably about 50/50 to 95/5. When an unsaturated bond-containing rubber (for example, polyoctylene) is used as the resin (B), the ratio of the resin (B) can be selected within a range that does not impair the properties of the resin (A). , Resin (A) / resin (B) (weight ratio) = 50/50 to 95Z5, preferably 60/40 to 955, more preferably 70Z30 to 95Z5 It is about.

The number of unsaturated bonds is, for example, 0.1 or more (for example, 0.1 to 100) on average per resin molecule, and preferably 1 or more (for example, 1 to 100). 0), more preferably an average of 2 or more (for example, about 2 to 50). The concentration of the unsaturated bond is, for example, about 0.001 to 6.6 mol, preferably about 0.01 to 4 mol, more preferably about 0.02 to 2 mol, based on 1 kg of the resin. is there.

Examples of the thermosetting resin having a crosslinkable functional group include functional groups that exhibit crosslinkability or curability in the presence of a crosslinking agent (or a curing agent) (for example, a methylol group, an alkoxymethyl group, an epoxy group, an isocyanate group). And the like. Examples of such thermosetting resins include polycondensation or addition condensation resins (phenol resins, amino resins, epoxy resins, thermosetting polyimide resins, thermosetting polyurethan resins, silicone resins). And the like, and addition polymerization resins (unsaturated polyester resins, vinyl ester resins, diaryl phthalate resins, thermosetting acrylic resins, etc.). These resins having an active atom or a crosslinkable group 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.

Hereinafter, examples of preferred thermoplastic resins and thermosetting resins will be described.

(Thermoplastic resin)

(1) Polyamide resin

Polyamide resins have an amide bond due to polycondensation of a carboxyl group and an amino group, and include, for example, an aliphatic polyamide resin, an alicyclic polyamide resin, an aromatic polyamide resin, and the like. In general, an aliphatic polyamide resin is used. Examples of the aliphatic polyamide resin include an aliphatic diamine component (e.g., tetramethylene diamine and hexamethylene diamine; alkylenediamine) and an aliphatic dicarboxylic acid component (adipic acid, sebacic acid, dodecane). C ₄ _ _2, such as diacids. alkylene such as carboxylic acid) and a condensate of (e.g., made of polyamide 4 6, made of polyamide 6 6, made of polyamide 6 1 0, made of polyamide 6 1 2, port Riami de 1 0 1 0 , made of polyamide 1 0 1 2, etc. made of polyamide 1 2 1 2) using a ring-opening polymerization of lactams, lactam (.epsilon. force caprolactam, C _4, such as ω one laurolactam -. etc. _{2 Q-lactam)} or Aminokarubo phosphate (number of carbon atoms in such ω- aminoundecanoic acid C ₄ _ _2. Aminokarubo like phosphate) homo- or copolymer (e.g., made of polyamide 6, made of polyamide 1 1, such as made of polyamide 1 2), this Copolymers obtained by copolymerizing these polyamide components (for example, polyamide 6Z11, polyamide 6/12, polyamide 66/11, polyamide 66/12, etc.) are examples. Can be

Examples of the alicyclic polyamide-based resin include a polyamide in which at least a part of the aliphatic diamine component and / or the alicyclic dicarboxylic acid component is replaced with an alicyclic diamine and / or an alicyclic dicarboxylic acid. Ceremony I can do it. The alicyclic polyamide includes, for example, the aliphatic dicarboxylic acid component and the alicyclic diamine component (C ₅ — such as cyclohexyldiamine).

8 cycloalkyldiamine; bis (aminocyclohexyl) methane,

Condensates with bis (aminocyclohexyl) alkanes such as 2,2-bis (aminocyclylhexyl) propane

Examples of the aromatic polyamide-based resin include polyamides in which at least one of the aliphatic diamine component and the aliphatic dicarboxylic acid component has an aromatic component. Aromatic polyamides include, for example, polyamides in which the diamine component has an aromatic component (eg, a condensate of an aromatic diamine such as MXD-6 (eg, meta-xylylenediamine) with an aliphatic dicarboxylic acid), Polyamides in which the acid component has an aromatic component [such as a condensate of an aliphatic diamine (such as trimethylhexamethylene diamine) and an aromatic dicarboxylic acid (such as terephthalic acid or isophthalic acid)], a diamine component, and a dicarboxylic acid component And polyamides (eg, wholly aromatic polyamides such as poly (m-phenyleneisophthalamide)) that both have aromatic components.

Examples of the polyamide resin include a polyamide containing dimer monoacid as a dicarboxylic acid component, a polyamide containing a small amount of a polyfunctional polyamine and / or a polycarboxylic acid component, and having a branched chain structure and a modified polyamide. (N-alkoxymethylpolyamide, etc.), high impact-resistant polyamide mixed or graft-polymerized with modified polyolefin, and polyamide elastomer using polyester as a soft segment are also included.

In a polyamide resin, for example, a hydrogen atom at the terminal amino group, a hydrogen atom bonded to a carbon atom at the α-position to the terminal amino group, or a carbon atom adjacent to a Ν Η- group of an amide bond Hydrogen atoms (hydrogen atom of methylene group ゃ hydrogen atom of methylidyne group), especially hydrogen atom of terminal amino group, constitute active hydrogen atom.

In the polyamide resin, the terminal Ν Η ₂ group and the terminal C 〇〇Η group The ratio is not particularly limited. For example, when an active hydrogen atom is constituted by a hydrogen atom at the terminal amino group and a hydrogen atom at the Q! -Carbon position, the terminal amino group and the terminal terminal lipoxyl group = 10/90 to It can be selected from the range of about 100 (molar ratio), preferably about 20/80 to 95/5 (molar ratio), more preferably about 25/75 to 95Z5 (molar ratio). . In addition, when an active hydrogen atom is constituted only by the hydrogen atom of the terminal amino group, the terminal amino group and the Z-terminal carboxyl group = 50/50-100/0 (mol ratio) -degree, preferably 6 It may be about 40 to 95/5 (molar ratio), and more preferably about 70/30 to 95Z5 (molar ratio).

In the case of introducing a unsaturated bond in the polyamide resin according to the above-mentioned embodiment (1), for example, the remaining hydroxyl group or amino group can be used as the reactive group (B). ), An unsaturated polycarboxylic acid (such as maleic acid) may be used as a part of the copolymer component.

(2) Polyester resin

Examples of the polyester resin include an aliphatic polyester resin and an aromatic polyester resin. Usually, an aromatic polyester resin, for example, a polyalkylene acrylate resin or a saturated aromatic polyester resin is used. And an aromatic polyester resin, e.g., polyethylene ethylene terephthalate evening rate (PET), Helsingborg C _{2 4} alkylene terephthalamide Yureichito such Poripuchi Renterefu evening rate (PBT); corresponding to the Helsingborg alkylene terephthalamide evening rate Poly C

₄ alkylene naphthalate (eg, polyethylene naphthalate); 1,4-six-hexyldimethylene terephthalate (PCT). The polyester resin may be a copolyester containing an alkylene acrylate unit as a main component (for example, 50% by weight or more), and the copolymerization components include ethylene glycol, propylene glycol, butanediol, and the like. C _{2 6} § such as hexane diol Ruki glycol, polyoxy C ₂ _ ₄ alkylene glycol, off tall acid, asymmetric aromatic dicarboxylic acids or their anhydrides such as Isofutaru acids, such as aliphatic dicarboxylic acids such as adipic acid can be exemplified. Furthermore, a branched structure may be introduced into the linear polyester by using a small amount of a polyol and / or a polycarboxylic acid.

When the aromatic polyester resin does not have the active atom at a predetermined concentration, a modified polyester resin modified with a modifying compound having an active atom (for example, at least one kind selected from an amino group and an oxyalkylene group) (Aromatic polyester resin having a). Compounds having an active atom, especially an active hydrogen atom, include polyamines (aliphatic diamines, for example, ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine). Alicyclic diamines, such as linear or branched alkylenediamines having about 2 to 10 carbon atoms, such as diamine, trimethylhexamethylene diamine, 1,7-diaminoheptane, 1,8-diaminooctane; For example, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane; and aromatic diamines such as phenylenediamine, xylylenediamine, diaminodiphenylmethane and the like. ), Boriols (eg, (poly) oxyethylene Rico one Le, (poly) O alkoxy trimethylene glycol, kill (poly) Okishipuropi glycol, etc. are for illustrative (poly) O alkoxy such as tetramethylene glycol (poly) Okishi C _{2 4} alkylene glycols, etc.). The modification can be performed, for example, by heating and mixing a polyester resin and a modifying compound, and utilizing amidation, esterification, or transesterification. Depending on the amount of active hydrogen atoms in the compound, the degree of modification of the polyester resin is determined based on 1 mol of the functional group (hydroxyl group or carboxyl group) of the polyester resin. 0.1 to 2 mol, preferably 0.2 to 1.5 mol, more preferably Or about 0.3 to 1 mol. If you are use in the transesterification reaction, (poly) Okishi C ₂ - ₄ The amount of alkylene render recall such is from 1 to 5 0 parts by weight approximately relative to the polyester resin 1 0 0 part by weight, good Mashiku the 5 It may be about 30 parts by weight.

In a polyester resin, the hydrogen atom of the methylene group of the (poly) oxyalkylene unit usually constitutes an active hydrogen atom. In a modified polyester resin, the hydrogen atom of the terminal amino group or the terminal amino group is usually used. Hydrogen atom bonded to the carbon atom at position 0 ;, hydrogen atom bonded to the carbon atom adjacent to the _NH- group of the amide bond (hydrogen atom of methylene group 水素 hydrogen atom of methylidyne group, etc.), especially at the terminal amino The hydrogen atoms of the group constitute active hydrogen atoms.

Further, in the case of introducing an unsaturated bond in the polyester-based resin according to the aspect (1), for example, the remaining hydroxyl group ゃ hydroxyl group can be used as the reactive group (B). ), An unsaturated polycarboxylic acid (such as maleic acid) or an unsaturated polyhydric alcohol (such as 2-butene-1,4-diol) may be used as a copolymer component. May be used as a part of.

(3) Poly (thio) ether-based resin

The polyether resin includes a polyoxyalkylene resin, a polyphenylene ether resin, and a polysulfide resin (polythioether resin). The polyoxyalkylene resin, volume Li oxymethylene glycol, polyoxyethylene glycol, Po polyoxypropylene glycol, polyoxyethylene one Boriokishi propylene block copolymer, polyoxy such polyoxytetramethylene glycolate one Le C i _ ₄ Alkylenedalicol and the like. Preferred polyester resins include polyacetone resins, polyphenylene ether resins, polysulfide resins and polyether ketone resins. In the case where an unsaturated bond is introduced according to the embodiment (1), the remaining hydroxyl group, mercapto group, etc. It may be used as a reactive group (B).

(3a) Polyacetal resin

The polyester resin may be a homopolymer (a homopolymer of formaldehyde) formed by regular repetition of acetal bonds, or a copolymer (trioxane and trioxane) obtained by ring-opening polymerization or the like. Ethylene oxide and a copolymer with Z or 1,3-dioxolane). In addition, the terminal of the polyacetal resin may be blocked and stabilized. In the polyacetal resin, for example, a hydrogen atom of an oxymethylene unit, a hydrogen atom of an alkoxy group (particularly a methoxy group) whose terminal is blocked, and particularly a hydrogen atom of an oxymethylene unit constitutes an active hydrogen atom. In the case of introducing an unsaturated bond in the polyacetal resin according to the above mode (1), a remaining hydroxyl group or the like may be used as the reactive group (B).

(3b) Polyphenylene ether resin

Polyphenylene ether resins include various resins containing 2,6-dimethylphenylene oxide as a main component, for example, copolymers of 2,6-dimethylphenylene oxoxide with phenols, styrene resins And a modified polyphenylene ether-based resin prepared by blending or grafting the same. Other modified polyphenylene ether resins include polyphenylene ether Z-polyamide, polyphenylene ether / saturated polyester, polyphenylene ether / boriphenylene sulfide, and boriphenylene ether / polyolefin. And the like. When the styrene resin is blended, the ratio of the styrene resin to 100 parts by weight of the polyolefin ether resin is, for example, 2 to 150 parts by weight, preferably 3 to 100 parts by weight, More preferably, it may be about 5 to 50 parts by weight. In a polyphenylene ether-based resin, for example, a hydrogen atom of a methyl group bonded to a benzene ring constitutes an active hydrogen atom.

(3c) Polysulfide resin (polythioether resin) The polysulfide resin is not particularly limited as long as it has a thio group (—S—) in the polymer chain. Examples of such a resin include a polyphenylene sulfide resin, a polydisulfide resin, a polyphenylene sulfide resin, a polyketone sulfide resin, a polyethylene sulfone resin, and the like. Further, the polysulfide resin may have a substituent such as an amino group like poly (aminophenylene sulfide). A preferred polysulfide resin is a polyphenylene sulfide resin. In polysulfide resins, the thio groups in the main chain constitute active sulfur atoms. For example, for polyphenylene sulfide resin, the average number N of active sulfur atoms in one molecule can be calculated based on the model basic unit C 1 -C ₆ H ₄ -SC ₆ H ₄ -SC ₆ H ₄ -C 1, N = 2.

(3d) Polyetherketone resin

Polyetherketone resins include polyetherketone resins obtained by polycondensation of dihalogenobenzophenones (such as dichloromethane) and dihydrobenzozophenone, and polycondensation of dihalogenobenzophenones with hydroquinone. The resulting polyetheretherketone resin can be exemplified.

(4) Polycarbonate resin

The polycarbonate-based resin may be an aliphatic polycarbonate-based resin, but is usually an aromatic poly-polycarbonate-based resin, for example, an aromatic dihydroxy compound (such as bisphenol A, bisphenol S, etc.). An aromatic polycarbonate obtained by reacting a bisphenol compound or the like) with phosgene or a polyester carbonate (diaryl carbonate such as diphenyl carbonate, dialkyl carbonate such as dimethyl carbonate) can be used. In the polycarbonate resin, when an unsaturated bond is introduced according to the embodiment (1), a remaining hydroxyl group or the like may be used as the reactive group (B). (5) Polyimide resin

Polyimide resins include thermoplastic polyimide resins such as aromatic tetracarboxylic acids or their anhydrides (such as benzophenonetetracarbonic acid) and aromatic diamines (such as diaminodiphenylmethane). Examples include polyimide resins, polyamide imide resins, and polyester imide resins obtained by the reaction. In the polyimide resin, when an unsaturated bond is introduced according to the above embodiment (1), the remaining carboxy group, anhydride group, amino group, imino group and the like can be used as the reactive group (B).

(6) Polysulfone resin

The polysulfone resins include polysulfone resins, polyethersulfone resins, and polysulfone resins obtained by polycondensation of dihalogenodiphenyl sulfone (eg, diphenyl diphenyl sulfone) and bisphenols (eg, bisphenol A or a metal salt thereof). Allyl sulfone resin (trade name: RADEL) can be exemplified.

(7) Polyurethane resin

The polyurethane resin can be obtained by reacting a diisocyanate, a polyol and, if necessary, a chain extender. Aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; 1,4-cyclohexanediisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenyl methane — aromatic diisocyanates such as 4,4, diisocyanate, and xylylene diisocyanate Aromatic diisocyanates can be exemplified. As the diisocyanates, compounds in which an alkyl group (for example, a methyl group) is substituted on a main chain or a ring may be used. Examples of the diols include polyesterdiol (a C _{4 12} aliphatic dicarboxylic acid component such as adipic acid, ethylene glycol, and propylene). Nguriko Ichiru, C 2 aliphatic diol component such as butane diol, neopentyl glycol, epsilon - C _4, such as the force Puroraku tons - such as _{1 2} polyester diols obtained from such lactone component), polyether Rujioru (polyethylene da recall, Polypropylene dalicol, polyoxyethylene-polyoxypropylene block copolymer, polyoxyte 1, ramethylene dalicol, bisphenol A-alkylenoxide adduct, etc., polyester ether diol (as part of the diol component) Polyester diol using the above polyether diol) can be used.

Further, as the chain extender, diamines can be used in addition to C 0 alkylene diols such as ethylene glycol and propylene glycol. Examples of the diamines include aliphatic diamines, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1 Straight or branched chain alkylenediamine having about 2 to 10 carbon atoms, such as 7,7-diaminoheptane and 1,8-diaminooctane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and dipropylenetriamine. Alicyclic diamines, for example, isophorone diamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, etc .; Diamines, for example, phenylenediamine, xylylenediamine And diaminodiphenylmethane.

In polyurethane resins, for example, hydrogen atoms of alkyl groups (particularly, hydrogen atoms at the benzyl position) bonded to the main chain or ring of diisocyanates, hydrogen atoms of alkylene groups of polyols and polyoxyalkylene glycols, chains The hydrogen atom of the amino group of the extender constitutes the active hydrogen source.

Further, in the case of the polyurethane resin, the unsaturated bond is formed according to the aspect (1). When introducing a bond, for example, the remaining hydroxyl group, amino group, isocyanate group or the like may be used as the reactive group (B), or when an unsaturated bond is introduced according to the embodiment (2), The unsaturated polycarboxylic acid (maleic acid or the like) or the unsaturated polyhydric alcohol (2-butene-1,4-diol or the like) may be used as a part of the copolymer component.

(8) Polyolefin resin

Polyolefin-based resins include, for example, homo- or copolymers of orefins such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (methylpentene-1), and copolymers of orefins with copolymerizable monomers. Polymers (e.g., ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer). These polyolefin resins can be used alone or in combination of two or more.

Preferred polyolefin resins include 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. And a propylene-ethylene butene copolymer. Also, the polyolefin resin is preferably crystalline.

In the polyolefin resin, for example, a hydrogen atom of a methylene group constituting the main chain of polyolefin, a hydrogen atom of a methyl group branched from the main chain, and the like constitute an active hydrogen atom.

(9) Halogen containing resin

Examples of the halogen-containing resin include chlorine-containing vinyl resins such as polyvinyl chloride, polyvinylidene chloride, pinyl chloride-pinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer, polyvinyl fluoride, polyvinylidene fluoride, and polyvinyl chloride. Mouth Fluorine such as trifluoroethylene, copolymer of tetrafluoroethylene and copolymerizable monomer Examples thereof include a vinyl resin. Preferred halogen-containing resins are fluorine-containing pinyl resins (eg, polyvinyl fluoride, polyvinylidene fluoride, etc.).

(10) Styrene resin

Examples of the styrene resin include homopolymers or copolymers of styrene monomers (such as polystyrene, styrene-vinyltoluene copolymer, and styrene-α-methylstyrene copolymer), and copolymerizable monomers of styrene monomers. Copolymer 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; acrylonitrile-butadiene-styrene copolymer (ABS resin), impact-resistant polystyrene (HIPS), acrylonitrile-acrylic acid ester-styrene copolymer (AAS resin), acrylonitrile chlorine Polyethylene-styrene copolymer (ACS resin), acrylonitrile-ethylene propylene Over scan styrene copolymer (A E S resin), an acrylonitrile - styrene graft copolymer, such as acetic acid Binirusu styrene copolymer (A X S resin), etc.) and the like.

(11) (Meth) acrylic resin

Examples of the (meth) acrylic resin include a (meth) acrylic monomer alone or a copolymer, 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, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic (meth) acrylic acid alkyl esters, such as hexyl acid .2- Echiru, main evening methacrylic acid C ₅ _ _{1 0} cycloalkyl esters such as cyclohexyl acrylic acid consequent opening, (meth) Akuriru acid phenyl such as (meth) acrylic acid c ₆ - _{j 0} § reel ester, (meth) such as accession acrylic acid arsenide Dorokishechiru (meth) Akuriru hydroxyalkyl C, _ _{1 0} § Le Examples include a kill ester, (meth) acrylamide, (meth) acrylonitrile, and glycidyl (meth) acrylate. Examples of the copolymerizable monomer include vinyl monomers such as vinyl acetate and vinyl chloride, and styrene monomers such as styrene and -methylstyrene. In the (meth) acrylic resin, when an unsaturated bond is introduced according to the aspect (1), a monomer having a reactive group (B) is used as a copolymerization component, whereby the reactive group (B) Can be introduced.

(1 2) Thermoplastic elastomer

Thermoplastic elastomers include polyamide-based elastomers (copolymers using polyamide as a hard phase and aliphatic polyether as a soft phase), and polyester-based elastomers (polyalkylene arylate as a hard phase, and Copolymers using aliphatic polyethers or aliphatic polyesters as the soft phase), polyurethane elastomers (copolymers using the short-chain dalicol polyurethane as the hard phase and aliphatic polyethers or aliphatic polyesters as the soft phase) For example, polyester urethane elastomer, polyether urethane elastomer, and polystyrene-based elastomer (a block copolymer having a polystyrene block as a hard phase and a gen-polymer block or a hydrogenated block thereof as a soft phase) , Polyolefin elastomer (polystyrene or Elastomers that use polypropylene as the hard phase and ethylene-propylene rubber or ethylene-propylene diene rubber as the soft phase, or olefin-based elastomers that consist of a hard phase and a soft phase with different degrees of crystallinity, etc. Includes vinyl chloride-based elastomers and fluorine-based thermoplastic elastomers. As was stated in the polyester resin, and poly Uretan resin (poly) Okishi C ₂ aliphatic polyether - such as ₄ Arukirendari call such (especially polyoxyethylene glycol) can be used as the aliphatic polyester, Polyester diol and the like described in the section of the polyurethane resin can be used. These thermoplastic elastomers can be used alone or in combination of two or more. When the thermoplastic elastomer is a block copolymer, the block structure is not particularly limited, and may be a triblock structure, a multiblock structure, a star block structure, or the like.

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

In the thermoplastic elastomer, for example, a hydrogen atom of an oxyalkylene unit constituting the soft phase may constitute an active hydrogen atom.

The thermoplastic resin may be used as a cross-linked resin cross-linked using a cross-linking agent. For example, in the case of a polyester resin, a trifunctional or higher polycarboxylic acid (for example, trimellitic anhydride) and / or a trifunctional or higher polyhydric alcohol (for example, glycerin) is mixed with a dicarboxylic acid component and Z or Crosslinking may be performed by using as a part of the diol component. In the polyamide resin, triamines (for example, tri (methylamino) hexane, etc.) may be used as a diamine component and a part of the Z or dicarboxylic acid component. An aliphatic polyamine, an aromatic polyamine such as triaminobenzene, etc.) and a Z or tri- or higher functional polycarboxylic acid (eg, trimellitic anhydride) may be used to obtain a crosslinking resin.

In addition, vinyl polymer-based resins [for example, (meth) acrylic resins (eg, methyl methyl acrylate, methyl methacrylate-styrene copolymer) and styrene resins (polystyrene; styrene copolymers such as AS resin; HIPS) And styrene-based graft copolymers such as ABS resin] are polyfunctional polymerizable compounds having two or more functional groups (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol diacrylate). Crosslinking may be carried out by copolymerizing (meth) acrylate, trimethylolpropanetri (meth) acrylate, etc.) with a constituent monomer. (Thermosetting resin)

Examples of the thermosetting resin include polycondensation or addition condensation resins (phenol resins, amino resins, epoxy resins, silicone resins, thermosetting polyimide resins, thermosetting polyurethane resins, etc.), and addition polymerization resins. Fats (thermosetting acrylic resins, pinyl ester resins, unsaturated polyester resins, diaryl phthalate resins, etc.) can be exemplified. The thermosetting resins may be used alone or in combination of two or more.

(13) Phenol resin

The phenolic resin includes a nopolak resin, a resol resin, and the like, but a nopolak resin is usually used. Nopolak resin is obtained by the reaction of phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, o—, m—, or! ) —Cresol, 2,5—, 3,5- or 3,4- xylenol, 2,3,5 _ trimethylphenol, ethyl phenol, propylylphenol and other C i _ ₄ alkylphenols, dihydroxybenzen, Examples thereof include resorcinol and naphthol. These phenols may be used alone or in combination of two or more. Examples of the aldehydes include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde and propionaldehyde, and aromatic aldehydes such as benzaldehyde and salicylaldehyde. These aldehydes may be used alone or in combination of two or more.

(14) Amino resin

Amino resins usually react with an amino group-containing compound and an aldehyde (eg, an aliphatic aldehyde such as formaldehyde, acetoaldehyde, propionaldehyde, or an aromatic aldehyde such as phenylacetaldehyde). Is obtained by Amino resins include urea resins (such as urea resins obtained by the reaction of urea and aldehydes), and aniline resins (anilin, naphthylamine, toluidine, xylin). Lysine, N, N-dimethylaniline, benzidine and other anilines and aldehydes, and aniline resins, and melamine resins (melamine and aldehydes, etc.) ), And guanamine resins (such as guanamine resins obtained by reacting guanamines such as benzoguanamine, acetoguanamine and formoguanamine with aldehydes).

(15) Epoxy resin

Epoxy resins include bisphenol-type epoxy resins, nopolak-type epoxy resins, and amine-based epoxy resins.

Examples of the bisphenol constituting the bisphenol-type epoxy resin include glycidyl ethers such as 4,4-biphenol, 2,2-biphenol, bisphenol F, bisphenol A D, and bisphenol A.

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

(16) Silicone resin

The silicone resin has a unit represented by the formula: R _a S i O ( 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 (where the coefficient b is about 0.9 to 1.1). In the formula, R is, for example, C i such as a methyl group, an ethyl group, a propyl group, and a butyl group. Halogenated C _ such as alkyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group. C ₂ —, such as alkyl, vinyl, aryl, and butenyl groups. Alkenyl group, phenyl group, tril group, naphthel group Which C ₆ i ₂ Ariru group, a cyclopentyl group, which C ₃ E a cyclohexyl group. Cycloalkyl group, a benzyl group, C ₆ E ₂ Ariru such phenethyl - like ci _ ₄ alkyl group.

(17) Thermosetting polyimide resin

The thermosetting polyimide-based resin includes the resins described in the section of the polyimide-based resin.

(18) Thermosetting polyurethane resin

The thermosetting polyurethane-based resin includes the resins described in the section of the polyurethane-based resin.

(19) Thermosetting acrylic resin

The thermosetting acrylic resin includes the resin described in the section of the (meth) acrylic resin.

(20) Vinyl ester resin

Examples of the vinyl ester resin include a resin obtained by reacting the epoxy resin with (meth) acrylic acid, and a resin obtained by reacting polyhydric phenols with glycidyl (meth) acrylate.

(21) Unsaturated polyester resin

As the unsaturated polyester resin, in the polyester-based resin, an unsaturated polyester obtained by using an unsaturated dicarboxylic acid or its anhydride (for example, maleic acid, maleic anhydride, fumaric acid, etc.) as a dicarboxylic acid component Is mentioned.

(22) Diaryl phthalate resin

Examples of the diaryl phthalate-based resin include resins obtained from diaryl phthalate monomers such as diaryl orthophthalate and di7-yl isophthalate.

When the resin is, for example, a thermoplastic resin having a melting point higher than a kneading and vulcanizing temperature of rubber, or a crosslinked or thermosetting resin, it may be used in the form of powder and granules. As such resin particles Examples thereof include a cross-linked polymethyl methacrylate resin, a cross-linked polystyrene resin, a cross-linked epoxy resin, a cross-linked phenol resin, a cross-linked benzoguanamine resin, a cross-linked silicone resin, and the like. The shape of the crosslinked or cured resin material is not particularly limited, and may be, for example, an amorphous shape, a spherical shape, an elliptical shape, a rod shape, or the like. The average particle diameter of the resin powder is, for example, 0.1 to 500 m, preferably 1 to 100 mm, more preferably 5 to 500; 5500 urn, preferably about 20 2200 m (for example, 50〜150 m).

The resin is made up of various additives, such as fillers or reinforcing agents, stabilizers (UV absorbers, antioxidants, heat stabilizers), coloring agents, plasticizers, lubricants, flame retardants, antistatic agents. Etc. may be included.

[Rubber]

Rubber is obtained by vulcanizing unvulcanized rubber. The rubber is not particularly limited as long as it can react with the resin, and various rubbers can be used.

Examples of the rubber include gen-based rubber, aged refin-based rubber, acrylic rubber, fluorine rubber, silicone-based rubber, epoxy rubber, epichlorohydrin hydrin rubber (epichlorohydrin homopolymer C, epichlorohydrin) ECO, copolymers of acrylglycidyl ether, etc.), chlorosulfonated polyethylene, propylene oxide rubber (GPO), ethylene monoacetate vinyl copolymer (E AM), polynorpolene rubber, and their modified rubbers (such as acid-modified rubber). These rubbers can be used alone or in combination of two or more. Of these rubbers, generally, gen rubber, olefin rubber, acryl rubber, fluorine rubber, silicone rubber, urethane rubber and the like are widely used from a practical viewpoint.

For example, natural rubber (NR), isoprene rubber (I R), polymers of gen-based monomers such as isobutylene isoprene rubber (butyl rubber) (IIR), butadiene rubber (BR), chloroprene rubber (CR); for example, acrylonitrile butadiene rubber (nitrile rubber) ( Acrylonitrile copolymer rubbers such as NBR), nitrile chloroprene rubber (NCR), nitrile isoprene rubber (NIR), acrylonitrile isoprene butadiene rubber (NBIR); styrene butadiene rubber (SBR, for example, styrene and butadiene Styrene-copolymer rubbers such as random copolymers, SB block copolymers composed of styrene blocks and butadiene blocks), styrene chloroprene rubber (SCR), styrene isoprene rubber (SIR), etc. . Gen-based rubber also includes hydrogenated rubber, for example, hydrogenated nitrile rubber (HNB R). In the styrene-copolymer rubber, the proportion of the styrene component is, for example, 10 to 80 mol%, preferably 20 to 70 mol%, more preferably 30 to 70 mol%, in terms of the monomers constituting the copolymer. It may be about 60 mol%.

Examples of the olefin rubber include ethylene propylene rubber (EPM), ethylene propylene gen rubber (EPDM, etc.), and polyoctenylene rubber.

Acrylic rubbers include rubbers containing alkyl acrylate as a main component, such as 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 acrylic rubber can be exemplified.

Examples of the fluororubber include rubbers containing a fluorine-containing monomer, such as a copolymer of vinylidene fluoride and polyfluoropropene, and if necessary, a copolymer of ethylene tetrafluoride and a copolymer of ethylene tetrafluoride and propylene. , With tetrafluoroethylene and perfluoromethyl vinyl ether Of the copolymer FF KM.

Silicone rubber (Q) is an organopolysiloxane composed of units represented by the formula: R _a S i 〇 ( ₄ − _a ) _{/ 2} . In the formula, R is, for example, C i such as a methyl group, an ethyl group, a propyl group, and a butyl group. Halogenated C — such as alkyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group. C ₂ -D such as alkyl group, vinyl group, aryl group and butenyl group. Alkenyl group, a phenyl group, a tolyl group, C _6, such as a naphthyl group - i ₂ Ariru group, C ₃ _ i, such as cyclopentyl group, cyclohexyl group. C ₆ — i ₂ aryl C i — ₄ alkyl groups such as a cycloalkyl group, a benzyl group, and a phenethyl group. Where the coefficient a is about 1.9 to 2.1. Desirable R is a methyl group, a phenyl group, an alkenyl group (such as a vinyl group), or a fluoro- ₆ alkyl group.

The molecular structure of the silicone rubber is usually linear, but may have a partially branched structure or a branched chain structure. The main chain of the silicone rubber is, for example, a dimethylpolysiloxane chain, a methylvinylpolysiloxane chain, a methylphenylpolysiloxane chain, a copolymer chain of these siloxane units [dimethylsiloxane-methylvinylsiloxane copolymer. Copolymer chain, dimethylsiloxane-methylphenylsiloxane copolymer chain, dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer chain, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane Polymer chains]. Both ends of the silicon Kongomu, for example, trimethylene Rushiriru group, dimethylvinylsilyl group, silanol group, it may be a preparative 'JC preparative ₂ alkoxysilyl group.

Silicone rubber (Q) includes, for example, methyl silicone rubber (MQ), vinyl silicone rubber (VMQ), phenyl silicone rubber (P MQ), phenyl vinyl silicone rubber (P VMQ), fluorinated silicone rubber ( F VMQ). In addition, silicone rubber Not only the above-mentioned high temperature vulcanizable HTV (High Temperature Vulcanizable) solid rubber but also room temperature vulcanizable RTV (Room Temperature Vulcanizable) or low temperature vulcanizable LTV (Low Temperature Vulcanizable) silicone rubber, for example, Liquid or pasty rubber is also included.

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

Examples of the modified rubber include acid-modified rubbers such as carboxylated styrene butadiene rubber (X-SBR), carboxylated nitrile rubber (X-NBR), carboxylated ethylene propylene rubber (X-EP (D) M), and the like. Rubbers having carboxylic acid groups or acid anhydride groups are included. The ratio between the resin and the rubber can be appropriately set within a range in which the characteristics of the composite dispersion can be effectively exhibited. 90 (weight ratio) [for example, 90/10 to 30/70 (weight ratio)], preferably 75 525 to 25Ζ75 (weight ratio) [for example, 75Ζ25 to 50 / 50 (weight ratio)], and may be about 60/40 to 40Ζ60 (weight ratio).

[Vulcanizing agent]

The vulcanizing agent not only vulcanizes (or crosslinks) the unvulcanized rubber, but also acts on the resin (or active resin) (for example, by extracting active hydrogen atoms of the resin and activating it by radicalization, etc.). By activating the crosslinkable group of the resin), the resin and the vulcanized rubber can be bonded. As the vulcanizing agent, a radical generator or sulfur can be used according to the type of the resin or rubber. Examples of the radical generator include organic peroxides, azo compounds, and sulfur-containing organic compounds. it can. In the present invention, the radical generator is effective for the resin having an active atom, the thermoplastic resin having an unsaturated bond, and the thermosetting resin having a crosslinkable functional group. Resin having unsaturated bond (The thermoplastic resin having an unsaturated bond, the unsaturated polyester-based resin, etc.), a specific resin / rubber combination [polyphenylene ether-based resin and the styrene-gen copolymer rubber (styrene-butadiene rubber, etc.) and , A combination of a polyether-based resin and rubber, etc.]. The vulcanizing agents can be used alone or in combination of two or more.

The vulcanizing agent may be added to at least one of the unvulcanized rubber and the resin, or may be added to both components.

Organic peroxides include diacyl peroxides (lauroyl peroxide, benzoyl peroxide, 4-chlorobenzoyl oxide, 2,4-dichlorobenzoyl peroxide, etc.), and peracids. Dialkyl halides (di-t-butylperoxide, 2,5-di (t-butylperoxy) -2,5-dimethylhexane, 1,1-bis (t-butylperoxy) —3,3,5-trimethylcyclo Hexane, 2,5-di (t-butylperoxy) -1,2,5-dimethylhexine — 3,1,3-bis (t-butylperoxyisopropyl) benzene, dicumylperoxide, etc. Alkyl oxides (t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexyl 1,2,5-dihydroperoxide, diisopropylbenzene To hydroperoxides), alkylidene peroxides (ethyl methyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t-butylperoxy) —3,3,5-trimethylcyclo) And peroxyesters (such as t-butyl peracetate and t-butyl perpivalate).

The azo compound includes azobisisobutyronitrile and the like. Examples of the sulfur-containing organic compounds include thiurams (tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TB TD ), Dipentamethylenethiura Mutetrasulfide (DPTT), morpholine disulfide, alkyl phenol disulfide, etc.).

Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Sulfur also includes sulfur chlorides such as sulfur monochloride and sulfur dichloride.

A photopolymerization initiator can also be used as a radical generator as long as light can be irradiated at the time of joining the resin phase and the rubber phase. Examples of the photopolymerization initiator include benzophenone or a derivative thereof (eg, 3,3′-dimethyl-4-methoxybenzophenone, 4,4 dimethoxybenzophenone), alkylphenyl ketone or a derivative thereof (acetophenone, diphenylbenzene). Ethoxyacetophenone, 2-hydroxy-2-methyl-11-phenylpropane, one-one, benzyldimethylketal, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-1 (morpholinov) Enyl) -butanone, etc.), anthraquinone or its derivatives (such as 2-methylanthraquinone), thioxanthone or its derivatives (such as 2-cyclothioxanthone, alkyl thioxanthones), benzoin ether or its derivatives (benzoin, benzoinalkyl) ether Etc.), etc. phosphine Nokishido or a derivative conductor can be exemplified. In addition, radical generators also include persulfates (ammonium persulfate, potassium persulfate, etc.).

Preferred vulcanizing agents among these compounds are organic peroxides. Vulcanizing agents are often added to unvulcanized rubber.

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

[Vulcanizing activator]

In the present invention, the vulcanization activator is not always necessary, but is often added in order to surely join the rubber phase and the resin phase. The vulcanization activator It may be added to at least one of unvulcanized rubber (or unvulcanized rubber composition) and resin (or resin composition), and may be added to both components.

The vulcanization activator can be selected according to the vulcanizing agent (for example, radical generator or the like) to be used, and the like. An organic compound having a carbon-carbon double bond (polymerizable unsaturated bond) [eg, vinyl Monomer (divinylbenzene, etc.), aryl monomer (diaryl phthalate, triaryl phosphate, triallyl (iso) cyanurate, etc.), (meth) acrylic monomer, etc.), maleimide compound, And carbon disulfide derivatives. These vulcanizing activators can be used alone or in combination of two or more.

(Meth) acrylic monomers include, for example, bifunctional (meth) acrylates [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol (meta) ) Akuri rate, hexanediol di (meth) Akuri rate, neopentyl tilde Rico one distearate (meth) Akuri rate C such as ₂ - Interview. Alkylene glycol di (meth) acrylate; diethylene dalicol di (meth) acrylate, triethylene dalichol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropropyl render recall di (main evening) Akuri rate, polypropylene glycol one distearate (meth) Akuri rate Bok, polytetramethylene glycolide one distearate (main evening) Akuri rate poly C ₂ such as - ₄ alkylene glycolate one distearate (meth) Akuri rate, glycerin di (meth) Akuri rate, trimethylene opening one Rupuropanji (meth) Akuri rate, pen evening erythritol Bok one distearate (main evening) Akuri rate Bok, C ₂ of the bisphenol a - ₄ alkylene O wherein de adduct di ( Meta) acrylate etc.], three Functional or polyfunctional (meth) acrylates [glycerintri (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpro Pantoli (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentyl erythritol tetra (meth) acrylate, dipentaerythritol hexa (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, N, N '— 3-Methyl-1-, 4-phenylenediimide, 4,4'-bis (N, N, 1-maleimide) diphenylmethane, 4,4'-bis (N, N'-maleimide) diphenylsulfone , 4,4, -bis (N, N, -maleimide) diphenyl ether, etc.), aliphatic bismaleimide (N, N'1-1,2-ethylenebismaleimide, N, N'-1,3 —Propylene bismaleide, N, N'-1,4-tetramethylene bismaleide, etc.).

The carbon disulfide derivatives, Jichio force Rubamin acid salts (dimethyl Jichio force Rubamin acid, and di-C! _ ₄ alkyl di Chio carbamate such Jechirujichi Sairyoku Rubamin acid, sodium, potassium, iron, copper, zinc, selenium or Tellurium, etc.), thiazoles (such as 2-mercaptobenzothiazole, 2- (4'-morpholinodithio) benzothiazole, etc.), thiopereas (such as thiocarpoanilide, diorthotril thioperia), and dithiocarbamates (dimethyldithiocarbamate) Minic acid, diethyl _4- dialkyldithiol, such as rubilic acid, and sodium, potassium, iron, copper, zinc, selenium or tellurium, etc.), sulfenamides (N-cyclohexyl) 2 Benzothiazolsulfenamide, etc.), Santogen acid salts (I isopropyl xanthate, and Al Kirukisantogen acid such as Petit xanthate, sodium, salts, such as zinc), and others. Preferred vulcanization activators include 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, for example, triaryl ( Iso) cyanurate, difunctional to polyfunctional (meth) acrylate (especially trifunctional or polyfunctional (meth) acrylate), aromatic maleimide compounds and the like. Vulcanizing activators are often added to unvulcanized rubber. The amount of the vulcanizing activator used is usually an amount capable of promoting the adhesion between the resin and the rubber, for example, 100 parts by weight of the unvulcanized rubber and Z or the resin. It can be selected from the range of about 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.

[Vulcanization aid]

In the present invention, a vulcanization aid may be further used. The vulcanization aid may be added to at least one of the unvulcanized rubber (or the unvulcanized rubber composition) and the resin (or the resin composition), or may be added to both components. Is also good.

The vulcanization aid can be selected according to the type of resin or rubber. For example, an oligomer of the condensation-based thermoplastic resin (for example, an oligomer of the polyamide-based resin, a number-average molecular weight of the oligomer of the polyester-based resin, and the like, 10) 0 to 1000 oligomers), polyamines (for example, the polyamines described in (2) Polyester Resin), and polyols (for example, (2) Polyester Resin) Polyhydric carboxylic acids or acid anhydrides thereof, compounds having a plurality of aldehyde groups, epoxy compounds, nitrogen-containing resins (such as amino resins), compounds having a methylol group or an alkoxymethyl group, and the like. Examples thereof include polyisocyanate. 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 among the active atoms represented by the formula (1), for example, oligomers of the condensation thermoplastic resin (for example, The polyamide tree Oligomers of fats, oligomers of the polyester-based resin, etc.), and 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.

[Silane coupling agent]

In the present invention, a silane coupling agent may be included in order to improve the adhesion between the resin phase and the vulcanized rubber phase. The silane coupling agent may be added to either one of the unvulcanized rubber (or unvulcanized rubber composition) and the resin (or the resin composition), and may be added to both components. Good.

Examples of the silane coupling agent include compounds having a reactive group (eg, a hydroxyl group, an alkoxy group, a vinyl group, an amino group, an epoxy group, a mercapto group, a carboxyl group, an isocyanate group, a (meth) acryloyl group, etc.). Is included.

For example, alkoxysilanes (e.g., trimethylamine Tokishishiran, tri C E and tri Etokishishiran - alkoxysilanes, tetramethylene Toki Shishiran, tetra Ji E tetraethoxysilane - ₄ A record thousand Shishira down);

Alkoxysilanes having vinyl groups (vinyltri-C- ₄ alkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane);

Alkoxysilane having an amino group (e.g., 2-aminoethyl trimethyl Tokishishiran, 2 - aminoethyl triethoxysilane, 3 - § amino propyl triethoxy silane and amino C ₂ - ₄ alkyl tri C Interview - ₄ alkoxy silane, 3- § ₄ alkyl di C ^ ₄ alkoxy silane) - amino propyl methyl dimethyl Tokishishi run, 3 § amino propyl amino di C ₂ such as methyl silane;

Alkoxysilanes with epoxy groups (for example, 3-glycidyl Dalicidyloxy C ₂ — ₄ triC i — ₄ alkoxysilane, such as oxypropyltrimethoxysilane, (epoxycycloalkyl) C ₂ — ₄ alkyltri C _4, such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Alkoxysilane);

Alkoxysilane having a mercapto group (e.g., 3-mercapto Topuropirutorime mercapto C E such Tokishishiran - ₄ Arukiruto Li C E _ ₄ alkoxy silane, 3-mercaptopropyl methyl dimethyl Bok Kishishiran Merukaputoji such C - ₄ alkyl di C E - ₄ alcoholic silane);

Alkoxysilanes having a hydroxyl group (for example, carboxymethyltrimethoxysilane, carboxymethyltriethoxysilane, carboxyshethyltrimethoxysilane, carboxypropyltrimethoxysilane, and other carpoxy C-4alkyltriC-4alkoxysilanes);

Isoshiane alkoxysilane having an preparative group (e.g., Isoshia sulfonates E tilt Increment Tokishishiran, I Société § sulfonates E tilt Rie preparative Kishishiran, I like Isoshiane one Topuropirutorime Tokishishiran Soshianeto C - ₄ alkyl tri C E - ₄ alkoxy silane); 'Alkoxysilanes having (meth) acryloyl groups (eg, N- (3- (meth) acryloxy-12-hydroxypropyl) -13-aminopropyltriethoxysilane, 3- (meth) acryloxypyl dimethyldimethylsilane, 3- (meth) acryloxypropyldimethylethoxysilane, 3- (meth) acryloxypropylmethyl ethoxysilane) and the like.

The amount of the silane coupling agent to be used is usually an amount capable of promoting adhesion between the resin and the rubber, for example, about 1 to 10 parts by weight of the silane coupling agent with respect to 100 parts by weight of the rubber or the resin. Can be selected from the range of about 2 to 8 parts by weight, more preferably about 2 to 6 parts by weight.

[Other additives] The resin composition and the rubber or rubber composition may contain various additives as needed, such as fillers, plasticizers or softeners, co-vulcanizing agents (metal oxides such as zinc oxide), aging. Inhibitors (thermal aging inhibitors, ozone deterioration inhibitors, antioxidants, UV absorbers, etc.), tackifiers, processing aids (polyalkenylene, etc.), lubricants, coloring agents (titanium oxide, power pump racks) ), A foaming agent, a dispersant, a flame retardant, an antistatic agent, and the like.

The filler (or reinforcing agent) includes, for example, a powdery or granular filler or a reinforcing agent (such as my strength, clay, talc, caic acids, silica, calcium carbonate, magnesium carbonate, carbon black, ferrite, etc.), Fiber-like fillers 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 plasticizer is not particularly limited as long as it can impart plasticity to the resin composition or the rubber composition, and may be a conventional plasticizer (phthalic acid ester, aliphatic dicarboxylic acid ester, polyester polymer plasticizer, etc.). Which can be used. In the rubber composition, conventional softeners (eg, vegetable oils such as linoleic acid, oleic acid, castor oil, and palm oil; mineral oils such as paraffin, process oil, and extender) can be used.

As the Poriaruke two lens, for example, it may have a substituent Helsingborg C ₅ - _2. And alkenylene [for example, polypentenamer, polyheptenamer, polyoctenamer, poly (3-methyloctenamer), polydecenamer, poly (31-methyldecenamer), polydodecenamer and the like. In polyalkenylene, the ratio of carbon-carbon double bonds to all the bonds constituting the polymer main chain may be about 1/5 or less (for example, 1/5 to 1/20). Polyalkylene is a cycloolefin (e.g., cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, etc.). C _{5 —} ₂ which may have a substituent. It can be obtained by metathesis polymerization of cycloolefin, etc., or partial hydrogenation of polyalkenedylene (eg, polybutenamer).

Examples of the lubricant include wax (for example, paraffin wax, Mike Chris Linn wax, polyethylene wax, etc.), fatty acids (such as stearic acid), aliphatic alcohols (such as stearyl alcohol), fatty acid derivatives (such as fatty acid such as butyl stearate). Esters, fatty acid amides such as stearic acid amide, and fatty acid metal salts such as zinc stearate).

Examples of the foaming agent include inorganic foaming agents such as hydrogen carbonate (for example, sodium hydrogen carbonate, ammonium hydrogen carbonate, etc.); and organic foaming agents such as p, p-oxybis (benzenesulfonylhydrazide) and dinitrosopentamethylenetetramamine. A foaming agent can be exemplified.

The content of the filler is, for example, about 0 to 300 parts by weight, preferably 0 to 200 parts by weight (for example, 0 to 100 parts by weight) based on 100 parts by weight of the resin or rubber. ), More preferably about 0 to 50 parts by weight (for example, 0 to 10 parts by weight). 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, more preferably about 0 to 150 parts by weight with respect to 100 parts by weight of the resin or rubber. It may be about 120 parts by weight. The content of the co-vulcanizing agent, anti-aging agent, processing aid or lubricant, coloring agent, etc. may be an effective amount. For example, the content of the co-vulcanizing agent is resin or rubber. The amount may be 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, based on parts by weight. The amount may be 0 to 30 parts by weight, preferably 0 to 15 parts by weight, more preferably about 0 to 8 parts by weight, based on 100 parts by weight of the resin or rubber.

In the composite dispersion of the present invention, the vulcanized rubber phase constitutes a continuous phase, and the resin phase constitutes a dispersed phase. In such a composite dispersion, the properties of the vulcanized rubber (elasticity, Resin properties (eg, slipperiness, abrasion resistance, etc.) can be imparted while taking advantage of cushioning and flexibility.

The composite dispersion may have a sea-island structure in which the dispersed phase is independently dispersed in the continuous phase, and the shape of the dispersed phase may be particulate, ellipsoidal, spherical, rod-like, fibrous, etc. Good. The preferred shape of the dispersed phase is spherical, and the dispersed phase is preferably uniformly dispersed in the continuous phase. The average particle size of the dispersed phase may be any value as long as the properties of the substance forming the dispersed phase can be exhibited. For example, 0:! ~ L OOO m, preferably 1 to 750 m, more preferably 1 It is about 0 to 500 / m (for example, 50 to 150ζm). When crosslinked or cured particles are used as the resin, the average particle size of the dispersed phase corresponds to the average particle size of the crosslinked or cured particles.

Further, the composite dispersion may be joined in a state where the dispersed phase particles are partially exposed on the surface. In such a composite dispersion, the surface can have the properties of a resin (eg, a low coefficient of friction, etc.) while having the properties of a continuous phase rubber (eg, high flexibility and cushioning properties). Wear.

Further, a composite in which the obtained composite dispersion and another molded body (for example, a resin molded body, a vulcanized rubber molded body, and the like) are joined at a contact surface may be used.

[Method for producing composite dispersion]

In the present invention, a dispersed composite in which a vulcanized rubber phase and a resin phase are joined is produced by kneading and molding a rubber and a resin. The rubber may be an unvulcanized rubber, and vulcanization or cross-linking of the unvulcanized rubber can be performed at an appropriate stage, for example, a molding step, a post-step after the molding, or the like.

At least one of the vulcanized rubber phase and the resin phase may be formed of a composition containing a vulcanizing agent, and at least one of the vulcanized rubber phase and the resin phase is formed of a vulcanizing activator (particularly, Vulcanizing agents such as radical generators (A sulfur activator). The vulcanizing agent and the vulcanizing activator are preferably added to the resin and / or the rubber in advance, but may be newly added during the kneading process, if necessary.

More specifically, the composite dispersion of the present invention is obtained by kneading a resin (or a thermoplastic or thermosetting resin composition) and an unvulcanized rubber (an unvulcanized rubber composition) into a predetermined shape. It can be obtained by molding or vulcanizing or cross-linking the unvulcanized rubber in a molding process or in a subsequent step after molding. In this method, when crosslinked or cured resin particles are used as the resin material, the rubber (or rubber composition) may be melted and kneaded without melting the crosslinked or cured resin. Prior to kneading, the crosslinked or cured resin is preferably used in the form of a powder having a shape (for example, spherical, elliptical, rod-like, etc.) suitable for the dispersed phase of the composite dispersion.

The kneading can be performed using a conventional kneader (eg, an extruder). When the thermosetting resin or its composition is kneaded with unvulcanized rubber or vulcanized rubber, it is usually kneaded at the non-curing temperature of the thermosetting resin. The kneading of the unvulcanized rubber is usually performed at a temperature lower than the vulcanization temperature of the rubber.

Examples of the molding method include extrusion molding, injection molding, and blow molding, and usually, extrusion molding or injection molding is used. The shape of the molded article is not particularly limited, and may be plate-like, sheet-like, tubular, or the like. The molding temperature can be appropriately set according to the raw materials used (for example, resin and rubber), and is, for example, 50 to 300 ° C., preferably 75 to 250 ° C. ° C More preferably, it is about 100 to 220 ° C (for example, 150 to 200 ° C).

The composite dispersion can be obtained by vulcanizing or crosslinking the molded article during or after the molding. Vulcanization may be performed in a reduced pressure atmosphere, but is generally performed at normal pressure. The vulcanization or crosslinking temperature can be selected, for example, from 70 to 250 ° C, preferably from 100 to 230 ° (: more preferably from about 150 to 220 ° C). . In the composite dispersion thus obtained, the vulcanized rubber phase formed by the vulcanization of the unvulcanized rubber is firmly joined with the continuous phase and the resin phase constituting the dispersed phase. Further, since the dispersed phase particles (resin phase) can be partially exposed on the surface of the composite dispersion, the properties of the resin and the rubber (the properties of the resin, for example, the sliding property) can be effectively exhibited. Therefore, the composite dispersion of the present invention can be used in various applications such as automotive parts (vibration absorbing bushings, spring plates, Rage mounts, etc.), anti-vibration rubber, valves, electric plugs and the like. It can be advantageously used as a member. Industrial applicability

In the present invention, the unvulcanized rubber and the resin are melt-kneaded and molded, and the unvulcanized rubber is vulcanized or crosslinked to form a vulcanized rubber phase as a continuous phase and a resin phase as a dispersed phase. Thus, a composite dispersion having both characteristics of rubber and resin can be obtained. In addition, the composite dispersion in which the dispersed phase particles (resin particles) are partially exposed on the surface exhibits the characteristics of the dispersed phase (resin) on the surface while having the characteristics of the continuous phase (rubber). be able to. Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples and comparative examples, the following resin compositions and rubber compositions were used.

[Resin compositions (A) to (H)]

Resin composition A 1 to A 4

The following resin compositions (A1 to A4) were prepared using polyamide 612 (polycondensate of hexamethylene diamine and dodecanedicarboxylic acid) as a thermoplastic resin. Note that the calculation of M〇P APC M 3 was performed based on the following basic units.

NH _2- (CH ₂ ) _fi -dish-C (= 0)-(CH ₂ ) _10- C (= 0) -OH Resin composition (A 1):

Polyamide 6 12 (NH ₂ terminal / COOH terminal = 9/1 (molar ratio))

(Preparation method): A predetermined amount of hexamethylenediamine was added to an 80% by weight aqueous solution of a salt of hexamethylenediamine and dodecanedicarboxylic acid, and the mixture was pressurized in a nitrogen-purged autoclave (17.5). The system was heated (220 ° C) under KGZcm ² ), and the water in the system was discharged with nitrogen gas out of the system in 4 hours. After one hour, the temperature was gradually increased (275 ° C) to remove water residues from the system, and the internal pressure of the autoclave was returned to normal pressure. After cooling, polyamide 612 was obtained. The obtained polymer had a molecular weight (M n) of about 20000 and a ratio of amino terminal to carboxyl terminal = 9/1. This polymer alone was used as a resin composition (A 1).

Resin composition (A2):

Polyamide 6 12 (NH ₂ terminal ZCO 0 H terminal = 1/1 (molar ratio))

(Preparation method): An 80 wt% aqueous solution of a salt of hexamethylenediamine and dodecanedicarboxylic acid was heated (220.C) under pressure (17.5 kg / cm2) in an autoclave purged with nitrogen. The water in the system together with nitrogen gas was discharged out of the system in 4 hours. Then, it took 1 hour to gradually raise the temperature (275 ° C) to remove water residues from the system and then return the internal pressure of the autoclave to normal pressure. After cooling, polyamide 612 was obtained. The obtained polymer had a molecular weight (Mn) of 20000 to 2500 and a ratio of amino terminal to carboxyl terminal = 1/1. This polymer was used alone as a resin composition (A 2).

Resin composition (A3):

Polyamide 6 12 (N H 2 terminal ZC O〇H terminal = 3/7 (molar ratio))

(Preparation method): The resin composition (A 1) and the following resin composition (A 4) were kneaded at a weight ratio of 1 Z3 using a twin-screw extruder. This is a resin composition (A3) was used alone.

Resin composition (A4):

Polyamide 6 12 (NH ₂ terminal COOH terminal = 1/9 (molar ratio))

(Preparation method): A predetermined amount of dodecanedicarboxylic acid was added to an 80% by weight aqueous solution of a salt of hexamethylenediamine and dodecanedicarboxylic acid, and the mixture was pressurized in a nitrogen-substituted autoclave (17.5 kg / cm). ² ) It was heated down (220 ° C) and the water inside the system was discharged out of the system together with nitrogen gas in 4 hours. After that, it took 1 hour to gradually raise the temperature (275 ° C) to remove water residues from the system.The internal pressure of the autoclave was returned to normal pressure, and after cooling, polyamide 612 was removed. Obtained. The obtained polymer had a molecular weight (Mn) of about 20000 and a ratio of amino terminal to carboxyl terminal = 1/9. This polymer alone was used as a resin composition (A4).

Resin composition (A5):

(i) Polyamide 6 12 (NH ₂ terminal ZC〇OH terminal = 3/7 (molar ratio)) 100 parts by weight

(ii) Vulcanizing activator (trimethylolpropane methyl chloride) 1

(Preparation method): A mixture obtained by mixing trimethylolpropane trimethyl methacrylate (TRIM) at a ratio of 1 part by weight to 100 parts by weight of the resin composition (A3) was mixed with a twin-screw extruder. And melt-kneaded to obtain a resin composition (A5).

Resin composition B 1 to B 2

The following resin compositions (B1 to B2) were prepared using polyamide 66 (polycondensate of hexamethylenediamine and adipic acid) as the thermoplastic resin. Note that the calculation of M〇PAC PM 3 was performed based on the following basic units.

NH (CH ₂ ) ₆ -NH-C (= 0)-(CH ₂ ) ₄ -C (= 0) -0H

Resin composition (B 1): Polyamide 66 (NH ₂ terminal / COOH terminal = 1/1 (molar ratio))

(Preparation method): Hexamethylenediamine and adipic acid are used as the combination of monomers, and the molecular weight (Mn) is 200 to 2,500, and the amino terminal and carboxy terminal are obtained by the same preparation method as in the above (A2). A polyamide 66 having a ratio of 1 Z1 was obtained, and this was used alone as a resin composition (B1).

Resin composition (B 2):

Polyamide 66 (NH ₂ terminal / C 00 H terminal = 1/3 (molar ratio))

(Preparation method): Hexamethylenediamine and adipic acid are used as a combination of monomers, and the molecular weight (Mn) is about 2000 by the same preparation method as in the above (A4), and the ratio of amino terminal to carboxylic acid terminal = Polyamide 66 of 1-9 was obtained. This polymer and the resin composition (B 1) were kneaded by a twin screw extruder at a weight ratio of 62.5 / 37.5 to obtain a resin composition (B 2).

Resin composition C1-C3

The following resin compositions (C 1 to C 3) were prepared using Polyamide 6 (ε-ring-opening polymer of force prolactam) as a thermoplastic resin. Note that the calculation of M〇P ACP M 3 was performed based on the following basic units.

NH _2- (CH ₂ ) 5-C (= 0) -NH- (CH ₂ ) ₅ -C OO) -OH

Resin composition (C I):

Polyamide 6 (NH ₂ terminal / C〇OH terminal = 1 Z 1 (molar ratio))

(Preparation method): An 80% by weight ice solution of ε-proprolactam was heated to 250 to 260 ° C in a nitrogen-purged autoclave in the presence of a small amount of phosphoric acid. Moisture in the system was discharged out of the system together with nitrogen gas in 4 hours. Then, it took 1 hour to gradually raise the temperature (275 ° C) to remove water residues from the system, and then cooled to obtain polyamide 6. Got The polymer had a molecular weight (Mn) of about 20000 to 2500, and the ratio of amino terminal to carboxyl terminal was 1/1. This polymer was used alone as a resin composition (C 1).

Resin composition (C2):

Polyamide 6 (NH ₂ terminal / COOH terminal = 1 to 3 (molar ratio))

(Preparation method): A predetermined amount of adipic acid is added to an 80% by weight aqueous solution of ε-caprolactam, in the presence of a small amount of phosphoric acid, in a nitrogen-purged autoclave at 250 to 260 ° C. And the water inside the system was discharged out of the system together with nitrogen gas in 4 hours. Thereafter, the temperature was gradually raised (275 ° C.) over 1 hour to remove water residues outside the system, and then cooled to obtain polyamide 6. The obtained polymer had a molecular weight (Mn) of about 20000 and a ratio of amino-terminal to lipoxyl-terminal = 1Z9. This polymer was used as a resin composition (C4). This (C4) and the resin composition (C1) were kneaded so as to have a weight ratio of 37.5 / 62.5 to obtain a resin composition (C2).

Resin composition (C3):

Polyamide 6 (NH ₂ terminal / COOH terminal = 1 Z4 (molar ratio))

(Preparation method): The above (C 1) and the above (C 4) were kneaded at a weight ratio of 25/75 to obtain a resin composition (C 3).

Resin composition D 1 to D 3

The following resin compositions (D1 to D3) were prepared using a polycondensate of terephthalic acid and trimethylhexamethylene diamine (aromatic nylon A5) as the thermoplastic resin. MOP AC PM 3 was calculated based on the following basic units.

Resin composition (D 1):

Aromatic polyamide A5 (NH ₂ terminal / COOH terminal = 1/1 (mol ratio))

(Preparation method): The molecular weight (Mn) 200 000 to 250 000, the amino terminal and the force were determined by the same preparation method as in the above (A2), using the combination of monomers as trimethylhexamethylene diamine and terephthalic acid. A polymer having a ratio of lipoxy terminal = 1/1 was obtained, and this was used alone as a resin composition (D 1).

Resin composition (D2):

Aromatic polyamide A 5 (NH ₂ terminal / C〇OH terminal = 1/3 (molar ratio))

(Preparation method): The combination of monomers is trimethylhexamethylene diamine and terephthalic acid, and the molecular weight (Mn) is about 20000 by the same preparation method as in the above (A4), and the ratio of the amino terminal to the olepoxyl terminal = 1. / 9 was obtained, and this polymer was used as the resin composition (D 4). The polymer (D4) and the resin composition (D1) were kneaded at a weight ratio of 62.5 / 37.5 by a twin-screw extruder to obtain a resin composition (D2).

Resin composition (D3):

Aromatic boramide A 5 (^^ «: ₂ terminal 7,00 1 terminal = 1 Z 4 (mol ratio)) alone

(Preparation method): The above (D1) and the above (D4) were kneaded in a weight ratio of 25 Z75 to obtain a resin composition (D3).

Resin composition E 1 to E 2

Using PBT (polycondensate of terephthalic acid and 1,4-butanediol) or amine-modified PBT (reaction product of the above PBT with hexamethylene diamine) as a thermoplastic resin, the following resin composition ( E1 to E2) were prepared. The calculation of M〇PACPM3 was performed based on the following basic units. For PBT: HO- (CH ₂ ) ₄ -0-C (= 0) — ^ C (= Q) -OHamine modified For PBT: NH _2- (CH ₂ ) ₆ -NH-C (= 0) "~ ^ ^ -C (= 0) -0- (CH ₂ ) ₄ -OH

Resin composition (E 1):

P BT (OH terminal ZCOOH terminal = 1 1 (molar ratio)) alone (Preparation method): dimethyl terephthalate 1 4 · 5 8 7 kg, 1, 4 1-butanediol 6. 7 6 7 kg, calcium acetate 30 g and 60 g of antimony oxide were charged into a polymerization vessel having a nitrogen gas inlet tube and a distillation side tube, heated to 180 ° C., and supplied with a small amount of nitrogen gas. When the outflow of methanol was confirmed, the temperature was gradually increased under stirring under reduced pressure, and the temperature was gradually lowered to 270 ° C and the degree of vacuum lO OPa or less. After confirming the distillation of ethylene glycol, the mixture was heated and maintained at 270 ° C. for 3 hours, then taken out and allowed to cool. The obtained polymer was defined as a resin composition (E 1).

Resin composition (E2):

Amine-modified PBT (NH ₂ terminal / OH terminal = 1/1 (molar ratio))

(Preparation method): The resin composition (E 1) and the lipoxyl group contained in (E 1) were kneaded with an equimolar amount of methylenediamine for 30 minutes at 230 ° C. using a single die. E 2).

Resin composition F

Poly (2,5-dimethylphenylene ether) (Vestoranl 900, manufactured by Dedasa AG) alone was used to prepare a resin composition. M〇PACPM 3 was calculated based on the following basic units.

Resin composition G

A resin composition was prepared using polypropylene alone. The calculation of MOPAC PM3 was performed based on the following basic units.

_{_{CH 3 -CH (CH 3) -CH}} 2 -CH (CH 3) - CH 2 - CH (CH 3) - CH 2 - CH 2 (CH 3)

Resin composition H

A resin composition was prepared solely from polyacetal (manufactured by Boliplastics Co., Ltd., Dyuracon M90). The calculation of MOPAC PM3 was performed based on the following basic units.

_{_{CH 3 - 0- CH 2 - 0-}} CH 2 - 0- CH 2 -CH 2 - 0- CH 3

Resin composition I 1 to I 3

Resin composition (II):

(Preparation method): 883 g of dimethyl terephthalate purified by distillation, 783 g of 1,4-butanediol and 35.2 g of 2-butene-1,4-diol were added to calcium acetate 1.82 g and antimony oxide 3.64 g were added, and the mixture was placed in a polymerization tube having a stirrer, nitrogen gas inlet tube and distillation side tube, and connected to a vacuum system, and brought to 180 ° C with an oil bath. The mixture was heated and a small amount of nitrogen gas was supplied. Stirring was started when the amount of methanol distilled out reached the theoretical value, and the temperature inside the system was gradually raised to 250 to 260 ° C, and the degree of vacuum was reduced to 100 Pa or less. . While distilling a small amount of the generated 1,4-butanediol, the condensation reaction takes 2 to 3 hours to proceed. In a mixed solvent of tetrachloroethane / phenol = 40/60 (volume ratio) as appropriate Was measured, and when the number average molecular weight reached 100,000, the reaction was terminated to obtain PBT. The concentration of unsaturated bonds in the obtained polymer is an average of 2 2 mol / kg, and this polymer was designated as a resin composition (I 1). Resin composition (1 2):

(Preparation method): Except that 1,4-butanediol was replaced by 819 g and 2-butene-1,4-diol by 70.4 g in the production of (I 1), A polymer having a number average molecular weight of about 1,000 was obtained in the same manner as in 1). The concentration of unsaturated bonds in the obtained polymer was 4 on average in the molecule, 0.4 mol / kg, and this polymer was used alone as a resin composition (12).

Resin composition (13):

(Preparation method): A mixture obtained by mixing trimethylolpropane trimethyl methyl acrylate (TRIM ') at a ratio of 1 part by weight to 100 parts by weight of the resin composition (I2) was subjected to twin-screw extrusion. The mixture was melt-kneaded using a mixer to obtain a resin composition (13).

Resin composition J

(Preparation method): Using a melamine resin (Sumicon MMC-50, a black-colored product) manufactured by Sumitomo BeiClient Co., Ltd., a flat plate of lO OmmX IOO m mx 4 mm is formed, and this flat plate is formed. Was used as a sample of the resin composition (J).

Resin composition K

(Preparation method): Bisphenol A-based epoxy resin (“EPIK〇TE 8288” manufactured by She 11 Co., Ltd.) was added with 100 parts by weight of getylaminopropylamine in a proportion of 6 parts by weight. The mixture was added and cured at 100 ° C. to form a 100 mm × 100 mm × 4 mm flat plate, and this flat plate was used as a sample of the resin composition (K).

Resin composition L

(Preparation method): 604 g of maleic anhydride and 507 g of propylene dalicol were prepared in the presence of 0.2 g of hydroquinone monomethyl ether and 0.6 g of dibutyltin oxide as an esterification catalyst. Dehydrated and condensed at 180 to 190 ° C in a nitrogen stream at normal pressure to obtain a weight average molecular weight of 5 800 unsaturated polyesters were obtained. 3.4 g of cobalt naphthenate was added to this unsaturated polyester, and dissolved and diluted with 600 g of ethyl methacrylate and 100 g of styrene. To 100 parts by weight of the diluted solution, 3 parts by weight of an organic peroxide (Verptyl O, manufactured by NOF Corporation) was added, and after stirring, the mixture was cured at 80 ° C. and cured to 100 mm XI. A flat plate of 00 mm × 4 mm was molded, and this flat plate was used as a sample of the resin composition (L).

[Unvulcanized rubber composition (R)]

The following components were blended in a predetermined ratio to prepare unvulcanized rubber compositions (R1 to R8).

Rubber composition R 1

(0 rubber 100 parts by weight (ethylene propylene diene rubber (gen content 8.2% by weight) 90 parts by weight, polyoctylene rubber 10 parts by weight) (ii) Filler [carbon black (FF)] 1 part by weight

(iii) Radical generator [organic peroxide (dicumyl peroxide)] 5 parts by weight

(iv) Vulcanizing activator 0 parts by weight

(V) Plasticizer (Process oil) 100 parts by weight

(vi) 5 parts by weight of zinc oxide

(vii) Stearic acid 1 part by weight

Rubber composition R 2

(0 rubber 100 parts by weight (ethylene propylene diene rubber (gen content 8.2% by weight) 90 parts by weight, polyoctenylene rubber 10 parts by weight) (ii) Filler [carbon black (FEF)] 1 Parts by weight

(iii) Radical generator [organic peroxide (dicumyl peroxide)] 5 parts by weight

(iv) 1 part by weight of a vulcanizing activator (trimethylolpropane trimethacrylate)

(v) Plasticizer (process oil) 100 parts by weight (vi) 5 parts by weight of zinc oxide

(vii) Stearic acid 1 part by weight

Rubber composition R 3

(i) 100 parts by weight of rubber (90 parts by weight of ethylene propylene diene rubber (8.2% by weight of gen content), 100 parts by weight of polyoctenylene rubber)

(ii) Filler [Carbon Black (FF)] 1 part by weight

(iii) Radical generator [organic peroxide (dicumyl peroxide)] 5 parts by weight

(iv) Vulcanizing activator (butanediol dimethacrylate) 2 parts by weight (v) Plasticizer (process oil) 100 parts by weight

(vi) 5 parts by weight of zinc oxide

(vii) Stearic acid 1 part by weight

Rubber composition R 4

(ii) Filler [Carbon Black (F E F)] 1 part by weight

(iii) Radical generator (tetramethylthiuram disulfide) 3 parts by weight

(iv) Vulcanizing activator (trimethylolpropane trimester acrylate) 1 part by weight

(v) Plasticizer (process oil) 100 parts by weight

(vi) 5 parts by weight of zinc oxide

(vii) Stearic acid 1 part by weight

Rubber composition R 5

(i) 100 parts by weight of rubber (60 parts by weight of natural rubber, 35 parts by weight of ethylene propylene rubber, 5 parts by weight of polyoctylene rubber)

(ii) Filler [Carbon Black (F E F)] 1 part by weight

(iii) Radical generator [organic peroxide (dicumyl peroxide)] 5 parts by weight (iv) Vulcanizing activator (trimethylolpropane trimethacrylate)

1 part by weight

(V) Plasticizer (Process oil) 100 parts by weight

(vi) 5 parts by weight of zinc oxide

(vii) Stearic acid 1 part by weight

Rubber composition R 6

(i) Silicone rubber (“SH851”, manufactured by Toray Dow Corning Co., Ltd.) 100 parts by weight

(ii) Filler 0 parts by weight

(iii) Radical generator [organic peroxide (dicumyl peroxide)] 3 parts by weight

(iv) Vulcanizing activator (trimethylolpropane trimethacrylate) 1 part by weight

(V) Plasticizer (oil) 0 parts by weight

(vi) Zinc oxide 0 parts by weight

(vii) 0 parts by weight of stearic acid

Rubber composition R 7

(0 Silicone rubber (“4104U”, manufactured by Dow Corning Toray) 100 parts by weight

(ii) Filler 0 parts by weight

(iii) Radical generator (2,5-dimethyl-2,5-di- (f-butylperoxy) hexyne-1 3 Nippon Yushi Co., Ltd.) 4 parts by weight

(iv) Vulcanizing activator 0 parts by weight

(v) Plasticizer (oil) 0 weight:: parts

(vi) Zinc oxide 0 parts by weight

(vii) 0 parts by weight of stearic acid

Rubber composition R 8

(0 Fluoro rubber (FKM) (Dai EL “G920” manufactured by Daikin Industries, Ltd.) 100 parts by weight (ii) Filler 0 parts by weight

(iii) Radical generator (dicumyl peroxide) 3 parts by weight

(iv) Vulcanizing activator (triallyl isocyanurate) 4 parts by weight

(v) Plasticizer (oil) 0 parts by weight

(vi) Zinc oxide 0 parts by weight

(vii) 0 parts by weight of stearic acid

Table 1 below shows the component compositions of the unvulcanized rubber compositions (R 1 to R 8).

Rubber composition R1 R2 R3 R4 R5 R6 R7 R8

Rubber EPDM90 EPD 90 EPDM90 EPDM90 EPDM35 (VMQ) (VMQ) (FKM)

V10 V10 V10 V10 Marauder 0 SH851 4104U Dai El G920

V5 100 100 100

Flyer-FEF FEF FEF FEF FEF 0 0 0

1 1 1 1 1

Rashi "Cal generator P-Cumyl P0 C-cumyl P0 C-cumyl P0 Ϊtramethylthiura V-cumyl P0 C-cumyl P0 / \ ° -Hexa ^: cumyl P0

5 5 5 Musi 'Sulfi 5 3 25B40 3

G '3 4

Vulcanizing activator 0 TRIM B 瞧 TRIM TRIM TRIM 0 TAIC

1 2 1 1 1 4

Plasticizer (oil) one. Roses Talent 7 Roses Talent Roses sir process oil. Roses Taylor 0 0 0

75

100 100 100 100 100

Zinc oxide 5 5 5 5 5 0 0 0

Stearic acid 1 1 1 1 1 0 0 0

The components in the table are as shown below.

[Rubber] EPDM: Ethylene propylene diene rubber,

V: Polyoctenylene rubber,

NR: natural rubber,

Q— 1: Silicone rubber (SH851),

Q-2: Silicone rubber (410 U), FKM: Fluorine rubber

[Filler] F E F: Rikiichi Pump Rack

[Radical generator] DKPO: dicumyl peroxyside,

TMTD: Tetramethylthiuram disulfide, perhexa 25 B 40: 2,5 -dimethyl 2,5 -di (t-butylperoxide) hex 3

[Vulcanizing activator] TR I M: Trimethylol mouth pantrimethacrylate,

BDMA: butanediol dimethacrylate,

T AIC: Triaryl isocyanurate. ' Example;! To 99 and Comparative Examples 1 to 4 1

The resin composition was powder-framed by a freeze-pulverization method to prepare a powder having a particle diameter of 8 O ^ m or less. The obtained resin powder (40 parts by weight) and the rubber composition (100 parts by weight) were used in combinations shown in Tables 2 to 10 and mixed and kneaded with a roll at a temperature of 80. At a temperature of 180 ° C., a 3 mm-thick flat plate was formed and vulcanized to produce a composite dispersion.

With respect to the obtained flat composite dispersion, the tensile strength at break and the abrasion loss of the fiber (polishing stone CS5 17) were measured at a temperature of 20 ° C. and a relative humidity of 65%. Note that the results of the tensile test were expressed as a relative value to the tensile strength of the rubber composition alone, where the tensile strength of the rubber composition alone without mixing the resin powder was 100. . The bonding strength between rubber and resin was measured as follows. Each of the above resin materials was formed into a flat plate having a thickness of 2 mm by injection molding. Separately, an unvulcanized sheet having a thickness of 2 mm was prepared from the above rubber material, and both were vulcanized and bonded by a compression molding machine at 180 ° C. for 10 minutes while in contact with each other. After bonding, the sample was left for 24 hours and subjected to a 180 ° peel test. In this peeling test, when the peeling of both proceeded due to cohesive rupture of the rubber material, the bonding strength was evaluated as “A”. On the other hand, when all of the peeling proceeded at the rubber / resin interface peeling, the bonding strength was evaluated as “C”, and when the cohesive failure on the rubber side and the interface peeling between the rubber and resin occurred combined, “B” It was evaluated.

The results are shown in Tables 2 to 10. In the table, “The number of active atoms in one molecule 丄 indicates the number of active atoms (S≥0.006) in one molecule of the thermoplastic resin obtained by the calculation of MOP AC PM3. In the above calculation, E c was −8 eV (when the radical generator was a peroxide) or 16 eV (when the radical generator was tetramethylthiuram disulfide). .

Table 9

Kets

Table 10

Resin rubber

Type Rubber Ζ Resin Tensile Taber Joint strength Strength Abrasion mg Example 79 1 1 R 1 Β 6 2 1 3.1 Example 80 1 1 R 2 A 9 3 1 1.3 Example 81 1 1 R 5 A 85 1 2.1 Example 82 1 1 R 6 B 75 3 1 Example 83 1 2 R 1 A 68 12.5 Example 84 1 2 R 2 A 89 1 1.9 Example 85 1 2 R 5 A 92 1 2.3 Example 86 1 2 R 6 A8 125 Example 87 1 3 R 1 A 92 11.1 Example 88 JR 1 B 63 14.0 Example 89 JR 2 B 68 14.8 Example Example 90 JR 5 B 65 1 3.6 Example 91 JR 6 B 6 3 3 9 Example 92 KR 1 B 7 3 1 2.3 Example 93 κ 2 B 78 12.5 Example 94 κ R 5 B 8 1 1 2.5 Example 95 κ R 6 B 7 1 3 5 Example 96 Example R 1 B 7 1 1 2.4 Example 97 Example R 2 A 8 9 12.1 Example 98 Example R 5 A 87 1 1.9 Example 99 R 6 B 75 3 3

Claims

The scope of the claims

1. A composite dispersion in which a vulcanized rubber phase and a resin phase are directly bonded, wherein the vulcanized rubber phase constitutes a matrix phase and the resin phase constitutes a dispersed phase.

2. The composite dispersion according to claim 1, wherein the vulcanized rubber phase and the resin phase form a sea-island structure.

3. The composite dispersion according to claim 1, wherein the dispersed phase particles are partially exposed on the surface.

4. The composite dispersion according to claim 1, wherein the resin phase is composed of at least one of a thermoplastic resin and a thermosetting resin.

5. The thermoplastic resin is a polyamide resin, polyester resin, poly (thio) ether resin, polycarbonate resin, polyimide resin, polysulfone resin, polyurethane resin, polyolefin resin, halogen-containing resin, At least one selected from a styrene resin, a (meth) acrylic resin and a thermoplastic elastomer, wherein the thermosetting resin is a phenol resin, an amino resin, an epoxy resin, a silicone resin, a thermosetting polyimide resin. The composite dispersion according to claim 4, wherein the composite dispersion is at least one selected from the group consisting of a thermosetting polyurethane resin, a thermosetting acryl resin, a vinyl ester resin, an unsaturated polyester resin, and a diaryl phthalate resin. .

6. The resin phase is composed of aliphatic polyamide resin, aromatic polyester resin, polyacetal resin, polyphenylene ether resin, polysulfide resin, polyolefin resin, polyurethane resin, and polyamide resin. 2. The method according to claim 1, wherein the resin is at least one resin selected from the group consisting of an elastomer, a polyester elastomer, a polyurethane elastomer, a polystyrene elastomer, and a polyolefin elastomer. Composite dispersion.

7. The rubber phase is gen-based rubber, ore-based rubber, acrylic-based 2. The composite dispersion according to claim 1, comprising at least one rubber selected from rubber, fluororubber, silicone rubber, and urethane rubber.

8. The composite dispersion according to claim 1, wherein the ratio of the vulcanized rubber phase to the resin phase is vulcanized rubber phase Z resin phase = 90/10 to 10/90 (weight ratio).

9. The composite dispersion according to claim 1, wherein at least one of the vulcanized rubber phase and the resin phase is formed of a composition containing at least one vulcanizing agent among a radical generator and sulfur.

1 0. The resin phase has the following formula (1)

-(Sh HOMO, ZI Lc— "^ ΗΟΜΟ, η I + (Sh LU O'ii), 1-^ c ^_ E _{LUM0> I1} I (1)

(Wherein, E _e, C positions _n, E positions ", C drowsiness, _n, E hide. _N are all a value calculated by the semiempirical-molecular orbital method M_〇 PACPM 3, E _c representing an orbital energy (e V) of a radical of La radical generating agent, C transliteration _0, "the highest occupied molecular orbital (HOMO of the n-th hydrogen atom and Z or sulfur atom constituting the basic unit of the resin a molecular orbital coefficients), E _{picture) n} representing an orbital energy (e V) of the HOMO, C _L丽, "the lowest unoccupied molecular orbital (LUMO of the n-th hydrogen atom and Z or a sulfur atom) Shows the molecular orbital coefficient of

Indicates the orbital energy (eV) of the LUMO)

10. The composite according to claim 9, comprising a resin having at least two hydrogen atoms and at least two Z or sulfur atoms per molecule on average, having an orbital interaction energy coefficient S of 0.06 or more. Dispersion.

1 1. The composite according to claim 1, wherein the resin phase is composed of at least one crosslinking resin selected from a thermoplastic resin having an unsaturated bond and a thermosetting resin having a crosslinkable functional group. body.

12. The composite according to claim 11, wherein the thermoplastic resin having an unsaturated bond is any one of the following (1) to (3).

(1) A polymerizable compound having a reactive group (A) and an unsaturated bond, and a thermosetting compound having a reactive group (B) reactive with the reactive group (A) Resin formed by reaction with plastic resin

(3) Polymer blend composed of resin having unsaturated bond and resin

13. The complex according to claim 11, wherein the concentration of the unsaturated bond is 0.01 to 6.6 mol per 1 kg of the resin.

14. The composite dispersion according to claim 9, wherein the radical generator is at least one selected from an organic peroxide, an azo compound, and a sulfur-containing organic compound.

1 5. The composite dispersion according to claim 9, wherein the radical generator is an organic peroxide.

10. The composite dispersion according to claim 9, wherein the vulcanized rubber phase is formed of a composition containing 1 to 10 parts by weight of a vulcanizing agent per 100 parts by weight of unvulcanized rubber.

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

18. The composite dispersion according to claim 17, wherein the vulcanization activator is an organic compound having at least two polymerizable unsaturated bonds in one molecule.

19. The composite dispersion according to claim 17, which is formed of a composition containing 0.1 to 5 parts by weight of a vulcanization activator based on 100 parts by weight of a vulcanized rubber phase and a Z or resin phase.

20. A method for producing a composite dispersion composed of a vulcanized rubber phase and a resin phase by kneading and molding a rubber and a resin, wherein an unvulcanized rubber is used as the rubber. A method for producing a composite dispersion.

21. The method according to claim 20, wherein at least one of the rubber and the resin contains a vulcanizing agent.

22. The method according to claim 20, wherein the resin is a granular material.