KR20030022329A - Composite Dispersion and Process for Production Thereof - Google Patents

Abstract

The resin and the unvulcanized rubber (particularly, a rubber composition comprising a radical generator and a vulcanizing activator) are melt kneaded and molded, and the vulcanized rubber is vulcanized or crosslinked, and the vulcanized rubber phase constitutes a continuous phase and the resin phase constitutes a dispersed phase. A composite dispersion can be produced. As said resin, resin which has an active atom (thermoplastic resin, such as a polyamide resin, thermosetting resin, crosslinked or hardened resin) is used. In the composite dispersion, since the rubber phase forms a matrix phase and the dispersed phase particles (resin) may be partially exposed on the surface, the rubber characteristics are expressed on the surface while having the rubber characteristics (for example, sliding properties). You can.

Description

Composite Dispersion and Process for Manufacturing {Composite Dispersion and Process for Production Thereof}

As the required quality for polymer materials increases, materials having various properties (for example, tensile strength, tensile elasticity, hardness, wear resistance, heat resistance, cold resistance, oil resistance, chemical resistance, weather resistance, molding processability, etc.) are expected. For example, the material which has the characteristic of a rubber and a characteristic different from the characteristic of this rubber (for example, low friction coefficient which is a characteristic of resin, etc.) is calculated | required. Then, the composite which has the characteristic of resin and rubber is proposed by joining and integrating a resin molding member and a rubber molding member.

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

Moreover, the method of directly bonding a resin molding member and a rubber molding member is proposed. For example, Japanese Unexamined Patent Publication (Kokai) No. 50-25682 discloses a thermoplastic resin and a vulcanized rubber having compatibility with the thermoplastic plastics in friction contact with each other at the contact surface, and in contact with the thermoplastic resin component in a molten state. It is proposed to solidify the rubber component to obtain a composite. However, in this method, it was difficult to obtain a complex shape complex with high productivity.

Japanese Patent Laid-Open No. 9-124803 discloses an acrylonitrile-containing thermoplastic resin (AS, ABS resin, etc.) and an acrylonitrile-containing rubber by heat-adhering the composite member by using a compatibility between the thermoplastic resin and the rubber. It is proposed to obtain. However, this method is limited to resins and rubbers containing acrylonitrile and its practicality is very narrow.

Japanese Patent Application Laid-Open No. Hei 8-156288 discloses vulcanization by contacting a resin composition containing an epoxy group with an elastic rubber having a vulcanized carboxyl group or an acid anhydride group, and utilizing a chemical reaction between an epoxy group and a carboxyl group, The method of obtaining the composite member joined by the contact surface of is proposed. However, in this method, since the chemical reaction of an epoxy group and a carboxyl group is used, the kind of resin and rubber | gum is largely limited, and it was difficult to obtain a composite in a wide range.

Japanese Patent Laid-Open No. 2-150439, Japanese Patent Laid-Open No. 3-133631, and Japanese Patent Laid-Open No. 3-138114 disclose polyamide resins and rubber components in the presence of vulcanization. In the method for producing a composite by vulcanizing, a rubber component comprising a carboxyl group or an acid anhydride-containing rubber, a peroxide, a vulcanizing activator (ethylene glycol dimethacrylate, triallyl isocyanurate, etc.) and an alkoxysilane compound as a rubber component It is proposed to use. In these documents, as the aliphatic polyamide-based resin, a polyamide resin having more terminal amino groups than the terminal carboxyl group is mainly used. That is, reaction with an amino group, a carboxyl group, or an acid anhydride group is used. Therefore, the kind of resin and rubber is restrict | limited greatly, and it was difficult to obtain a composite of resin and rubber in a wide range.

Japanese Patent Laid-Open No. 7-11013 discloses a method of obtaining a composite member of a polyamide molded body and a vulcanized rubber by vulcanization by contacting and vulcanizing a polyamide molded body with rubber, a rubber pound containing a peroxide vulcanizing agent and a silane compound. It is proposed.

However, the composite obtained by this method is joined at the contact surface of the resin member and the rubber member. Therefore, the surface of the said composite surface showed only the characteristic of either resin and rubber | gum, and could not show the characteristic of both resin and rubber | gum.

It is therefore an object of the present invention to provide a composite dispersion in which a resin phase and a vulcanized rubber phase are firmly bonded 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 and a method for producing the same, which can effectively express both properties of resin and rubber.

Another object of the present invention is to provide a composite dispersion and a method for producing the same, which can effectively express the properties of the resin on the surface while having the properties of rubber.

The present invention relates to a composite dispersion (or composite dispersion member) composed of a resin and rubber, and also useful as a mechanical component, an automobile component, and the like, and a manufacturing method thereof.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said subject, when the rubber and resin are kneaded and shape | molded, the vulcanized or crosslinked vulcanized rubber phase and resin phase are firmly joined, and the characteristic of both resin and rubber is expressed effectively. It was found 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 bonded to each other. In addition, "direct bonding" can be defined as "a state in which the vulcanized rubber phase and the resin phase are adhered without using an adhesive, and the peeling progresses along the cohesive failure of the rubber phase when the sheet-like two phases are mechanically peeled off. Can be.

The composite dispersion may form an island-in-an ocean structure with a vulcanized rubber phase and a resin phase. In addition, the dispersed phase particles may be partially exposed on the surface.

In addition, the dendritic phase may be composed of at least one component of a thermoplastic resin and a thermosetting resin. The resin phase may be various resins such as polyamide resins, polyester resins, poly (thio) ether resins, polycarbonate resins, polyimide resins, polysulfone resins, polyurethane resins, and polyolefins. 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, diallyl 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 dendritic phase exhibits high activity with respect to the radical generator, and at least an average of at least 2 hydrogen atoms and / or sulfur atoms having a specific orbital interaction energy coefficient S of 0.006 or more by one molecular orbital method represented by Equation 1 below: It can also be comprised with resin which has a dog.

S = (C _{HOMO, n} ) ² / | E _C -E _{HOMO, n} | + (C _{LUMO, n} ) ² / | E _C -E _{LUMO, n} |

( _Wherein E _C , C _{HOMO, n} , E _{HOMO, n} , C _{LUMO, n} , E _{LUMO, n} are all values calculated by semi-empirical molecular orbital method MOPACPM3, where E _C is the radical orbit of the radical generator) Represents energy (eV), and C _{HOMO, n} represents the molecular orbital coefficient of the highest peak molecular orbital (HOMO) of the nth hydrogen atom and / or sulfur atom constituting the basic unit of the resin, and E _{HOMO, n} Represents the orbital energy (eV) of the HOMO, C _{LUMO, n} represents the molecular orbital coefficient of the lowest co-molecular orbital (LUMO) of the n-th hydrogen atom and / or sulfur atom, E _{LUMO, n} is the Orbital energy (eV) of LUMO)

Further, the dendritic phase may be composed of at least one crosslinkable resin selected from a thermoplastic resin having an unsaturated bond and a thermosetting resin having a crosslinkable functional group. The thermoplastic resin having an unsaturated bond may be in the form of any one of the following (1) to (3), and the concentration of the unsaturated bond may be about 0.01 to 6.6 moles per 1 kg of the resin.

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

(2) Thermoplastic resins in which unsaturated bonds are introduced by copolymerization or cocondensation

(3) polymer blends composed of resins and resins having unsaturated bonds

Vulcanizing agents include radical generators such as organic peroxides, azo compounds, sulfur-containing organic compounds, sulfur and the like. At least one component of the unvulcanized rubber and resin may contain a vulcanizing activator, for example an organic compound having at least two polymerizable unsaturated bonds in one molecule.

In the method of the present invention, a composite dispersion composed of a vulcanized rubber phase and a resin phase is produced by kneading and molding a rubber (unvulcanized rubber) and a resin. In this method, at least one component of the rubber and the resin may include a vulcanizing agent. In addition, the said resin can also be used in the form of a granular material.

In addition, in this invention, resin shall contain the graft copolymer (for example, HIPS, ABS resin, etc.) containing a rubber component.

<Best Mode for Carrying Out the Invention>

[Suzy]

Thermoplastic resin, thermosetting resin, etc. can be used as resin.

As the thermoplastic resin, for example, polyamide resin, polyester resin, polyurethane resin, poly (thio) ether resin (polyacetal resin, polyphenylene ether resin, polysulfide resin, polyether ketone Condensed thermoplastic resins such as polycarbonate resins, polycarbonate resins, polyimide resins, polysulfone resins, and polyurethane resins; Vinyl polymerization thermoplastic resins, such as polyolefin resin, (meth) acrylic resin, styrene resin, halogen-containing resin, and vinyl resin (for example, polyvinyl acetate, polyvinyl alcohol, etc.); Thermoplastic elastomers and the like can be exemplified.

As a thermosetting resin, For example, polycondensation or addition condensation-type resin, such as a phenol resin, an amino resin, an epoxy resin, a silicone resin, a thermosetting polyimide resin, a thermosetting polyurethane resin; Addition polymerization resin, such as a thermosetting acrylic resin, vinyl ester resin, unsaturated polyester resin, and diallyl phthalate resin, can be illustrated.

These resins (thermoplastic resin, thermosetting resin) can be used individually or in combination of 2 or more types.

Moreover, it is preferable that the said resin is resin which shows high activity with respect to a vulcanizing agent (especially radical generating agent). As such a resin,

(i) resins having active atoms, (ii) resins having crosslinkable groups, (iii) resins having active atoms and crosslinkable groups, and the like can be exemplified (hereinafter, these resins are simply referred to as resins or active resins). There). When the resin (active resin) having the active atom and / or the crosslinkable group is used, the rubber phase and the resin phase can be reliably bonded even if a wide range of rubber is selected as the rubber component.

(Resin with active atoms)

In this invention, an active atom represents the atom (for example, active hydrogen atom and active sulfur atom) which shows high activity with respect to a radical generating agent. Specifically, the resin can be selected according to the type of radical generating agent, for example, an active atom whose orbital interaction energy coefficient S represented by the following formula (1) is equal to or greater than a certain value (for example, 0.006, preferably 0.008). May have Preferred orbital interaction energy coefficients S of the active atoms are 0.006 to 0.06, preferably about 0.007 to 0.05 (particularly 0.01 to 0.045). The number of these active atoms depends on the binding site (terminal, branched or main chain, etc.) of the functional group having the active atoms, for example, on average 2 or more (about 2 to 10000), preferably average, 1 molecule of the resin It is 2.5 or more (about 2.5-5000 pieces), More preferably, it is an average of 3 or more (about 3-1000 pieces). The number of active atoms in one molecule of resin is usually about 2 to 100 (preferably 2.5 to 50, more preferably 3 to 25, especially 3 to 20).

<Equation 1>

S = (C _{HOMO, n} ) ² / | E _C -E _{HOMO, n} | + (C _{LUMO, n} ) ² / | E _C -E _{LUMO, n} |

( _Wherein E _C , C _{HOMO, n} , E _{HOMO, n} , C _{LUMO, n} , E _{LUMO, n} are all values calculated by semi-empirical molecular orbital method MOPACPM3, where E _C is the radical orbit of the radical generator) Energy (eV), and C _{HOMO, n} represents the molecular orbital coefficient of the highest peak molecular orbital (HOMO) of the nth hydrogen atom and / or sulfur atom constituting the basic unit of the resin, and E _{HOMO, n} is Represents the orbital energy (eV) of the HOMO, C _{LUMO, n} represents the molecular orbital coefficient of the lowest co-molecular orbital (LUMO) of the n-th hydrogen atom and / or sulfur atom, E _{LUMO, n} is the LUMO Represents the orbital energy (eV) of

MOPACPM3 of Equation 1 is one of molecular orbital methods (MO). The molecular orbital method is one of the approximation methods for discussing the electronic state of molecules, and can be roughly divided into three types: empirical methods such as Huckel's method, semi-empirical method that increases the approximation of Huckel's method, and non-experimental method that calculates molecular orbital function by exact calculation. Can be. In recent years, with the development of computers, semi-empirical and non-empirical methods have become main methods. Molecular trajectory is one of the most powerful ways to link molecular structures with their chemical reactivity. For example, the number of registrations about the molecular orbital method in the Japanese scientific and technical literature information database (JOIS) is about 53000 cases when the keyword is searched by the "molecular orbital method" (period: 1980 to May 2000). )to be. MOPACPM3 is a method that forms the core of the NDD0 (Neglect of Diatomic Differential 0verlap) method, which is one of the semi-empirical methods.

MOPACPM3 is mainly used for the purpose of considering the reaction of organic compounds, and many literatures and books ("Molecular Orbital MOPAC Guidebook" (Hiranotsuneo, Watanabegazuto, Gaibunto, 1991), 3rd Edition: Introduction to Quantum Chemistry ”(Yazawa Sadaziro et al., Kagaku-dojin, 1983), Computational Chemistry Guidebook (Osawa Age et al., TimClark, Maruzen, 1985). .

The basic unit in Equation 1 refers to a model molecular structure formed by the terminal of the polymer and about 1 to 3 repeating units. That is, when calculating with respect to a high molecular compound by MOPACPM3, since the number of the atoms which comprise a molecule is too large, it is difficult to calculate for the molecule itself. Therefore, calculation can also be performed with respect to the molecular structure model (basic unit) formed from the terminal of a polymer and about 2-3 repeating units. For example, the molecular structure (repeating unit) of polybutylene terephthalate (PBT) is generally represented by the formula-(CH ₂ -CH ₂ -CH ₂ -CH ₂ -OC (= 0) -C ₆ H ₄ -C ( = O) -O) _n -but, in Equation 1, the basic unit is conveniently HO-CH ₂ -CH ₂ -CH ₂ -CH ₂ -OC (= O) -C ₆ H ₄ -C (= It can also be calculated as O) -OH.

The orbital interaction energy coefficient S of Equation 1 is sometimes referred to as a reactivity index, is defined and explained in various books, and the like, and is a parameter that is very commonly used when discussing chemical reactivity. For example, introductory frontier orbital theory (p. 72, Yamanabe Shinichi, Inagakitoshi Book, Godansha Scientific, 1989) states that the orbital interaction energy coefficient S is `` when two orbitals interact ( a) the smaller the energy difference, the larger the overlap (b), the stronger the interaction. Equation 1 is based on the superdelocalozability (Sr) mindset published in 1954 by Dr. Kofukui, a Nobel Prize-winning doctor (in order to use the molecular orbital method, p. 71, Imotominoru, Kagaku Dojin, 1986). From Sr's way of thinking, the same equation as in Equation 1 is derived from many books and literature.

What is important here is that molecular orbitals are already widely recognized methods for discussing molecular structures and their chemical reactivity. Therefore, the orbital interaction energy coefficient S [1 / eV] defined in Equation 1 is not merely a conceptual value but a value having the same meaning as a parameter or physical property value (molecular weight, functional group, etc.) for specifying a material.

The radical orbital energy E _c (eV) of the radical generator is preferably calculated by MOPACPM3 based on the molecular structure of the radical, but a predetermined value may be used for convenience based on the type of the radical generator. For example, a radical generating agent is an organic peroxide in the E _c = -8 eV, a sulfur-containing organic compound other than the E _c = -5 eV, sulfur in the azo compound may be calculated as E _c = -6 eV.

Orbital interaction energy coefficient S is a predetermined value (e.g., 0.006) or more as the hydrogen atoms (active hydrogen atoms), and when a radical-generating agent is an organic peroxide, an amino (-NH ₂₎ group (e.g., a terminal amino group), Imino (-NH-) groups (e.g., main or terminal imino groups, (-NH-) groups of amide bonds), methyl (-CH ₃ ) groups, methylene (-CH _2- ) groups (backbone or Hydrogen atoms, such as a terminal methylene group) and a methylidine (-CH =) group (backbone or terminal methylidine group), are mentioned.

Moreover, as a sulfur atom (active sulfur atom) whose orbital interaction energy coefficient S is more than a fixed value (for example, 0.006), when the radical generator is an organic peroxide, a thio group (-S-) and a mercapto (-SH) group And sulfur atoms such as alkylthio group (C _1-4 alkylthio group such as methylthio group and ethylthio group) and sulfinyl group (-SO-).

As said methyl group, the methyl group couple | bonded with an alkylene chain, the cycloalkylene chain, or an aromatic ring, the methyl group couple | bonded with an oxygen atom (methyl group of a methoxy group), etc. can be illustrated, for example. As a methylene group, For example, the methylene group of the linear or branched alkylene group which forms a main chain or a side chain, the methylene group of (poly) oxyalkylene units, such as a (poly) oxymethylene unit and a (poly) oxyethylene unit, Methylene groups adjacent to nitrogen atoms, such as an amino group and an imino group, etc. can be illustrated. As a methylidine group, the methylidine group of the (alpha) -position adjacent to an amino group or an imino group, for example, the methylidine group of the (alpha) -position with respect to the amino group of an aminocycloalkyl group, etc. can be illustrated.

The resin having an active atom may have a plurality of active atoms (eg, two or more on average) in one molecule. That is, the resin is generally not a single molecule, but a plurality of molecular mixtures that differ somewhat in structure, chain length, and the like. Therefore, it is not necessary for every molecule to have a plurality of active atoms, and the average number of active atoms per molecule may be two or more when calculated for the expected main plurality of basic units. For example, the activity contained in a polymer having a repeating unit-(NH- (CH ₂ ) ₆ -NH-C (= 0)-(CH ₂ ) _4- (C = 0) _n- (polyamide 66) The number of hydrogen atoms can be calculated based on the model basic unit NH ₂ — (CH ₂ ) ₆ —NH—C (═O) — (CH ₂ ) ₄ —C (═O) —OH, and the radical generator is organic. When peroxide, two hydrogen atoms in 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 polyamide 66 can be calculated based on the following formula (2) by the ratio of the terminal NH ₂ group and the terminal COOH group of the polymer (polyamide 66) as an aggregate. .

N = 2 × A

(Wherein A represents the number of average terminal NH ₂ groups in 1 molecule)

For example, in the case of terminal NH ₂ group / terminal COOH group = 1/1 (molar ratio), the number A = 1 of terminal NH ₂ groups in one molecule and the number N of active hydrogen atoms in one molecule are N = 2. In the case of the terminal NH ₂ group / terminal COOH group = 1/2 (molar ratio), the number A = 2/3 of the terminal NH ₂ groups in one molecule and the number N = 4/3 of the active hydrogen atoms in one molecule .

In the case where the resin is a mixed resin composed of a plurality of resins having different active atom numbers, the active atom number of the mixed resin may be represented by an average value of the active atom numbers of each resin. That is, by calculating the number of active atoms individually from the basic units of each resin constituting the mixed resin, and calculating the average of the number of active atoms based on the weight ratio of each resin, the apparent number of active atoms of the mixed resin can be calculated. Can be. For example, the mixed resin consists of the said N = 2 polyamide 66 (A) and said N = 4/3 polyamide 66 (B), and (A) / (B) = 1/1 (molar ratio) In the case of, the number of active atoms in one molecule of the mixed resin can be regarded as N = 5/3. In addition, the mixed resin consists of said N = 2 polyamide 66 (A) and the polyamide 66 (C) whose total terminal is a carboxyl group (that is, N = 0), (A) / (C) = 3/1 In the case of (molar ratio), the number of active atoms in 1 molecule of mixed resin can be regarded as N = 3/2.

Examples of the thermoplastic resin having such active atoms include polyamide resins, polyester resins, polyacetal resins, polyphenylene ether resins, polysulfide resins, polyolefin resins, polyurethane resins, and the like. Thermoplastic elastomer, amino resin, etc. can be illustrated.

Moreover, even if it does not have a plurality of said active atoms, it can also be used as modified resin which introduce | transduced active atoms (amino group, oxyalkylene group, etc.). As such a thermoplastic resin, vinyl polymer type resin ((meth) acrylic-type resin (methyl polymethacrylate, methyl methacrylate-styrene copolymer (MS resin), polyacrylonitrile etc.), styrene resin (polystyrene, for example) Styrene copolymers such as AS resins and styrene-methyl methacrylate copolymers: styrene-based graft copolymers such as HIPS and ABS resins, etc., alone or copolymers of halogen-containing monomers (polyvinyl chloride, vinylidene chloride copolymer); Etc.), vinyl resins (polyvinyl acetate, polyvinyl alcohol, etc.), condensed resins [polycarbonates (such as bisphenol A polycarbonate resins), polyimide resins, polysulfone resins, poly Ether sulfone resin, polyether ether ketone resin, polyarylate resin and the like].

In the said vinyl polymerization resin, a carboxyl group or an acid anhydride group is introduce | transduced into vinyl-polymer type resin by copolymerization of a vinyl monomer, and carboxyl groups, such as (meth) acrylic acid and maleic anhydride, or an acid anhydride group containing monomer, for example. According to the present invention, a modified resin may be produced by reacting with thionyl chloride to generate an acid chloride group, and reacting with ammonia, monosubstituted amines (monoalkylamine, monoarylamine, etc.) or diamines exemplified above to introduce amino groups. Furthermore, an active hydrogen atom is obtained by copolymerizing (poly) oxyalkylene glycol mono (meth) acrylate and (poly) oxyalkylene glycol monoalkyl ether (meth) acrylate with the vinyl monomer or by graft polymerization on a vinyl polymerization resin. It can also be modified by introducing.

In addition to the vinyl-based resin as well as the condensed system, the carboxyl group or the acid anhydride group-containing monomer may be grafted to the resin to introduce a carboxyl group or an acid anhydride group into the resin, and the reaction may be carried out with thionyl chloride as necessary in the same manner as above to react with an acid. It is also possible to generate a chloride group and react with ammonia, monosubstituted amines or the diamines exemplified above to introduce and modify the amine group.

Moreover, resin can also be comprised by resin composition (or modified resin) which contains the said active atom in predetermined concentration, and the resin composition of another resin. In another thermoplastic resin, an unmodified thermoplastic resin corresponding to the modified resin, for example, a styrene resin, a (meth) acrylic resin, a single or copolymer of a halogen-containing monomer (such as a fluorine resin), a vinyl resin, a polycar Carbonate resins, polyimide resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, polyarylate resins, liquid crystalline polyester resins, and the like.

Moreover, in thermosetting resin (for example, amino resin, such as urea resin, aniline resin, melamine resin, guanamine resin, condensation system resin, such as a phenol resin and an epoxy resin), it bridge | crosslinks using a hardening | curing agent which has an active atom, or Active atoms can also be introduced by curing. As a hardening | curing agent, it can select according to the kind of resin, For example, an amine-type hardening | curing agent (For example, aliphatic polyamines, such as triethylenetetramine, an aromatic polyamine, such as metaphenylenediamine, diaminodiphenylmethane, etc.), an amide A system hardening | curing agent (for example, polyamide amine etc.) etc. are mentioned.

In addition polymerization system resins (for example, unsaturated polyester, vinyl ester resin, diallyl phthalate resin, etc.), such as radical polymerization with a small active atom concentration, an active atom can also be introduce | transduced by copolymerizing with the monomer which has an active atom. . Examples of the monomer having an active atom include (poly) oxyalkylene glycol mono (meth) acrylates such as monomer ((poly) oxyethylene glycol mono (meth) acrylate) having an oxyC _2-4 alkylene unit, (Poly) oxyalkylene glycol monoalkyl ether (meth) acrylates, such as (poly) oxyethylene glycol monomethyl ether (meth) acrylate, a polyfunctional monomer, for example, (poly) oxyethylene glycol di (meth) acryl (Poly) oxyalkylene glycol di (meth) acrylates, such as the rate, di (meth) acrylate of a bisphenol A alkylene oxide adduct, etc., monomer (acrylamide, methylene bis (meth) acryl) which has an amide bond Amides, such as acrylamides such as 1,1-bisacrylamide-ethane, and the like.

In the thermosetting acrylic resin, an amino resin (for example, melamine resin, guanamine resin, etc.) may be crosslinked using a crosslinking agent, and an active atom may be introduced therein, and the constituent monomer and active atom of the thermosetting acrylic resin may be used. An active atom can also be introduce | transduced by copolymerizing with a polyfunctional polymerizable monomer.

The ratio of resin which has an active atom is 30-100 weight% with respect to the whole resin component, Preferably it is 50-100 weight%, More preferably, it is about 80-100 weight%.

(Resin having a crosslinkable group)

The resin having a crosslinkable group (hereinafter sometimes referred to as crosslinkable resin) can be broadly divided into a thermoplastic resin having an unsaturated bond (polymerizable or crosslinkable unsaturated bond) and a thermosetting resin having a crosslinkable functional group. Crosslinkable resin may have the said unsaturated bond and crosslinkable functional group. When such a crosslinkable resin is used, since the crosslinking reaction advances also at the interface between the rubber component and the resin component in the vulcanization of the rubber component, even when a wide range of rubber components are selected as the rubber component, it is rubbery (or vulcanized rubbery). And dendritic phase can be firmly bonded.

In the 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 various bonds exhibiting crosslinkability or polymerizability by applying heat or light (particularly polymerization) Sex unsaturated bonds). The unit having such an unsaturated bond or an unsaturated bond is a linking group (ester bond (-OC (= 0)-, -C (= 0) O-), amide bond (-NHCO-, -CONH-, imino bond (- NH-), urethane bonds (-NHC (= O) O-), urea bonds, burette bonds, etc.) may be bonded to the thermoplastic resin, and the unsaturated bond or unit thereof is the end of the resin (main chain end) And / or may be located in the side chain, in the main chain of the resin, or in both of them.

Examples of the group having an unsaturated bond include C _2-6 alkenes such as vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, allyl group, 2-methyl-2-propenyl group and 2-butenyl group. Nyl group; C _2-6 alkenyl-C _6-20 aryl groups such as 4-vinylphenyl group and 4-isopropenylphenyl group; C _6-20 aryl-C _2-6 alkenyl groups such as styryl group; C _2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 1-butynyl group, propargyl group, 2-butynyl group and 1-methyl-2-propynyl group; Vinylene groups which may have substituents such as mono or diC _1-6 alkylvinylene groups such as vinylene group, methylvinylene group, ethylvinylene group and 1,2-dimethylvinylene group, and halovinylene groups such as chlorovinylene group; Vinylidene group; An ethynylene group etc. can be illustrated.

As a specific form of the thermoplastic resin which has an unsaturated bond, the form like the following (1)-(4) can be illustrated, for example.

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

(2) Thermoplastic resins in which unsaturated bonds are introduced by copolymerization or cocondensation

(3) polymer blends composed of resins and resins having unsaturated bonds

(4) Various organic reactions (for example, introduction of vinyl groups by the Reppe reaction using acetylene, introduction of unsaturated bonds using organometallic reagents such as vinyllithium, and unsaturated bonds by coupling reactions). Thermoplastic resin into which an unsaturated bond is introduced

Preferred resin among these resin is resin (1), (2) or (3).

In the said resin (1), it has a polymeric compound which has at least 1 reactive group (A) and at least 1 unsaturated bond, and has a reactive group (B) reactive with respect to the reactive group (A) of the said polymeric compound. An unsaturated bond can be introduce | transduced into resin by making resin react.

As a typical reactive group (A) of a polymeric compound, (A1) hydroxyl group, (A2) carboxyl group or its acid anhydride group, (A3) amino group, (A4) epoxy group, (A5) isocyanate group, etc. can be illustrated. As a combination of the reactive group (A) of a polymeric compound and the reactive group (B) of resin, the following combinations can be illustrated. In addition, the parenthesis shows the coupling | bonding form of a reactive group (A) and a reactive group (B).

(A1) hydroxyl group:

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

(A2) carboxyl group or anhydride group thereof:

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

(A5) isocyanate group:

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

As the polymerizable compound, a hydroxyl group-containing compound [for example, allyl alcohol, 2-buten-1-ol, such as C _3-6 al kenol, propargyl alcohol, 3-butene-2-ol C ₃ C _2-6 alkylene glycol mono (meth) acrylates such as _-6 alkynol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate such as polyoxyethylene C _2-6 alkylene glycol mono (meth) acrylate, 4-hydroxystyrene, 4-hydroxy--α- methyl styrene, etc. C _2-6 alkenyl Phenol, dihydroxy styrene, vinyl naphthol, and the like], a carboxyl group or an acid anhydride group-containing compound [for example, C _3-6 alkencarboxylic acid, itaconic acid such as (meth) acrylic acid, crotonic acid, 3-butene acid, C _4-8 alkenedicarboxylic acids such as maleic acid and maleic anhydride or anhydrides thereof, and unsaturated aromatic carboxylic acids such as vinyl benzoic acid, Namsan etc.], amino group containing compound (for example, C _3-6 alkenylamine, such as allylamine, 4-amino styrene, diamino styrene, etc.), epoxy group containing compound (for example, allyl glycidyl ether, glyc Cyl (meth) acrylate, etc.), an isocyanate group compound (for example, vinyl isocyanate etc.) etc. can be illustrated.

In the resin (1), the resin may be modified by introducing a reactive group (B). As a method of introducing the reactive group (B) into the resin, in the production of the resin (1), a monomer having a reactive group (B) (for example, the polymerizable compound exemplified above) and a resin material (or resin) Monomers and oligomers as raw materials), and (ii) various organic reactions such as introduction of carboxyl groups by oxidation reaction, halogenation method, and graft method of polymerizable monomer can be used. Moreover, as vinyl polymer type resin, the said reactive group (B) is introduce | transduced in many cases by using the monomer which has the said reactive group (B) as a copolymerization component normally, and it has the said reactive group in any number including vinyl polymer type resin. The reactive group (B) can be easily introduced by the graft reaction of the polymerizable compound.

In the resin (2), as a method of introducing an unsaturated bond, for example, in the production of a condensed resin (e.g., a polyamide resin, a polyester resin, etc.), a part of the reaction component (comonomer) As a compound having a polyfunctional unsaturated bond, for example, an aliphatic unsaturated dicarboxylic acid (maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, metaconic acid, etc. Unsaturated polyhydric carboxylic acids such as C _4-10 aliphatic unsaturated dicarboxylic acids, etc .: unsaturated polyhydric alcohols such as aliphatic unsaturated diols (such as C _4-10 aliphatic unsaturated diols such as 2-butene-1,4-diol) Etc.] can be exemplified. In addition, in addition polymerization resin (for example, olefin resin, etc.), the monomer (for example, 1, 3- butadiene, 2-methyl- 1, which has a conjugated unsaturated bond as a part (commonomer) of a reaction component) And a method of copolymerizing conjugated C _4-10 alkadiene which may have substituents such as 3-butadiene, 2,3-dimethyl-1,3-butadiene, and chloroprene).

In the said resin (3), unsaturated bond can be introduce | transduced into a thermoplastic resin by mixing a thermoplastic resin (A) and resin (B) which has an unsaturated bond, and forming a polymer blend (or resin composition).

It does not specifically limit as said thermoplastic resin (A), Various thermoplastic resins (for example, the thermoplastic resin (polyamide resin, polyester resin, etc.) mentioned later) can be illustrated. In addition, the thermoplastic resin (A) may be a resin having no unsaturated bond, or may be a resin having an unsaturated bond.

As resin (B) which has an unsaturated bond, thermoplastic resin in which unsaturated bonds, such as the said aspect (1), (2) or (4), were introduce | transduced, unsaturated bond containing rubber (for example, polybutadiene, polyisoprene, a polypene) PolyC _4-15 alkenes such as tenamers, polyheptenamers, polyoctenamers, poly (3-methyloctenamers), polydecenamers, poly (3-methyldecenamers), and polydodecenamers Copolymers of C _4-15 alkadienes such as butylene and butadiene-isoprene copolymers, rubber-modified polyolefins such as butadiene-modified polyethylene, and the like). In addition, the poly C _4-15 alkenylene is a cycloolefin (for example, C _5-20 cycloolefin which may have a substituent such as cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, etc.) It can also be obtained by metathesis polymerization, partial hydrogenation of polyalkenylene (for example, polybutadiene, etc.).

In the said resin (4), the ratio of the said resin (B) is the range which can introduce an unsaturated bond into a polymer blend in a predetermined density | concentration, for example, resin (A) / resin (B) (weight ratio) = 5 / 95 to 95/5, preferably 30/70 to 95/5, more preferably 50/50 to 95/5. In addition, when using an unsaturated bond containing rubber (for example, polyoctenylene etc.) as resin (B), the ratio of resin (B) can be selected in the range which does not impair the property of resin (A), For example, resin (A) / resin (B) (weight ratio) = 50/50-95/5, Preferably it is 60/40-95/5, More preferably, it is about 70/30-95/5.

The number of unsaturated bonds is, for example, 0.1 or more (for example, 0.1 to 1000) on average per molecule of resin, preferably 1 or more (for example, 1 to 100) on average, and more preferably Is an average of 2 or more (for example, about 2 to 50). The concentration of the unsaturated bond is, for example, 0.001 to 6.6 mol, preferably 0.01 to 4 mol, and more preferably about 0.02 to 2 mol relative to 1 kg of the resin.

As a thermosetting resin which has a crosslinkable functional group, resin which has a functional group (for example, a methylol group, an alkoxy methyl group, an epoxy group, an isocyanate group, etc.) which shows crosslinkability or curability in presence of a crosslinking agent (or a hardening | curing agent) etc. is mentioned. As such thermosetting resins, polycondensation or addition condensation resins (phenol resins, amino resins, epoxy resins, thermosetting polyimide resins, thermosetting polyurethane resins, silicone resins, etc.), addition polymerization resins (unsaturated polyester resins, vinyls) Ester resin, diallyl phthalate resin, thermosetting acrylic resin, etc.) can be illustrated.

Resin which has these active atoms and a crosslinkable group can be used individually or in combination of 2 or more types. When using in combination of 2 or more types of resins, the resin composition may form a composite resin composition such as a polymer alloy.

It demonstrates about a preferable thermoplastic resin and a thermosetting resin below.

(Thermoplastic)

(1) polyamide-based resin

The polyamide resin has an amide bond by polycondensation of a carboxyl group and an amino group, and examples thereof include aliphatic polyamide resins, alicyclic polyamide resins, aromatic polyamide resins, and the like. System resins are used. The aliphatic polyamide-series resin, an aliphatic diamine component, such as (tetramethylenediamine, hexamethylenediamine, etc. of C _4-10 alkylene diamine) and aliphatic dicarboxylic acids (adipic acid, sebacic acid, dodecanedioic C _{4 -20} alkylene dicarboxylic acid and the like) and the condensate (e.g., polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 1212), the lactam Lactam using the ring-opening polymerization of C _4-20 lactam such as ε-caprolactam, ω-laurolactam, etc. or aminocarboxylic acid (C _4-20 aminocarboxylic acid such as ω-aminoundecanoic acid, etc.) Single or copolymers of polyamide 6, polyamide 11, polyamide 12 and the like, copolyamides copolymerized with these polyamide components (eg polyamide 6/11, polyamide 6/12) , Polyamide 66/11, polyamide 66/12 and the like).

As alicyclic polyamide type resin, the polyamide which substituted at least one part of the said aliphatic diamine component and / or aliphatic dicarboxylic acid component with alicyclic diamine and / or alicyclic dicarboxylic acid is mentioned. The alicyclic polyamide includes, for example, the aliphatic dicarboxylic acid component and the alicyclic diamine component (C _5-8 cycloalkyldiamine such as cyclohexyldiamine; bis (aminocyclohexyl) methane, 2,2-bis (amino And condensates with bis (aminocyclohexyl) alkanes such as cyclohexyl) propane).

Examples of the aromatic polyamide-based resin include polyamides in which at least one component of the aliphatic diamine component and aliphatic dicarboxylic acid component has an aromatic component. The aromatic polyamide is, for example, a polyamide having a diamine component having an aromatic component (condensation product of an aromatic diamine such as MXD-6 and the like) with an aliphatic dicarboxylic acid and a dicarboxylic acid component. The polyamides (condensates of aliphatic diamines (such as trimethylhexamethylenediamine) with aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.), etc.) having the aromatic component, the diamine component and the dicarboxylic acid component are all aromatic components. Polyamides (such as all aromatic polyamides (aramid) such as poly (m-phenylene isophthalamide)) and the like that are included.

Polyamide resins also include polyamides having dimer acid as a dicarboxylic acid component, polyamides having a branched chain structure using a small amount of polyfunctional polyamines and / or polycarboxylic acid components, and modified polyamides (N Alkoxy methyl polyamide, etc.), high impact polyamide obtained by mixing or graft polymerizing modified polyolefin, and polyamide elastomer having a polyether as a soft segment.

In a polyamide resin, for example, a hydrogen atom bonded to a hydrogen atom of a terminal amino group, a hydrogen atom bonded to a carbon atom in the α-position to a terminal amino group, or a carbon atom adjacent to an -NH-group of an amide bond ( The hydrogen atom of a methylene group, the hydrogen atom of a methylidine group, etc.), especially the hydrogen atom of a terminal amino group comprise an active hydrogen atom.

In the polyamide-based resin, the ratio between the terminal NH ₂ group and the terminal COOH group is not particularly limited. For example, when the active hydrogen atom is constituted by the hydrogen atom of the terminal amino group and the hydrogen atom of the α-carbon position, the terminal amino group / terminal Carboxyl group = about 10/90-100/0 (molar ratio), Preferably it is selectable in the range of about 20/80-95/5 (molar ratio), More preferably, about 25/75-95/5 (molar ratio). . Moreover, when an active hydrogen atom is comprised only by the hydrogen atom of a terminal amino group, terminal amino group / terminal carboxyl group = about 50/50-100/0 (molar ratio), Preferably it is about 60/40-95/5 (molar ratio), More Preferably, it may be about 70/30 to 95/5 (molar ratio).

In addition, in polyamide resin, when an unsaturated bond is introduce | transduced by the said aspect (1), the remaining carboxyl group and an amino group can be used as a reactive group (B), for example, and also unsaturated by the said aspect (2) When introducing a bond, the unsaturated polyhydric carboxylic acid (maleic acid or the like) or the like may be used as part of the copolymerization component.

(2) polyester resin

Examples of the polyester resins include aliphatic polyester resins and aromatic polyester resins. Usually, aromatic polyester resin, for example, polyalkylene arylate resin or saturated aromatic polyester resin is used. The aromatic polyester-series resin, for example polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and poly C _2-4 alkylene terephthalate; PolyC _2-4 alkylene naphthalate (for example, polyethylene naphthalate, etc.) corresponding to this polyalkylene terephthalate; 1,4-cyclohexyldimethylene terephthalate (PCT)) and the like. The polyester resin may be a copolyester containing an alkylene arylate unit as a main component (for example, 50% by weight or more), and the copolymerized component may be C ₂ such as ethylene glycol, propylene glycol, butanediol, hexanediol, or the like. _-6 there can be mentioned an alkylene glycol, polyoxyalkylene C _2-4 alkylene glycol, phthalic acid, isophthalic acid, such as an asymmetric aromatic dicarboxylic acid or its anhydride, adipic acid, aliphatic dicarboxylic acids such as. It is also possible to use a small amount of polyols and / or polycarboxylic acids to introduce branched chain structures into the linear polyester.

When the aromatic polyester resin does not have the active atom at a predetermined concentration, the modified polyester resin modified with a modified compound having an active atom (for example, having at least one selected from an amino group and an oxyalkylene group) Aromatic polyester resin) can also be used. Examples of the compound having an active atom, especially an active hydrogen atom, include polyamines (aliphatic diamines such as ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1, Linear or branched alkylenediamines having 2 to 10 carbon atoms, such as 7-diaminoheptane and 1,8-diaminooctane; alicyclic diamines such as isophoronediamine and bis (4-amino-3- Methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, etc .; aromatic diamines such as phenylenediamine, xylylenediamine, diaminodiphenylmethane, and the like; polyols (such as (poly) oxyethylene And (poly) oxy C _2-4 alkylene glycols such as glycol, (poly) oxytrimethylene glycol, (poly) oxypropylene glycol, and (poly) oxytetramethylene glycol). Modification can be carried out, for example, by heating and mixing a polyester resin and a modified compound and using amidation, esterification or transesterification. The degree of modification of the polyester resin is, for example, 0.1 to 2 moles of the modified compound, preferably 0.2 to 1 mole of the functional group (hydroxyl group or carboxyl group) of the polyester resin depending on the amount of active hydrogen atoms in the compound. To 1.5 mol, more preferably about 0.3 to 1 mol. When used for the transesterification reaction, the amount of the (poly) oxy C _2-4 alkylene glycols may be about 1 to 50 parts by weight, preferably about 5 to 30 parts by weight based on 100 parts by weight of the polyester resin. have.

In polyester-based resins, hydrogen atoms of methylene groups of (poly) oxyalkylene units usually constitute active hydrogen atoms, and in modified polyester-based resins, hydrogen atoms of terminal amino groups and carbon atoms in the α-position relative to terminal amino groups are usually used. The hydrogen atom to be bonded, the hydrogen atom bonded to the carbon atom adjacent to the -NH- group of the amide bond (such as a hydrogen atom of a methylene group or a hydrogen atom of a methylidine group), particularly a hydrogen atom of a terminal amino group constitutes an active hydrogen atom.

In addition, in polyester type resin, when an unsaturated bond is introduce | transduced by the said aspect (1), the remaining carboxyl group and a hydroxyl group can be used as a reactive group (B), for example, and also in said aspect (2) In the case of introducing an unsaturated bond, the unsaturated polyhydric carboxylic acid (maleic acid and the like), the unsaturated polyhydric alcohol (2-butene-1,4-diol and the like) and the like can also be used as part of the copolymerization component.

(3) poly (thio) ether resin

The polyether resins include polyoxyalkylene resins, polyphenylene ether resins, and polysulfide resins (polythioether resins). Examples of the polyoxyalkylene resins include polyoxymethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-polyoxypropylene block copolymers, polyoxy C _1-4 alkylene glycols such as polyoxytetramethylene glycol, and the like. Included. Preferred polyether resins include polyacetal resins, polyphenylene ether resins, polysulfide resins and polyether ketone resins. In addition, when an unsaturated bond is introduce | transduced by the said aspect (1), remaining hydroxyl group, a mercapto group, etc. can also be used as a reactive group (B).

(3a) polyacetal resin

The polyacetal resin may be a homopolymer (monopolymer of formaldehyde) constituted by regular repetition of acetal bonds, or a copolymer obtained by ring-opening polymerization or the like (trioxane and ethylene oxide and / or 1,3 -Copolymer with dioxolane or the like). In addition, the terminal of the polyacetal resin may be blocked and stabilized. In polyacetal resin, for example, the hydrogen atom of the oxymethylene unit, the hydrogen atom of the alkoxy group (particularly a methoxy group) which sealed off the terminal, especially the hydrogen atom of an oxymethylene unit comprise an active hydrogen atom. Moreover, in polyacetal resin, when introducing an unsaturated bond by the said aspect (1), the remaining hydroxyl group etc. can also be used as a reactive group (B).

(3b) polyphenylene ether resin

The polyphenylene ether-based resin is a modified resin obtained by blending or grafting a styrene resin with a copolymer of 2,6-dimethylphenylene oxide as a main component, for example, a copolymer of 2,6-dimethylphenylene oxide and phenols. Polyphenylene ether resins and the like. Examples of other modified polyphenylene ether resins include polyphenylene ether / polyamide, polyphenylene ether / saturated polyester, polyphenylene ether / polyphenylene sulfide, polyphenylene ether / polyolefin, and the like. Can be. In the case where the styrene resin is blended, the ratio of the styrene resin to 100 parts by weight of the polyphenylene ether resin is, for example, 2 to 150 parts by weight, preferably 3 to 100 parts by weight, more preferably 5 It may be about 50 parts by weight. In polyphenylene ether resin, the hydrogen atom of the methyl group couple | bonded with a benzene ring, for example comprises an active hydrogen atom.

(3c) polysulfide resin (polythioether resin)

The polysulfide resin is not particularly limited as long as it is a resin having a thi group (-S-) in the polymer chain. As such resin, polyphenylene sulfide resin, polydisulfide resin, polybiphenylene sulfide resin, polyketone sulfide resin, polythioether sulfone resin, etc. can be illustrated, for example. In addition, the polysulfide resin may have a substituent such as an amino group, such as poly (aminophenylene sulfide). Preferred polysulfide-based resins are polyphenylene sulfide resins. In polysulfide-based resins, the thi group in the main chain constitutes an active sulfur atom. For example, with respect to the polyphenylene sulfide resin, the average number N of active sulfur atoms in one molecule can be calculated based on the model base unit Cl-C ₆ H ₄ -SC ₆ H ₄ -SC ₆ H ₄ -Cl, N = 2.

(3d) polyether ketone resin

The polyether ketone resin includes a polyether ketone resin obtained by polycondensation of dihalogenobenzophenone (such as dichlorobenzophenone) and dihydrobenzophenone, and a polyether obtained by polycondensation of dihalogenobenzophenone and hydroquinone. Ether ketone resin etc. can be illustrated.

(4) polycarbonate resin

As polycarbonate resin, although aliphatic polycarbonate resin may be sufficient, Usually, aromatic polycarbonate resin, For example, aromatic dihydroxy compound (such as bisphenol compound, such as bisphenol A, bisphenol S), Aromatic polycarbonate obtained by reaction with phosgene or diester carbonate (diaryl carbonates, such as diphenyl carbonate, dialkyl carbonates, such as dimethyl carbonate), etc. can be used. In polycarbonate resin, when an unsaturated bond is introduce | transduced by the said aspect (1), the remaining hydroxyl group etc. can also be used as a reactive group (B).

(5) polyimide resin

The polyimide resin may be a thermoplastic polyimide resin, for example, an aromatic tetracarboxylic acid or an anhydride thereof (benzophenone tetracarboxylic acid or the like) and a polyimide obtained by the reaction of an aromatic diamine (diaminodiphenylmethane or the like). Resins, polyamideimide resins, polyesterimide resins and the like. In polyimide-type resin, when a unsaturated bond is introduce | transduced by the said aspect (1), the remaining carboxyl group, an acid anhydride group, an amino group, an imino group, etc. can be used as a reactive group (B).

(6) polysulfone resin

Polysulfone resins include polysulfone resins, polyethersulfone resins and polyallylsulfone resins obtained by polycondensation of dihalogenodiphenylsulfone (such as dichlorodiphenylsulfone) and bisphenols (such as bisphenol A or a metal salt thereof). Brand name = RADEL) etc. can be illustrated.

(7) polyurethane-based resin

Polyurethane resin can be obtained by reaction of diisocyanate, polyol, and chain extender as needed. Examples of the diisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate and phenylenedi. Aromatic diisocyanates, such as an isocyanate, tolylene diisocyanate, diphenylmethane-4,4'- diisocyanate, aromatic aliphatic diisocyanates, such as xylylene diisocyanate, etc. can be illustrated. As diisocyanate, the compound which substituted the alkyl group (for example, methyl group) to the main chain or ring can also be used.

Examples of the diols include polyester diols (C _4-12 aliphatic dicarboxylic acid components such as adipic acid, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and other C _2-12 aliphatic diol components, ε-caprolactone, etc.). Polyester diol obtained from C _4-12 lactone component and the like), polyetherdiol (polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyoxytetramethylene glycol, bisphenol A-alkylene oxide Adducts), and polyester ether diols (polyester diols using the above polyether diols as part of the diol component).

As the chain extender, diamines other than C _2-10 alkylenediol such as ethylene glycol and propylene glycol can also be used. As diamines, aliphatic diamines, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane Linear or branched polyalkylene polyamines such as linear or branched alkylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine and the like having about 2 to 10 carbon atoms; Alicyclic diamines such as isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane and the like; Aromatic diamines, for example, phenylenediamine, xylylenediamine, diaminodiphenylmethane and the like can be exemplified.

In the polyurethane-based resin, for example, a hydrogen atom (particularly, a hydrogen atom at the benzyl position) of an alkyl group bonded to a main chain or a ring of diisocyanates, a hydrogen atom of an alkylene group of polyols or polyoxyalkylene glycol, and an amino group of a chain extender Hydrogen atoms and the like constitute active hydrogen atoms.

In addition, in a polyurethane-type resin, when introducing an unsaturated bond according to the said aspect (1), the remaining hydroxyl group, an amino group, an isocyanate group, etc. can also be used as a reactive group (B), and the said aspect ( When introducing an unsaturated bond by 2), the said unsaturated polyhydric carboxylic acid (maleic acid etc.), the said unsaturated polyhydric alcohol (2-butene-1, 4-diol etc.) etc. can also be used as a part of copolymerization component.

(8) polyolefin resin

The polyolefin resin may be, for example, polyethylene or polypropylene, an ethylene-propylene copolymer, or a copolymer of olefins such as poly (methylpentene-1) alone or a copolymer of an olefin and a copolymerizable monomer (ethylene-vinyl acetate copolymer). , Ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, and the like). These polyolefin resins can be used individually or in combination of 2 or more types.

Preferred polyolefin resins include polypropylene resins having a propylene content of at least 50% by weight (particularly 75 to 100% by weight), for example polypropylene, propylene-ethylene copolymer, propylene-butene copolymer, propylene-ethylene-butene Copolymers and the like. Moreover, it is preferable that polyolefin resin is crystalline.

In polyolefin resin, the hydrogen atom of the methylene group which comprises the main chain of polyolefin, the hydrogen atom of the methyl group branched from the said main chain, etc. comprise an active hydrogen atom, for example.

(9) halogen-containing resin

Examples of the halogen-containing resin include chlorine-containing vinyl resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer, polyvinyl fluoride, polyvinylidene fluoride, Fluorine-containing vinyl resins such as polychlorotrifluoroethylene, copolymers of tetrafluoroethylene and copolymerizable monomers, and the like can be exemplified. Preferred halogen-containing resins are fluorine-containing vinyl resins (for example, polyvinyl fluoride, polyvinylidene fluoride and the like).

(10) styrene resin

As the styrene resin, a styrene monomer alone or a copolymer (polystyrene, styrene-vinyltoluene copolymer, styrene-α-methyl styrene copolymer, etc.), a copolymer of a styrene monomer and a copolymerizable monomer (styrene-acrylonitrile Styrene copolymers, such as a copolymer (AS resin), (meth) acrylic acid ester-styrene copolymer (MS resin etc.), a styrene maleic anhydride copolymer, and a styrene-butadiene copolymer: Acrylonitrile- butadiene-styrene copolymer (ABS resin), impact polystyrene (HIPS), acrylonitrile-acrylic acid ester-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile-ethylene propylene rubber Styrene copolymers (AES resin), styrene-based graft copolymers such as acrylonitrile-vinyl acetate-styrene copolymer (AXS resin) and the like), and the like. .

(11) (meth) acrylic resin

As (meth) acrylic-type resin, the single or copolymer of a (meth) acrylic-type monomer, the copolymer of a (meth) acrylic-type monomer, and a copolymerizable monomer, etc. are mentioned. (Meth) acrylic acid, such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Methacrylic acid, such as C _1-10 alkyl ester and cyclohexyl methacrylate, C _5-10 cycloalkyl ester, and (meth) acrylic acid C _6-10 aryl ester, such as phenyl (meth) acrylate, and hydroxyethyl (meth) acrylate (Meth) acrylic-acid hydroxy _C2-10 alkyl ester, (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic-acid glycidyl, etc. are mentioned. Examples of the copolymerizable monomers include vinyl monomers such as vinyl acetate and vinyl chloride, and styrene monomers such as styrene and α-methylstyrene.

In (meth) acrylic-type resin, when introducing an unsaturated bond by the said aspect (1), the said reactive group (B) can be introduce | transduced by using the monomer which has a reactive group (B) as a copolymerization component.

(12) Thermoplastic Elastomers

Thermoplastic elastomers include polyamide elastomers (copolymers having polyamides in the hard phase and aliphatic polyethers in the soft phase), polyester elastomers (polyalkylene arylates in the hard phase), and aliphatic polyethers or aliphatic polys. Copolymer having an ester as a soft phase) and a polyurethane elastomer (copolymer having a polyurethane of short chain glycol as a hard phase and an aliphatic polyether or an aliphatic polyester as a soft phase, for example, a polyester urethane elastomer or a polyether) Urethane elastomers, etc.), polystyrene-based elastomers (polystyrene blocks in hard phase, diene polymer blocks or hydrogenated blocks in soft phase), polyolefin-based elastomers (polystyrene or polypropylene in hard phase, ethylene -Propylene high Or ethylene-diene rubber, and the like a soft elastomer onto the olefin crystallinity is composed of different hard phase and a soft segment based elastomer and the like), polyvinyl chloride-based elastomer, fluorine-based thermoplastic elastomer, polypropylene. As the aliphatic polyether, (poly) oxy C _2-4 alkylene glycols (particularly polyoxyethylene glycol) and the like mentioned in the section of polyester resin and polyurethane resin can be used, and as the aliphatic polyester, The polyesterdiol etc. which were stated in the term can be used. These thermoplastic elastomers can be used individually or in combination of 2 or more types.

When the thermoplastic elastomer is a block copolymer, the block structure is not particularly limited and may be a tree block structure, a multi block 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 a thermoplastic elastomer, the hydrogen atom of the oxyalkylene unit which comprises a soft phase, for example may comprise an active hydrogen atom.

In addition, the said thermoplastic resin can also be used as crosslinking resin bridge | crosslinked using a crosslinking agent. For example, in polyester-based resins, a trifunctional or higher polyhydric carboxylic acid (e.g., trimellitic anhydride, etc.) and / or a trifunctional or higher polyhydric alcohol (e.g., glycerin, etc.) are dicarboxylic acid. It can also be bridge | crosslinked by using as a part of a component and / or a diol component, and in a polyamide resin, triamines (for example, tri (methylamino) hexane etc. as a part of a diamine component and / or a dicarboxylic acid component) Aromatic polyamines, such as aliphatic polyamine, and triaminobenzene, etc.), and / or a trifunctional or more than trifunctional polycarboxylic acid (for example, trimellitic anhydride etc.) can also be obtained.

Furthermore, vinyl polymerization resins (for example, (meth) acrylic resins (methyl polymethacrylate, methyl methacrylate-styrene copolymer, etc.) and styrene resins (polystyrene; AS resin, styrene copolymers, such as HIPS, Styrene-based graft copolymers such as ABS resins, etc.], a bifunctional or higher polyfunctional polymerizable compound (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, etc.) and a structural monomer can also be bridge | crosslinked.

(Thermosetting resin)

As the thermosetting resin, polycondensation or addition condensation resin (phenol resin, amino resin, epoxy resin, silicone resin, thermosetting polyimide resin, thermosetting polyurethane resin, etc.), addition polymerization resin (thermosetting acrylic resin, vinyl ester resin) , Unsaturated polyester resin, diallyl phthalate resin, etc.) can be illustrated. Thermosetting resin can also be used individually or in combination of 2 or more types.

(13) Phenolic Resin

Phenolic resins include novolak resins, resol resins, and the like, but usually novolak resins are used. Novolak resins are obtained by the reaction of phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, o-, m- or p-cresol, 2,5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, ethylphenol and propylphenol. And C _1-4 alkylphenols, dihydroxybenzene, resorcinol, naphthol and the like can be exemplified. These phenols can also be used individually or in combination of 2 or more types. Examples of the aldehydes include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, aromatic aldehydes such as benzaldehyde, salicylic aldehyde and the like. These aldehydes can also be used individually or in combination of 2 or more types.

(14) amino resin

An amino resin is usually obtained by reaction of an amino group containing compound with aldehydes (for example, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and aromatic aldehydes such as phenylacetaldehyde). Examples of amino resins include urea resins (urea resins obtained by the reaction between urea and aldehydes), aniline resins (aniline, naphthylamine, toluidine, xyldine, N, N-dimethylaniline, and benzidine). Aniline resins obtained by the reaction of aldehydes with aldehydes, melamine resins (such as melamine resins obtained by the reaction of melamine with aldehydes), guanamine resins (benzoguanamine, acetoguanamine, and formoguanamine). Guanamine resin obtained by the reaction of guanamines and aldehydes).

(15) epoxy resin

As an epoxy resin, a bisphenol-type epoxy resin, a novolak-type epoxy resin, an amine epoxy resin, etc. are contained.

As bisphenol which comprises a bisphenol-type epoxy resin, glycidyl ether, such as 4, 4- biphenol, 2, 2- biphenol, bisphenol F, bisphenol AD, bisphenol A, can be illustrated, for example.

As a novolak resin which comprises a novolak-type epoxy resin, the novolak resin etc. which are obtained by reaction of the phenols and aldehydes of the term of the said novolak resin can be illustrated, for example.

As an amine component which comprises an amine epoxy resin, aromatic diamines, such as an aromatic amine, such as aniline and toluidine, diaminobenzene, and xylylenediamine, aminohydroxybenzene, diaminodiphenylmethane, etc. can be illustrated, for example. have.

(16) silicone resin

The silicone resin has a unit represented by the formula: R _a SiO _{(4-a) / 2} (wherein the coefficient a is about 1.9 to 2.1) and a unit represented by the formula: R _b SiO _{(4-b) / 2} (In the formula, the coefficient b is about 0.9 to 1.1). Wherein, R is for example methyl group, ethyl group, propyl group, butyl group of C _1-10 alkyl group, a 3-chloropropyl group, a halide group, such as propyl 3,3.3- trifluoro-C _1-10 alkyl group, a vinyl C _3-10 cycloalkyl groups, benzyl groups such as C _6-10 aryl groups such as C _2-10 alkenyl groups, phenyl groups, tolyl groups, naphthyl groups, cyclopentyl groups, and cyclohexyl groups such as groups, allyl groups, and butenyl groups And C _6-12 aryl-C _1-4 alkyl groups such as phenethyl group and the like.

(17) Thermosetting Polyimide Resin

The thermosetting polyimide resin includes the resin described in the section of the polyimide resin.

(18) Thermosetting Polyurethane Resin

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

(19) Thermosetting Acrylic Resin

Thermosetting acrylic resin contains resin of the term of the said (meth) acrylic-type resin.

(20) vinyl ester resins

As vinyl ester type resin, resin obtained by reaction of the said epoxy resin and (meth) acrylic acid, resin obtained by reaction of polyhydric phenols, and glycidyl (meth) acrylate, etc. are mentioned.

(21) unsaturated polyester resin

Examples of the unsaturated polyester resin include unsaturated polyesters using unsaturated dicarboxylic acid or anhydrides thereof (for example, maleic acid, maleic anhydride, fumaric acid, etc.) as the dicarboxylic acid component in the polyester resin. Can be mentioned.

(22) diallyl phthalate resin

The diallyl phthalate resin includes resins obtained from diallyl phthalate monomers such as diallyl orthophthalate and diallyl isophthalate.

The resin material may be used in the form of a granular material when the resin is a thermoplastic resin having a melting point higher than the kneading or vulcanization temperature of the rubber, for example, or a crosslinking or thermosetting resin. As such a resin particle, crosslinked polymethyl methacrylate type resin, crosslinked polystyrene resin, crosslinked epoxy resin, crosslinked phenol resin, crosslinked benzoguanamine type resin, crosslinked silicone resin, etc. can be illustrated, for example. The shape of the crosslinked or cured resin material is not particularly limited, and may be, for example, amorphous, spherical, elliptical, rod-shaped, or the like. The average particle diameter of the resin powder is, for example, 0.1 to 5000 µm, preferably 1 to 1000 µm, more preferably about 5 to 500 µm, usually 10 to 500 µm, preferably 20 to 200 µm (eg For example, it is about 50-150 micrometers.

In addition, the resin may include various additives such as fillers or reinforcing agents, stabilizers (ultraviolet absorbers, antioxidants, heat stabilizers), colorants, plasticizers, lubricants, flame retardants, antistatic agents and the like.

[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.

As the rubber, diene rubber, olefin rubber, acrylic rubber, fluorine rubber, silicone rubber, urethane rubber, epichlorohydrin rubber (epichlorohydrin homopolymer C0, copolymer ECO of epichlorohydrin and ethylene oxide, Copolymers also copolymerized with allylglycidyl ether), chlorosulfonated polyethylene, propylene oxide rubber (GPO), ethylene-vinyl acetate copolymer (EAM), polynorbornene rubber, and modified rubbers thereof (acid Modified rubber and the like). These rubbers can be used alone or in combination of two or more thereof. Among these rubbers, diene rubbers, olefin rubbers, acrylic rubbers, fluorine rubbers, silicone rubbers, urethane rubbers, and the like are usually widely used from a practical point of view.

In diene rubber, for example, diene monomers such as natural rubber (NR), isoprene rubber (IR), isobutylene isoprene rubber (butyl rubber) (IIR), butadiene rubber (BR), and chloroprene rubber (CR) polymer; For example, Acrylonitrile-diene copolymer rubbers, such as an acrylonitrile butadiene rubber (nitrile rubber) (NBR), a nitrile chloroprene rubber (NCR), a nitrile isoprene rubber (NIR), and an acrylonitrile isoprene butadiene rubber (NBIR); Styrene-diene such as styrene butadiene rubber (SBR, for example, a random copolymer of styrene and butadiene, SB block copolymer composed of styrene block and butadiene block), styrene chloroprene rubber (SCR), styrene isoprene rubber (SIR) Copolymer rubber and the like. The diene rubber also includes hydrogenated rubber such as hydrogenated nitrile rubber (HNBR) and the like. In addition, in the styrene-diene copolymer rubber, the ratio of the styrene component is, for example, 10 to 80 mol%, preferably 20 to 70 mol%, more preferably 30 to 60 mol% in terms of monomers constituting the copolymer. It may be enough.

As an olefin type rubber, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM etc.), a polyoctenylene rubber etc. can be illustrated, for example.

The acrylic rubber may be a rubber having an alkyl acrylate as a main component, for example, copolymer ACM of an alkyl acrylate and a chlorine-containing crosslinkable monomer, copolymer ANM of an alkyl acrylate and an acrylonitrile, an alkyl acrylate and a carboxyl group, and ( Or a copolymer with an epoxy group-containing monomer, ethylene acrylic rubber, and the like.

Examples of the fluorine rubber include rubbers using fluorine-containing monomers, for example, vinylidene fluoride and perfluoropropene, copolymer FKM of ethylene tetrafluoride, copolymer of ethylene tetrafluoride and propylene, and ethylene tetrafluoride if necessary. The copolymer FFKM with perfluoromethyl vinyl ether, etc. can be illustrated.

Silicone rubber (Q) is an organopolysiloxane composed of units represented by the formula: R _a SiO _{(4-a) / 2} . In the formula, R is a halogenated C _1-10 alkyl group such as C _1-10 alkyl group such as methyl group, ethyl group, propyl group, butyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. C _3-10 cycloalkyl groups such as C _6-10 aryl groups such as C _2-10 alkenyl, phenyl, tolyl and naphthyl, cyclopentyl and cyclohexyl groups such as vinyl, allyl and butenyl groups; C _6-12 aryl-C _1-4 alkyl groups, such as a benzyl group and a phenethyl group, etc. are mentioned. In the formula, the coefficient a is about 1.9 to 2.1. Preferred R is a methyl group, a phenyl group, an alkenyl group (vinyl group etc.), and a fluoroC _1-6 alkyl group.

The molecular structure of the silicone rubber is usually linear, but may have some branched structure or may be branched. 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 chain, dimethylsiloxane-methylphenylsiloxane copolymer chain, dimethyl Siloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer chain, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer chain, or the like]. Both ends of the silicone rubber may be, for example, trimethylsilyl group, dimethylvinylsilyl group, silanol group, triC _1-2 alkoxysilyl group, or the like.

The silicone rubber Q includes methyl silicone rubber (MQ), vinyl silicone rubber (VMQ), phenyl silicone rubber (PMQ), phenyl vinyl silicone rubber (PVMQ), silicon fluoride rubber (FVMQ), and the like. In addition, the silicone rubber is not limited to the solid rubber of the high temperature vulcanized HTV (High Temperature Vulcanizable), but room temperature vulcanized RTV (Low Temperature Vulcanizable) or low temperature vulcanized LTV (Low Temperature Vulcanizable) silicone rubber, for example, liquid Or paste rubbers.

Examples of the urethane rubber (U) include polyester type urethane elastomers, polyether type urethane elastomers, and the like.

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

The ratio of the resin and the rubber can be appropriately set in a range in which the properties of the composite dispersion can be expressed effectively, for example, a vulcanized rubber phase / resin phase = 90/10 to 10/90 (weight ratio) [for example , 90/10 to 30/70 (weight ratio)], preferably 75/25 to 25/75 (weight ratio) [for example, 75/25 to 50/50 (weight ratio)], and about 60/40 to 40 It may be about / 60 (weight ratio).

[Vulcanizer]

The vulcanizing agent not only vulcanizes (or crosslinks) the unvulcanized rubber, but also acts on the resin (or active resin) (e.g., releases active hydrogen atoms of the resin, activates it by radicalization, or crosslinks of the resin). Activating the penis can bond the resin and the vulcanized rubber. As the vulcanizing agent, a radical generator or sulfur can be used depending on the type of the resin or rubber. Examples of the radical generator include organic peroxides, azo compounds, sulfur-containing organic compounds, and the like. Moreover, in this invention, a radical generating agent is effective with respect to the resin which has the said active atom, the thermoplastic resin which has the said unsaturated bond, and the thermosetting resin which has the said crosslinkable functional group, and sulfur is resin which has an unsaturated bond (the said unsaturated bond) Thermoplastic resins, such as unsaturated polyester resins), specific resins / rubber combinations [polyphenylene ether resins and styrene-diene copolymer rubbers (such as styrene-butadiene rubbers), polythioether resins, Combinations with rubber, etc. are often effective. The vulcanizing agents may be used alone or in combination of two or more thereof.

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

Examples of the organic peroxide include diacyl peroxides (lauroyl peroxide, benzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and the like), dialkyl peroxides (di-t-butyl peroxide, 2, 5-di (t-butylperoxy) -2,5-dimethylhexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-di (t-butyl Peroxy) -2,5-dimethylhexane-3,1,3-bis (t-butylperoxyisopropyl) benzene, dicumylperoxide, etc.), alkyl peroxides (t-butylhydroperoxide, cumene hydroperoxide Seeds, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzenehydroperoxide and the like, alkylidene peroxides (ethylmethylketone peroxide, cyclohexanone peroxide, 1,1- Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane etc.), peracid esters (t-butyl peracetic acid, t-butyl perpibalate, etc.) etc. are mentioned.

Azo compounds include azobisisobutyronitrile and the like. As the sulfur-containing organic compound, thiurams (tetramethyl thiuram monosulfide (TMTM), tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide (TETD), tetrabutyl thiuram disulfide (TBTD), Dipentamethylenethiuram tetrasulfide (DPTT), morpholine sulfide, alkylphenol disulfide and the like) and the like.

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

If light irradiation is possible at the joining of a dendritic phase and a rubber | gum phase, a photoinitiator can also be used as a radical generator. As a photoinitiator, benzophenone or its derivatives (3,3'- dimethyl- 4-methoxy benzophenone, 4, 4- dimethoxy benzophenone etc.), alkylphenyl ketone or its derivatives (acetophenone, diethoxy, for example) Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (morpholinophenyl ) -Butanone, etc.), anthraquinone or derivatives thereof (2-methylanthraquinone, etc.), thioxanthone or derivatives thereof (2-chlorothioxanthone, alkyl thioxanthone, etc.), benzoin ether or a derivative thereof (benzo Phosphorus, benzoin alkyl ether, etc.), phosphine oxide, or its derivative (s) can be illustrated. Radical generators also include persulfates (ammonium persulfate, potassium persulfate, and the like).

Preferred vulcanizing agents of these compounds are organic peroxides. Vulcanizing agents are usually added to unvulcanized rubber.

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

[Vulcanization Activator]

Although a vulcanization activator is not necessarily required in the present invention, it is often added in order to reliably bond a rubber phase and a resin phase. The vulcanizing active agent may be added to at least one component of the unvulcanized rubber (or unvulcanized rubber composition) and the resin (or resin composition), or may be added to both components.

As said vulcanizing activator, it can select according to the vulcanizing agent (for example, radical generating agent etc.) etc. which are used, and the organic compound which has a carbon-carbon double bond (polymerizable unsaturated bond) [for example, a vinylic monomer (di Vinylbenzene etc.), an allyl-type monomer (diallyl phthalate, triallyl phosphate, triallyl (iso) cyanurate etc.), (meth) acrylic-type monomer etc.], a maleimide type compound, a carbon disulfide derivative, etc. are mentioned. These vulcanizing active agents can be used alone or in combination of two or more thereof.

As the (meth) acrylic monomer, for example, difunctional (meth) acrylates [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, hexane C _2-10 alkylene glycol di (meth) acrylates such as diol di (meth) acrylate and neopentyl glycol di (meth) acrylate; Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, poly PolyC _2-4 alkylene glycol di (meth) acrylates, such as propylene glycol di (meth) acrylate and polytetramethylene glycoldi (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropanedi (meth ) Acrylate, pentaerythritol di (meth) acrylate, di (meth) acrylate of C _2-4 alkylene oxide adduct of bisphenol A, etc.], trifunctional or polyfunctional (meth) acrylates [glycerine tree (Meth) acrylate, trimethylol ethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerytri Toltetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like].

The maleimide compound which has a some maleimide group can be obtained by reaction of a polyamine and maleic anhydride. Examples of the maleimide compound include aromatic bismaleimide (N, N'-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, and N, N'-3-methyl). -1,4-phenylenedimaleimide, 4,4'-bis (N, N'-maleimide) diphenylmethane, 4,4'-bis (N, N'-maleimide) diphenylsulfone, 4, 4'-bis (N, N'-maleimide) diphenyl ether, etc.), aliphatic bismaleimide (N, N'-1,2-ethylenebismaleimide, N, N'-1,3-propylenebismaleimide) Mead, N, N'-1,4- tetramethylenebismaleimide, etc.) etc. can be illustrated.

Examples of the carbon disulfide derivatives include dithiocarbamic acid salts (diC _1-4 alkyldithiocarbamic acids such as dimethyldithiocarbamic acid and diethyldithiocarbamic acid and sodium, potassium, iron, copper, zinc, selenium or tellurium). Salts, and the like), thiazoles (2-mercaptobenzothiazole, 2- (4'-morpholinodithio) benzothiazole, etc.), thioureas (thiocarboanilide, diorthotolylthiourea, etc.) Salts of dithiocarbamic acid salts (such as dimethyldithiocarbamic acid and diethyldithiocarbamic acid with di C _1-4 alkyldithiocarbamic acid and sodium, potassium, iron, copper, zinc, selenium or tellurium); ), Sulfenamides (N-cyclohexyl-2-benzothiazolesulfenamide, etc.), xanthogenic acid salts (salts of alkylxanthogenic acids such as isopropyl xanthogenic acid, butyl xanthogenic acid, sodium, zinc, etc.) ) May be exemplified.

Preferred vulcanizing actives include compounds having a plurality of carbon atoms (for example, about 2 to 6, in particular about 3 to 6) in one molecule of carbon-carbon double bonds (polymerizable unsaturated bonds), for example triallyl (iso) Nourates, di- to polyfunctional (meth) acrylates (particularly tri- or polyfunctional (meth) acrylates), aromatic maleimide compounds and the like.

The vulcanizing active agent is often added to unvulcanized rubber. The amount of the vulcanizing activator is usually about 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on an amount capable of promoting adhesion between the resin and the rubber, for example, 100 parts by weight of unvulcanized rubber and / or resin. It may be selected in the range of about 5 parts by weight, more preferably about 0.1 to 3 parts by weight.

[Vulcanization aid]

In the present invention, vulcanization aids can also be used. The vulcanizing aid may be added to at least one component of unvulcanized rubber (or unvulcanized rubber composition) and resin (or resin composition), or may be added to both components.

The vulcanizing aid can be selected according to the type of resin or rubber, and for example, the number average molecular weight of the oligomer of the condensed thermoplastic resin (for example, oligomer of the polyamide resin, oligomer of the polyester resin, etc.) To about 1000 to about oligomers), polyamines (e.g., polyamines described in the above item (2) polyester resins), polyols (e.g., (2) polyester resins) Polyols and the like), polyhydric carboxylic acid or acid anhydride thereof, a compound having a plurality of aldehyde groups, an epoxy compound, a nitrogen-containing resin (such as an amino resin), a compound having a methylol group or an alkoxymethyl group, a polyisocyanate, etc. have. These vulcanizing aids may be used alone or in combination of two or more thereof.

Preferred vulcanizing 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 condensed thermoplastic resins (for example, Oligomer, oligomer of the said polyester resin, etc.), the said polyamine, etc. can be illustrated.

The proportion of the vulcanizing aid is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably about 1 to 15 parts by weight, based on 100 parts by weight of the rubber and / or resin.

[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 component of the unvulcanized rubber (or unvulcanized rubber composition) and the resin (or resin composition), and may be added to both components.

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

For example, an alkoxysilane (for example, _{triC 1-4} alkoxysilanes, such as a trimethoxysilane and a triethoxysilane, tetraC _1-4 alkoxysilanes, such as tetramethoxysilane and tetraethoxysilane);

Alkoxysilanes having vinyl groups (vinyltriC _1-4 alkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane);

Alkoxysilanes having amino groups (e.g., amino C _2-4 alkyltriC _1-4 alkoxysilanes such as 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltriethoxysilane, etc.) , AminodiC _2-4 alkyldiC _1-4 alkoxysilane, such as 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethylethoxysilane);

Alkoxysilanes having an epoxy group (for example, glycidyloxy C _2-4 triC _1-4 alkoxysilanes such as 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) (Epoxycycloalkyl) C _2-4 alkyltri C _1-4 alkoxysilanes such as ethyltrimethoxysilane;

Alkoxysilane which has a mercapto group (For example, mercaptodi, such as mercaptoC _1-4 alkyl triC _1-4 alkoxysilane, 3-mercaptopropylmethyldimethoxysilane, such as 3-mercaptopropyl trimethoxysilane, etc.). C _1-4 alkyldiC _1-4 alkoxysilane);

Alkoxysilanes having a carboxyl group (e.g., carboxy methyl trimethoxysilane, methyl triethoxysilane carboxy, carboxy ethyltrimethoxysilane, carboxy propyl trimethoxy silane, such as a carboxy C _1-4 alkyl, C _1-4 tree Alkoxysilane);

Alkoxysilanes (e.g., isocyanate ethyl trimethoxysilane, isocyanate ethyl triethoxysilane, isocyanate propyl trimethoxysilane and so on of the isocyanate C _1-4 alkyl tree C _1-4 alkoxy silane) having an isocyanate group;

Alkoxysilanes having a (meth) acryloyl group (for example, N- (3- (meth) acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3- (meth) acryloxypropyl Dimethylmethoxysilane, 3- (meth) acryloxypropyldimethylethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane), and the like.

The amount of the silane coupling agent used is usually about 1 to 10 parts by weight of the silane coupling agent, preferably 2 to 8 parts by weight, based on the amount capable of promoting adhesion between the resin and the rubber, for example, 100 parts by weight of the rubber or the resin. Degree, More preferably, it can select from the range of about 2-6 weight part.

[Other additives]

The resin composition and / or rubber composition may contain various additives, for example, fillers, plasticizers or softeners, co-vulcanizing agents (such as metal oxides such as zinc oxide), anti-aging agents (thermal antioxidants, ozone deterioration inhibitors, and oxidation agents) as necessary. Inhibitors, ultraviolet absorbers and the like), tackifiers, processing aids (polyalkenylene and the like), lubricants, colorants (titanium oxide, carbon black and the like), foaming agents, dispersants, flame retardants, antistatic agents and the like.

Such fillers (or reinforcing agents) include, for example, particulate fillers or reinforcing agents (mica, clay, talc, silicates, silica, calcium carbonate, magnesium carbonate, carbon black, ferrite, etc.), fibrous fillers or reinforcing agents (rayon, nylon). And organic fibers such as vinylon and aramid, inorganic fibers such as carbon fiber and glass fiber).

The plasticizer is not particularly limited as long as plasticity can be imparted to the resin composition or the rubber composition, and conventional plasticizers (phthalic acid ester, aliphatic dicarboxylic acid ester, polyester polymer plasticizer, etc.) can be used. In the rubber composition, conventional softeners (plant oils such as linoleic acid, oleic acid, castor oil, palm oil: mineral oil such as paraffin, processed oil, extender oil, etc.) and the like can be used.

Examples of the polyalkenylene include polyC _5-20 alkenylene which may have a substituent, for example, polypentenamer, polyheptenamer, polyoctenamer, poly (3-methyloctenamer). , Polydecenamer, poly (3-methyldecenamer), polydodecenamer and the like]. The polyalkenylene may have a carbon-carbon double bond ratio of 1/5 or less (for example, 1/5 to 1/20) in the total bonds constituting the polymer main chain. In addition, polyalkenylene is metathesis polymerization of cycloolefins (e.g., C _5-20 cycloolefin which may have substituents such as cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, etc.), It can obtain by partial hydrogenation of polyalkenylene (for example, polybutadiene etc.).

Examples of the lubricant include waxes (for example, paraffin wax, microcrystalline wax, polyethylene wax, etc.), fatty acids (such as stearic acid), aliphatic alcohols (such as stearyl alcohol), and fatty acid derivatives (fatty acids such as butyl stearate). Fatty acid amides such as esters and stearic acid amides, fatty acid metal salts such as zinc stearate, and the like).

As a blowing agent, inorganic foaming agents, such as hydrogencarbonate (for example, sodium hydrogencarbonate, ammonium hydrogencarbonate, etc.); organic blowing agents such as p, p-oxybis (benzenesulfonylhydrazide) and dinitrosopentamethylenetetramine;

The content of the filler is, for example, about 0 to 300 parts by weight, preferably 0 to 200 parts by weight (eg, 0 to 100 parts by weight), more preferably 0 to 200 parts by weight with respect to 100 parts by weight of the resin or rubber. It may be about 50 parts by weight (eg, 0 to 10 parts by weight). The content of the plasticizer or the softener may be, for example, about 0 to 200 parts by weight, preferably about 0 to 150 parts by weight, and more preferably about 0 to 120 parts by weight with respect to 100 parts by weight of the resin or rubber. In addition, the content of the co-vulcanizing agent, anti-aging agent, processing aid or lubricant, colorant, etc. may be an effective amount, for example, the content of the co-vulcanizing agent is about 0 to 20 parts by weight, preferably 0.5 to 100 parts by weight of the resin or rubber. It may be about 15 parts by weight, more preferably about 1 to 10 parts by weight, and the content of polyalkenylene is 0 to 30 parts by weight, preferably 0 to 15 parts by weight, more preferably to 100 parts by weight of the resin or rubber. Preferably it may be about 0-8 weight part.

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 (for example, slip resistance, abrasion resistance, etc.) of the resin can be imparted while utilizing the properties of the vulcanized rubber (elasticity, buffering property, flexibility, and the like).

The composite dispersion may have a sea island structure in which the dispersed phases are independently dispersed in a continuous phase, and the dispersed phase may be in the form of particles, ellipsoids, spheres, rods, or fibers. The preferable shape of the dispersed phase is spherical, and the dispersed phase is preferably uniformly dispersed in the continuous phase. The average particle diameter of the dispersed phase may be one capable of expressing the properties of the substance forming the dispersed phase, for example, 0.1 to 1000 µm, preferably 1 to 750 µm, more preferably 10 to 500 µm (eg, For example, it is about 50-150 micrometers. In addition, when using crosslinked or hardened particle | grains as resin, the average particle diameter of the said dispersed phase respond | corresponds to the average particle diameter of crosslinked or hardened particle.

In addition, the dispersed phase particles may be bonded to the surface of the composite dispersion in a partially exposed state. In such a composite dispersion, the surface can have the properties of the resin (for example, a low coefficient of friction, etc.) while having the properties (for example, high flexibility and buffering properties) of the rubber in a continuous phase.

Moreover, the composite body which bonded together the obtained molded object different from the obtained composite dispersion (for example, resin molded object, vulcanized rubber molded object, etc.) may be sufficient.

[Method for Producing Composite Dispersion]

In the present invention, by dispersing and molding rubber and resin, a dispersion composite in which the vulcanized rubber phase and the resin phase are bonded to each other is produced. In addition, the rubber may be an unvulcanized rubber, and the vulcanization or crosslinking of the unvulcanized rubber may be performed at a suitable step, for example, a molding process or a subsequent process after molding.

In addition, 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 contains a vulcanizing activator (especially a vulcanizing agent such as a radical generator and a vulcanizing activator). You may form with the composition to make. The vulcanizing agent and / or vulcanizing active agent is preferably added to the resin and / or rubber in advance, but may be newly added in the kneading process as necessary.

More specifically, the composite dispersion of the present invention is kneaded with a resin (or a thermoplastic or thermosetting resin composition) and an unvulcanized rubber (unvulcanized rubber composition) to form a predetermined shape, and the unvulcanized rubber is formed in a molding process or subsequent to molding. It can be obtained by vulcanization or crosslinking in the step. 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. Moreover, it is preferable to use crosslinked or cured resin in the form of the granule which has a shape (for example, spherical shape, elliptical shape, rod shape, etc.) suitable for the dispersion phase of a composite dispersion before kneading | mixing.

Kneading can be performed using a conventional kneader (for example, an extruder or the like). In addition, when kneading a thermosetting resin or a composition thereof with an unvulcanized rubber or a vulcanized rubber, it is usually kneaded at the non-curing temperature of the thermosetting resin. Also, kneading of the unvulcanized rubber is usually carried out at a temperature below the vulcanization temperature of the rubber.

Examples of the molding method include extrusion molding, injection molding, blow molding, and the like, and extrusion molding or injection molding is usually used. The shape of the molded article is not particularly limited, and may be a plate, sheet, tubular, or the like. In addition, the molding temperature can be appropriately set according to the raw materials (for example, resin and rubber) used, for example, 50 to 300 ° C, preferably 75 to 250 ° C, more preferably 100 to 225. It is about (degreeC) 150-200 degreeC.

The composite dispersion can be obtained by vulcanizing or crosslinking the molded article after the molding process or after molding. The vulcanization may be carried out under a reduced pressure atmosphere, but is generally carried out at normal pressure. In addition, the vulcanization or crosslinking temperature can be selected, for example, in the range of 70 to 250 ° C, preferably 100 to 230 ° C, and more preferably 150 to 220 ° C.

The composite dispersion thus obtained is firmly bonded in a state in which the vulcanized rubber phase generated by vulcanization of the unvulcanized rubber is in a continuous phase and the resin phase constitutes a dispersed phase. In addition, 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 (such as the properties of the resin, for example, the sliding property) can be effectively expressed. . For this reason, the composite dispersion of the present invention can be used in various applications, for example, as a member for automobile parts (vibration absorbing bushes, spring plates, radiator mounts, etc.), dustproof rubbers, valves, electrical plugs, and the like. Available.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples. In addition, the following resin composition and rubber composition were used in the Example and the comparative example.

[Resin Compositions (A) to (H)]

Resin Compositions A1 to A4

The following resin compositions (A1 to A4) were prepared using polyamide 612 (polycondensate of hexamethylenediamine and dodecanedicarboxylic acid) as the thermoplastic resin. In addition, calculation of MOPACPM3 was performed based on the following basic unit.

NH _2- (CH ₂ ) ₆ -NH-C (= O)-(CH ₂ ) ₁₀ -C (= O) -OH

Resin composition (A1):

Polyamide 612 (NH ₂ termini / COOH term = 9/1 (molar ratio)) alone

(Production method): A predetermined amount of hexamethylenediamine was added to an 80% by weight aqueous solution of a salt of hexamethylenediamine and dodecanedicarboxylic acid, and heated (220 ° C.) under pressure (17.5 kg / cm ² ) in a nitrogen-substituted autoclave. ), And moisture in the system along with nitrogen gas was discharged out of the system for 4 hours. Thereafter, the mixture was gradually warmed up (275 ° C) to remove moisture residues out of the system, and the internal pressure of the autoclave was returned to normal pressure to obtain polyamide 612 after cooling. The obtained polymer had a molecular weight (Mn) of about 20000 and the ratio of the amino terminal to the carboxyl terminal = 9/1. This polymer was used alone as the resin composition (A1).

Resin composition (A2):

Polyamide 612 (NH ₂ ends / COOH ends = 1/1 (molar ratio)) alone

(Manufacturing method): 80weight% of aqueous solution of the salt of hexamethylenediamine and dodecanedicarboxylic acid was heated (220 degreeC) under pressurization (17.5 kg / cm <^2> ) in nitrogen-substituted autoclave, and water in system with nitrogen gas Was discharged out of the system for 4 hours. Thereafter, the temperature of the autoclave was returned to normal pressure after gradually raising the temperature (275 ° C.) for 1 hour to remove moisture residues from the system. After cooling, polyamide 612 was obtained. The obtained polymer had a molecular weight (Mn) of 20000 to 25000 and the ratio of amino terminal and carboxyl terminal = 1/1. This polymer was used alone as the resin composition (A2).

Resin composition (A3):

Polyamide 612 (NH ₂ termini / COOH term = 3/7 (molar ratio)) alone

(Manufacturing method): The resin composition (A1) and the next resin composition (A4) were kneaded using a twin screw extruder at a weight ratio of 1/3. This was used independently as a resin composition (A3).

Resin composition (A4):

Polyamide 612 (NH ₂ terminus / COOH terminus = 1/9 (molar ratio)) alone

(Manufacturing method) A predetermined amount of dodecanedicarboxylic acid was added to an 80 wt% aqueous solution of a salt of hexamethylenediamine and dodecanedicarboxylic acid, and heated under pressure (17.5 kg / cm ² ) in a nitrogen-substituted autoclave ( 220 ° C.), and moisture in the system along with nitrogen gas was discharged out of the system for 4 hours. Thereafter, the temperature of the autoclave was returned to normal pressure after gradually raising the temperature (275 ° C.) for 1 hour to remove moisture residues from the system. After cooling, polyamide 612 was obtained. The obtained polymer had a molecular weight (Mn) of about 20000 and the ratio of the amino terminal to the carboxyl terminal = 1/9. This polymer was used alone as the resin composition (A4).

Resin composition (A5):

(i) 100 parts by weight of polyamide 612 (NH ₂ termini / COOH term = 3/7 (molar ratio))

(ii) 1 part by weight of vulcanization activator (trimethylolpropane methacrylate)

(Manufacturing method): The mixture which mixed trimethylol propane trimethyl methacrylate (TRIM) in 1 weight part with respect to 100 weight part of said resin compositions (A3) was melt-kneaded using a twin screw extruder, and the resin composition (A5) Got.

Resin Compositions B1 to B2

The following resin compositions (B1 to B2) were prepared using polyamide 66 (polycondensate of hexamethylenediamine and adipic acid) as the thermoplastic resin. In addition, calculation of MOPACPM3 was performed based on the following basic unit.

NH _2- (CH ₂ ) ₆ -NH-C (= 0)-(CH ₂ ) ₄ -C (= 0) -OH

Resin composition (B1):

Polyamide 66 (NH ₂ terminal / COOH terminal = 1/1 (molar ratio)) alone

(Manufacturing method): Polyamide 66 having a molecular weight (Mn) of 20000 to 25000, the ratio of the amino terminal to the carboxy terminal = 1/9 by the same production method as in the above (A2), using a combination of monomers as hexamethylenediamine and adipic acid. Was obtained and it was set as the resin composition (B1) independently.

Resin composition (B2):

Polyamide 66 (NH ₂ terminus / COOH terminus = 1/3 (molar ratio)) alone

(Manufacturing method): Polyamide whose monomer combination is hexamethylenediamine and adipic acid, and the molecular weight (Mn) is about 20000, ratio of amino terminal and carboxyl terminal = 1/9 by the same manufacturing method as said (A4). 66 was obtained. This polymer and the resin composition (B1) were kneaded with a twin screw extruder at a weight ratio of 62.5 / 37.5 to obtain a resin composition (B2).

Resin Compositions C1 to C3

The following resin compositions (C1 to C3) were prepared using polyamide 6 (opening polymer of ε-caprolactam) as the thermoplastic resin. In addition, calculation of MOPACPM3 was performed based on the following basic unit.

NH _2- (CH ₂ ) ₅ -C (= O) -NH- (CH ₂ ) ₅ -C (= O) -OH

Resin composition (C1):

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

(Manufacturing method): The 80 weight% aqueous solution of (epsilon) -caprolactam was heated to 250-260 degreeC in nitrogen-substituted autoclave in presence of a small amount of phosphoric acid, and the moisture in system with nitrogen gas was discharged out of the system for 4 hours. Thereafter, the temperature was gradually elevated (275 ° C) for 1 hour, and the residue of moisture was removed from the system, and then cooled to obtain polyamide 6. The obtained polymer had a molecular weight (Mn) of about 20000 to 25000, and the ratio of amino terminal and carboxyl terminal = 1/1. This polymer was used alone as the resin composition (C1).

Resin composition (C2):

Polyamide 6 (NH ₂ terminus / COOH terminus = 1/3 (molar ratio)) alone

(Manufacturing method): A predetermined amount of adipic acid was added to an 80 wt% aqueous solution of ε-caprolactam, and heated to 250 to 260 ° C. in an autoclave substituted with nitrogen in the presence of a small amount of phosphoric acid, followed by nitrogen gas in the system. Moisture was drained out of the system for 4 hours. Thereafter, the temperature was gradually elevated (275 ° C) for 1 hour, and the residue of water was removed from the system, and then cooled to obtain polyamide 6. The obtained polymer had a molecular weight (Mn) of about 20000 and the ratio of the amino terminal to the carboxyl terminal = 1/9. This polymer was used as the resin composition (C4). This (C4) and the said resin composition (C1) were knead | mixed so that it might become weight ratio 37.5 / 62.5, and it was set as the resin composition (C2).

Resin composition (C3):

Polyamide 6 (NH ₂ terminus / COOH terminus = 1/4 (molar ratio)) alone

(Manufacturing method): The said (C1) and said (C4) were knead | mixed so that it might become a weight ratio 25/75, and it was set as the resin composition (C3).

Resin Compositions D1 to D3

The following resin compositions (D1 to D3) were prepared using a polycondensate (aromatic nylon A5) of terephthalic acid and trimethylhexamethylenediamine as the thermoplastic resin. In addition, calculation of MOPACPM3 was performed based on the following basic unit.

Resin composition (D1):

Aromatic polyamide A5 (NH ₂ terminus / COOH terminus = 1/1 (molar ratio)) alone

(Manufacturing method): The combination of monomers was made into trimethylhexamethylenediamine and terephthalic acid, and a polymer having a molecular weight (Mn) of 20000 to 25000, an amino terminal ratio and a carboxy terminal ratio = 1/1 was obtained by the same production method as in the above (A2), This was made into the resin composition (D1) independently.

Resin composition (D2):

Aromatic polyamide A5 (NH ₂ terminus / COOH terminus = 1/3 (molar ratio)) alone

(Manufacturing method): The combination of monomers was made into trimethylhexamethylenediamine and terephthalic acid, and a polymer having a molecular weight (Mn) of about 20000, a ratio of amino terminal to carboxyl terminal = 1/9 was obtained by the same method as described above for (A4), This polymer was used as the resin composition (D4). This polymer (D4) and the resin composition (D1) were kneaded with a twin screw extruder at a weight ratio of 62.5 / 37.5, and this was used as the resin composition (D2).

Resin composition (D3):

Aromatic polyamide A5 (NH ₂ terminus / COOH terminus = 1/4 (molar ratio)) alone

(Manufacturing method): The said (D1) and said (D4) were knead | mixed so that it might become a polymerization ratio 25/75, and it was set as the resin composition (D3).

Resin Compositions E1 to E2

The following resin compositions (E1 to E2) were prepared using PBT (polycondensate of terephthalic acid and 1,4-butanediol) or amine modified PBT (reaction product of the PBT with hexamethylenediamine) as the thermoplastic resin. In addition, calculation of MOPACPM3 was performed based on the following basic unit.

For PBT:

For Amine Modified PBT:

Resin composition (E1):

PBT (OH terminal / COOH terminal = 1/1 (molar ratio)) alone

(Manufacturing method): 14.587 kg of dimethyl terephthalate, 6.767 kg of 1,4-butanediol, 30 g of calcium acetate and 60 g of antimony oxide were placed in a polymerization tank having a nitrogen gas introduction tube and a side tube for distillation, and superheated at 180 ° C, Nitrogen gas was supplied in small portions. When the outflow of methanol was confirmed, temperature rising was gradually started under reduced pressure, and it gradually led to 270 degreeC and the vacuum degree 100 Pa or less. After confirming the outflow of ethylene glycol, it heated and maintained at 270 degreeC for 3 hours, and extracted and left to cool. The obtained polymer was used as the resin composition (E1).

Resin composition (E2):

Amine-modified PBT (NH ₂ termini / OH term = 1/1 (molar ratio)) alone

(Manufacturing method): The carboxyl group contained in said (E1) and (E1) was knead | mixed for 30 minutes using the kneading machine at 230 degreeC, and it was set as the resin composition (E2).

Resin Composition F

The resin composition was manufactured independently of poly (2,5-dimethylphenylene ether) (manufactured by Degusa AG Co., Ltd., Vestoran 1900). In addition, calculation of MOPACPM3 was performed based on the following basic unit.

Resin Composition G

The resin composition was prepared by polypropylene alone. In addition, calculation of MOPACPM3 was performed based on the following basic unit.

CH ₃ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ (CH ₃ )

Resin Composition H

The resin composition was manufactured by polyacetal (Polyplastics Co., Ltd. product, Juracon M90) alone. In addition, calculation of MOPACPM3 was performed based on the following basic unit.

CH ₃ -O-CH ₂ -O-CH ₂ -O-CH ₂ -CH ₂ -O-CH ₃

Resin Compositions I1 to I3

Resin composition (I1):

(Manufacturing method): To 883 g of distilled and purified dimethyl terephthalate, 783 g of 1,4-butanediol and 35.2 g of 2-butene-1,4-diol, 1.82 g of calcium acetate and 3.64 g of antimony oxide were added to the stirrer and nitrogen. The gas introduction tube and the side tube for distillation were also placed in a polymerization tube connected to a vacuum system, heated to 180 ° C by an oil bath, and nitrogen gas was supplied in small portions. When the amount of methanol discharged reached the theoretical value, stirring was started, the temperature in the system was gradually raised to 250 to 260 ° C, and the vacuum was induced up to 100 Pa or less. The condensation reaction was allowed to proceed for 2 to 3 hours while distilling the resulting 1,4-butanediol in small portions, and the relative viscosity in the mixed solvent of tetrachloroethane / phenol = 40/60 (volume ratio) was measured suitably, and the number average molecular weight When this reached 10,000, the reaction was terminated and PBT was obtained. The density | concentration of the unsaturated bond of the obtained polymer was 2 in average and 0.2 mol / kg in a molecule | numerator, and made this polymer the resin composition (I1).

Resin composition (I2):

(Manufacturing method) In the manufacture of said (I1), it carried out similarly to said (I1) except having replaced 1, 4- butanediol by 819g and 2-butene-1,4-diol by 70.4g. A polymer having an average molecular weight of about 10000 was obtained. The concentration of the unsaturated bond of the obtained polymer was an average of four and 0.4 mol / kg in a molecule | numerator, and this polymer was made into resin composition (I2) independently.

Resin composition (I3):

(Manufacturing method): The mixture which mixed trimethylol propane trimethyl methacrylate (TRIM) in 1 weight part with respect to 100 weight part of said resin compositions (I2) was melt-kneaded using a twin screw extruder, and the resin composition (I3) )

Resin Composition J

(Manufacturing method): Using a melamine resin (Sumicon MMC-50 manufactured by Sumitomo Beclite Co., Ltd.), a 100 mm × 100 mm × 4 mm flat plate was molded, and the flat plate was It was used as a sample of the composition (J).

Resin Composition K

(Manufacturing method) diethylaminopropylamine was added at a ratio of 6 parts by weight based on 100 parts by weight of a bisphenol A epoxy resin (EPELLOTE 828 manufactured by Shell Co., Ltd.), cured at 100 ° C, and 100 mm × 100 mm. A flat plate of 4 mm was molded and the flat plate was used as a sample of the resin composition (K).

Resin Composition L

(Manufacturing method): 604 g of maleic anhydride and 507 g of propylene glycol were dehydrated and condensed at 180 to 190 ° C. in an atmospheric nitrogen stream in the presence of 0.22 g of hydroquinone monomethyl ether and 0.6 g of dibutyltin oxide as an esterification catalyst. The unsaturated polyester of the weight average molecular weight 5800 was obtained. 3.4 g of cobalt naphthenate was added to this unsaturated polyester, and it dissolved and diluted with 600 g of ethyl methacrylate and 100 g of styrene. To 100 parts by weight of this diluent, an organic peroxide (Nippon Yushi Co., Ltd., Verbutylo) was added at a ratio of 3 parts by weight, stirred, and cured at 80 ° C. to form a 100 mm × 100 mm × 4 mm flat plate. This flat plate was used as a sample of the resin composition (L).

[Unvulcanized Rubber Composition (R)]

The following components were mix | blended in the predetermined ratio, and the unvulcanized rubber composition (R1-R8) was produced.

Rubber composition R1

(i) 100 parts by weight of rubber (90 parts by weight of ethylene propylene diene rubber (diene content 8.2% by weight), 10 parts by weight of polyoctenylene rubber)

(ii) 1 part by weight of filler [carbon black (FEF)]

(iii) 5 parts by weight of a radical generator [organic peroxide (dicumylperoxide)

(iv) 0 parts by weight of vulcanizing activator

(v) 100 parts by weight of plasticizer

(vi) 5 parts by weight of zinc oxide

(vii) 1 part by weight of stearic acid

Rubber composition R2

(i) 100 parts by weight of rubber (90 parts by weight of ethylene propylene diene rubber (diene content 8.2% by weight), 10 parts by weight of polyoctenylene rubber)

(ii) 1 part by weight of filler [carbon black (FEF)]

(iii) 5 parts by weight of a radical generator [organic peroxide (dicumylperoxide)]

(iv) 1 part by weight of a vulcanization activator (trimethylolpropanetrimethacrylate)

(v) 100 parts by weight of plasticizer

(vi) 5 parts by weight of zinc oxide

(vii) 1 part by weight of stearic acid

Rubber composition R3

(i) 100 parts by weight of rubber (90 parts by weight of ethylene propylene diene rubber (diene content 8.2% by weight), 10 parts by weight of polyoctenylene rubber)

(ii) 1 part by weight of filler [carbon black (FEF)]

(iii) 5 parts by weight of a radical generator [organic peroxide (dicumylperoxide)]

(iv) 2 parts by weight of a vulcanizing activator (butanediol dimethacrylate)

(v) 100 parts by weight of plasticizer

(vi) 5 parts by weight of zinc oxide

(vii) 1 part by weight of stearic acid

Rubber composition R4

(i) 100 parts by weight of rubber (90 parts by weight of ethylene propylene diene rubber (diene content 8.2% by weight), 10 parts by weight of polyoctenylene rubber)

(ii) 1 part by weight of filler [carbon black (FEF)]

(iii) 3 parts by weight of a radical generator (tetramethylthiuram disulfide)

(iv) 1 part by weight of a vulcanization activator (trimethylolpropanetrimethacrylate)

(v) 100 parts by weight of plasticizer

(vi) 5 parts by weight of zinc oxide

(vii) 1 part by weight of stearic acid

Rubber composition R5

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

(ii) 1 part by weight of filler [carbon black (FEF)]

(iii) 5 parts by weight of a radical generator [organic peroxide (dicumylperoxide)]

(iv) 1 part by weight of a vulcanization activator (trimethylolpropanetrimethacrylate)

(v) 100 parts by weight of plasticizer

(vi) 5 parts by weight of zinc oxide

(vii) 1 part by weight of stearic acid

Rubber composition R6

(i) 100 parts by weight of rubber (silicone rubber ("SH851", manufactured by Toray Dow Corning Co., Ltd.))

(ii) 0 parts by weight of filler

(iii) 3 parts by weight of a radical generator [organic peroxide (dicumylperoxide)]

(iv) 1 part by weight of a vulcanization activator (trimethylolpropanetrimethacrylate)

(v) 0 parts by weight of plasticizer (oil)

(vi) 0 parts by weight of zinc oxide

(vii) 0 parts by weight of stearic acid

Rubber composition R7

(i) 100 parts by weight of silicone rubber ("4104U", manufactured by Toray Dow Corning Co., Ltd.)

(ii) 0 parts by weight of filler

(iii) 4 parts by weight of a radical generator (2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, manufactured by Nippon Yushi Co., Ltd.)

(iv) 0 parts by weight of vulcanizing activator

(v) 0 parts by weight of plasticizer (oil)

(vi) 0 parts by weight of zinc oxide

(vii) 0 parts by weight of stearic acid

Rubber composition R8

(i) 100 parts by weight of fluororubber (FKM) (Dai EL "G920" manufactured by Daikin Kogyo Co., Ltd.)

(ii) 0 parts by weight of filler

(iii) 3 parts by weight of a radical generator (dicumylperoxide)

(iv) 4 parts by weight of vulcanization activator (triallyl isocyanurate)

(v) 0 parts by weight of plasticizer (oil)

(vi) 0 parts by weight of zinc oxide

(vii) 0 parts by weight of stearic acid

The component composition of the unvulcanized rubber composition (R1 to R8) is shown in Table 1 below.

The component in a table | surface is as showing below.

[Rubber] EPDM: ethylene propylene diene rubber,

V: polyoctenylene rubber,

NR: natural rubber,

Q-1: silicone rubber (SH851),

Q-2: silicone rubber (4104U),

FKM: Fluorine Rubber

[Filler] FEF: Carbon Black

[Radical generator] DKPO: dicumyl peroxide,

TMTD: tetramethylthiuram disulfide,

Perhexa 25B40: 2,5-dimethyl-2,5-di (t-butylperoxide) hexin-3

[Vulcanization activator] TRIM: trimethylolpropane trimethacrylate,

BDMA: butanediol dimethacrylate,

TAIC: triallyl isocyanurate.

<Examples 1 to 99 and Comparative Examples 1 to 41>

The resin composition was ground by a freeze grinding method to prepare a powder having a particle size of 80 μm or less. 40 parts by weight of the obtained resin powder and 100 parts by weight of the rubber composition are used in the combinations shown in Tables 2 to 10, mixed and kneaded with a roll at a temperature of 80 ° C, and the mixture is 3 mm thick at a temperature of 180 ° C using a compression molding machine. It was molded into a flat plate and vulcanized at the same time to prepare a composite dispersion.

Tensile strength at break and taper wear (abrasive stone CS517) were measured at a temperature of 20 ° C. and a relative humidity of 65% for the obtained flat composite dispersion. In addition, the result of the tensile test showed the tensile strength of each test piece as the relative value with respect to the tensile strength of the rubber composition single-piece when the tensile strength of the rubber composition single-unit which does not mix resin powder was 100. In addition, the joint strength between rubber | gum / resin was measured as follows.

Each resin material was molded into a flat plate having a thickness of 2 mm by injection molding. To the rubber material separately, an unvulcanized sheet having a thickness of 2 mm was produced, and both were vulcanized and bonded by a compression molding machine under conditions of 180 ° C. for 10 minutes under contact. It was left for 24 hours after adhesion and used for 180 ° peeling test. In this peeling test, when peeling of both advanced by the cohesive failure of all the rubber materials, the joint strength was evaluated as "A". On the other hand, when the whole peeled off progressed in the interface peeling between rubber | gum / resin, when the joint strength was evaluated as "C", and when the cohesive fracture of the rubber side and the interface peeling between rubber resin generate | occur | produced, it is "B". Evaluated.

The results are shown in Tables 2-10. In addition, "the number of active atoms in 1 molecule" in a table | surface shows the number of active atoms (S≥0.006) in 1 molecule of thermoplastic resin obtained by calculation of MOPACPM3. In addition, in the said calculation, Ec was -8 eV (when a radical generator is a peroxide), or -6 eV (when a radical generator is tetramethyl thiuram disulfide).

In the present invention, by melting and kneading and vulcanizing the unvulcanized rubber and resin, and vulcanizing or crosslinking the unvulcanized rubber, the vulcanized rubber phase is firmly bonded in a state in which the vulcanized rubber phase is composed of a disperse phase and a resin phase. A composite dispersion can be obtained. Further, in the composite dispersion in which the dispersed phase particles (resin particles) are partially exposed on the surface, the dispersed phase (resin) properties can be expressed on the surface while having the characteristics of the continuous phase (rubber).

Claims (22)

A composite dispersion comprising a vulcanized rubber phase constituting a matrix phase and a resin phase bonded directly to the vulcanized rubber phase to form a dispersed phase. The composite dispersion according to claim 1, wherein an vulcanized rubber phase and a resinous island form an island-in-an ocean structure. The composite dispersion according to claim 1, wherein the dispersed phase particles are partially exposed on the surface. The composite dispersion according to claim 1, wherein the resinous phase comprises at least one component of a thermoplastic resin and a thermosetting resin. The thermoplastic resin of claim 4, wherein the thermoplastic resin is a polyamide resin, a polyester resin, a poly (thio) ether resin, a polycarbonate resin, a polyimide resin, a polysulfone resin, a polyurethane resin, or a polyolefin resin. At least one selected from resins, halogen-containing resins, styrene resins, (meth) acrylic resins and thermoplastic elastomers, and the thermosetting resin is a phenol resin, an amino resin, an epoxy resin, a silicone resin, a thermosetting polyimide resin, or a thermosetting polyurethane type The composite dispersion which is at least 1 sort (s) chosen from resin, thermosetting acrylic resin, vinyl ester resin, unsaturated polyester resin, and diallyl phthalate resin. The resinous resin according to claim 1, wherein the dendritic resin is aliphatic polyamide resin, aromatic polyester resin, polyacetal resin, polyphenylene ether resin, polysulfide resin, polyolefin resin, polyurethane resin, polyamide elastomer A composite dispersion comprising at least one resin selected from polyester elastomers, polyurethane elastomers, polystyrene elastomers, and polyolefin elastomers. The composite dispersion according to claim 1, wherein the rubber phase comprises at least one rubber selected from diene rubber, olefin rubber, acrylic rubber, fluorine rubber, silicone rubber and urethane rubber. The composite dispersion according to claim 1, wherein the ratio of the vulcanized rubber phase and the resin phase is vulcanized rubber phase / resin phase = 90/10 to 10/90 (weight ratio). 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 radical generator and at least one vulcanizing agent of sulfur. The composite dispersion according to claim 9, wherein the dendritic resin includes a resin having an average of two or more hydrogen atoms and / or sulfur atoms having an orbital interaction energy coefficient S of 0.006 or more in one molecule. sieve. <Equation 1> S = (C _{HOMO, n} ) ² / | E _C -E _{HOMO, n} | + (C _{LUMO, n} ) ² / | E _C -E _{LUMO, n} | ( _Wherein E _C , C _{HOMO, n} , E _{HOMO, n} , C _{LUMO, n} , E _{LUMO, n} are all values calculated by semi-empirical molecular orbital method MOPACPM3, where E _C is the radical orbit of the radical generator) Represents energy (eV), and C _{HOMO, n} represents the molecular orbital coefficient of the highest peak molecular orbital (HOMO) of the nth hydrogen atom and / or sulfur atom constituting the basic unit of the resin, and E _{HOMO, n} Represents the orbital energy (eV) of the HOMO, C _{LUMO, n} represents the molecular orbital coefficient of the lowest co-molecular orbital (LUMO) of the n-th hydrogen atom and / or sulfur atom, E _{LUMO, n} is the Orbital energy (eV) of LUMO) The composite dispersion according to claim 1, wherein the resinous phase comprises at least one crosslinkable resin selected from a thermoplastic resin having an unsaturated bond and a thermosetting resin having a crosslinkable functional group. The thermoplastic resin of claim 11, wherein the thermoplastic resin having an unsaturated bond (1) a resin produced by the reaction of a polymerizable compound having a reactive group (A) and an unsaturated bond with a thermoplastic resin having a reactive group (B) reactive with the reactive group (A), (2) a thermoplastic resin in which an unsaturated bond is introduced by copolymerization or co-condensation, and (3) polymer blends composed of resins and resins having unsaturated bonds It is any one of the composite dispersion. The composite dispersion according to claim 11 or 12, wherein the concentration of the unsaturated bond is 0.01 to 6.6 mol per 1 kg of resin. The composite dispersion according to claim 9, wherein the radical generator is at least one selected from organic peroxides, azo compounds and sulfur containing organic compounds. The composite dispersion according to claim 9, wherein the radical generator is an organic peroxide. 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 based on 100 parts by weight of unvulcanized rubber. 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 vulcanizing active agent. 18. The composite dispersion according to claim 17, wherein the vulcanizing active agent is an organic compound having two or more polymerizable unsaturated bonds in one molecule. The composite dispersion according to claim 17, which is formed of a composition comprising 0.1 to 5 parts by weight of the vulcanizing activator with respect to 100 parts by weight of the vulcanized rubber and / or dendritic phase. The manufacturing method of the composite dispersion which uses unvulcanized rubber as said rubber which manufactures the composite dispersion containing a vulcanized rubber phase and a resin phase by kneading rubber | gum and resin and shape | molding. The method of claim 20, wherein at least one component of the rubber and the resin comprises a vulcanizing agent. The manufacturing method of Claim 20 whose resin is a granular material.