JP2008031263A - Curable composition and cured material of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition containing a vinyl-based polymer giving a cured material showing generally good mechanical properties, oil resistance, heat resistance, etc., and capable of being cured by hydrosilylation reaction and omitting a secondary curing, and the cured material of the same. <P>SOLUTION: This curable composition contains (A) a vinyl-based polymer (I) containing at least one alkenyl group capable of performing hydrosilylation reaction in its molecule, (B) a hydrosilyl group-containing compound (II), (C) a hydrosilylation catalyst, and (D) coal ash. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a curable composition and a cured product thereof. More specifically, the present invention relates to a curable composition containing an alkenyl group-containing vinyl polymer, a hydrosilyl group-containing compound, a hydrosilylation catalyst, and coal ash and capable of omitting secondary vulcanization, and a cured product thereof.

A molded body containing a vinyl polymer as a main component can be obtained by kneading a high molecular weight polymer together with various additives in a heated state using a roll, a mill, or the like and molding the polymer. Among them, an acrylic rubber molded body mainly composed of a (meth) acrylic polymer is kneaded with a compounding agent such as a filler and a vulcanizing agent in an unvulcanized rubber (acrylic rubber), followed by heat vulcanization molding. Can be obtained. However, it is inferior in workability, such as sticking to a roll during kneading and being difficult to smooth during sheeting, and it has poor workability such as non-fluidity during molding and a low vulcanization rate, and is easy to scorch. There is a problem such as poor curability (Non-Patent Document 1).
As a method for solving these problems, use of a (meth) acrylic polymer having a reactive functional group at the molecular end can be considered. When a (meth) acrylic polymer having a reactive functional group at the molecular end is used, the molecular weight between the crosslinking points can be effectively obtained, and the molecular weight of the main chain itself can be reduced. As a result, it is expected that processability will be improved. In addition, since it has a reactive functional group at the molecular end, a cured product having a high molecular weight between cross-linking points can be obtained, so that it has physical properties such as elongation and hardness as compared with conventional acrylic rubber having a functional group in the side chain. It is expected to obtain an excellent cured product. Therefore, many researchers are studying an industrial production method of a (meth) acrylic polymer having a reactive functional group at the molecular end. For example, there is a method for synthesizing a (meth) acrylic polymer having an alkenyl group at both ends using an alkenyl group-containing disulfide as a chain transfer agent (Patent Document 1). However, it is difficult to reliably introduce alkenyl groups at both ends, and since the resulting copolymer is a latex, a complicated operation of removing moisture is required when used for molded products. There is a problem such as. In addition, (meth) acrylic polymers having hydroxyl groups at both ends were synthesized using disulfides having hydroxyl groups, and (meth) acrylic having alkenyl groups at both ends using the reactivity of hydroxyl groups. There is a method of synthesizing a polymer (Patent Document 2). This method also has the problem that it is difficult to reliably introduce alkenyl groups at both ends, and that complicated work such as long-time post-curing is required for curing with peroxide. is there.
Therefore, in order to solve such a problem, the present inventors have obtained a (meth) acrylic compound having a specific terminal structure obtained by a polymerization method using an organic halide or the like as an initiator and a transition metal complex as a catalyst. Developed a method (Patent Document 3) for producing a (meth) acrylic polymer having a narrow molecular weight distribution having an alkenyl group at the terminal by converting the halogen of the polymer into an alkenyl group-containing substituent. Manufacturing is possible. Moreover, the molded object (patent document 4) and the on-site molded gasket (patent document 5, patent document 6) which harden | cure the curable composition containing the vinyl polymer containing an alkenyl group at the terminal, and a hydrosilyl group containing compound. Has proposed. The hydrosilylation reaction used for curing a curable composition comprising a vinyl polymer containing an alkenyl group at the terminal and a hydrosilyl group-containing compound is very slow or does not proceed substantially at low temperatures. , It has a feature with excellent thermal potential that the reaction is completed quickly by heating. Therefore, this curable composition has an advantage that a cured product can be obtained quickly without scorching during molding.
A curable composition containing a (meth) acrylic polymer having an alkenyl group at the terminal obtained by the above method (Patent Document 3), a vinyl polymer containing an alkenyl group at the terminal, and a hydrosilyl group-containing compound. The curable composition to be contained (Patent Document 4) is expected to be usable for a wide variety of uses because the cured product obtained from these has excellent physical properties. Particularly, the property before curing is liquid, and promptly by heating. Since the reaction is completed, it is useful as a liquid injection molding rubber. However, this type of molded rubber as it is has a low resistance to compression under heating, and cannot be applied to sealing material applications that require low compression set, which is one index indicating resistance to compression. Therefore, in order to obtain a compression set sufficient for practical use, it is necessary to further heat-treat (secondary vulcanization) the molded product obtained by injection molding or press molding at a high temperature of 150 to 200 ° C. is there. However, this method requires a process in which molded rubber once molded is placed in a high-temperature oven and heated for a long time, and there is a problem that work efficiency is low and productivity is poor. Under such circumstances, an acrylic rubber composition having a small compression set and not requiring secondary vulcanization is desired.
Japanese Patent Laid-Open No. 5-255415 JP-A-5-262808 JP-A-9-272714 JP 2000-154255 A JP 2000-154370 A JP 2003-113288 A Journal of the Japan Rubber Association, Vol. 73, No. 10, 555 (2000)

The object of the present invention is to provide a cured product that generally exhibits good mechanical properties, oil resistance, heat resistance, and the like, contains a vinyl polymer, and can be cured by a hydrosilylation reaction. An object of the present invention is to provide a curable composition having a practical compression set without vulcanization.

As a result of intensive studies in view of the above-described present situation, the present inventors have found that the above problems can be improved by using coal ash as a filler, and have completed the present invention.

That is, the present invention
(A) vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule, (B) hydrosilyl group-containing compound (II), (C) hydrosilylation catalyst, and (D) The present invention relates to a curable composition containing coal ash as a component.

  The vinyl polymer (I) preferably has a molecular weight distribution of less than 1.8.

  The vinyl polymer (I) is a monomer whose main chain is selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. Those produced mainly by polymerization of can be used.

  The vinyl polymer (I) is preferably a (meth) acrylic polymer, more preferably an acrylic polymer, and even more preferably an acrylic ester polymer. In particular, at least one selected from the group consisting of ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, 2-methoxybutyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate is mainly produced by polymerization. It is particularly preferred that

  The main chain of the vinyl polymer (I) is preferably produced by a living radical polymerization method, and the living radical polymerization is more preferably atom transfer radical polymerization.

  The atom transfer radical polymerization is carried out using a complex selected from the group consisting of transition metal complexes having a central metal of Group 7, 8, 9, 10, or 11 of the periodic table as a catalyst. It is more preferable that it is selected from the group consisting of a complex of copper, nickel, ruthenium or iron, and it is more preferable that it is a complex of copper.

The vinyl polymer (I) has the following steps:
(1a) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the general formula (1)
-C (R ¹ ) (R ² ) (X) (1)
(Wherein R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer; X represents chlorine, bromine or iodine), and a vinyl polymer having a terminal structure represented by ,
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation reaction;
It is preferable that it is obtained by.

The vinyl polymer (I) has the following steps:
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two alkenyl groups having low polymerizability;
It is preferable that it is a vinyl polymer obtained by this.

  The vinyl polymer (I) preferably has an alkenyl group capable of hydrosilylation at the terminal.

  The (B) hydrosilyl group-containing compound (II) is preferably an organohydrogenpolysiloxane.

  The (D) coal ash is more preferably fly ash.

  The curable composition may further contain (D) reinforcing silica.

  The present invention relates to a cured product obtained from the curable composition.

  According to the present invention, in a curable composition containing a vinyl polymer and capable of being cured by a hydrosilylation reaction, which gives a cured product generally exhibiting good mechanical properties, oil resistance, heat resistance, etc. A curable composition having a practical compression set and a cured product thereof can be obtained without vulcanization.

  Below, the curable composition of this invention and its hardened | cured material are explained in full detail.

<< (A) Vinyl Polymer (I) >>
<Main chain>
The vinyl polymer (I) in the present invention is a vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule, and is not particularly limited as a vinyl monomer constituting its main chain. In addition, various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethyl methyl (meth) acrylate), T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic acid monomers such as hexadecylethyl; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, fluoride Fluorine-containing vinyl monomers such as vinylidene; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; monomers of fumaric acid and fumaric acid Alkyl es And maleic monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitriles such as acrylonitrile and methacrylonitrile Group-containing vinyl monomers; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Alkenes such as ethylene and propylene Conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used singly or a plurality thereof may be copolymerized. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
The main chain of the vinyl polymer (I) is at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that the polymer is mainly produced by polymerization. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer (I) is the above monomer, and preferably 70 mol% or more.
Of these, aromatic vinyl monomers and (meth) acrylic acid monomers are preferred from the physical properties of the product. More preferred are acrylic ester monomers and / or methacrylic ester monomers, and particularly preferred are acrylic ester monomers. Specifically preferable examples of the acrylate monomer include ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxybutyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  The molecular weight distribution of the vinyl polymer (I) in the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is Although not limited, Preferably it is less than 1.8, More preferably, it is 1.7 or less, More preferably, it is 1.6 or less, More preferably, it is 1.5 or less, Especially preferably, it is 1.4. Or less, most preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer (I) in the present invention is not particularly limited, but when measured by GPC, a range of 500 to 1,000,000 is preferable, and 1,000 to 100,000 is more preferable. If the molecular weight is too low, the original characteristics of the vinyl polymer (I) tend to be difficult to be expressed. Conversely, if the molecular weight is too high, handling tends to be difficult.

<Synthesis Method of Vinyl Polymer (I)>
The vinyl polymer (I) used in the present invention can be obtained by various polymerization methods, and is not particularly limited, but is a polymer obtained by radical polymerization from the viewpoints of versatility and ease of control of monomers. Is preferred. Among radical polymerizations, controlled radical polymerization is more preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable.

  Examples of a method for introducing an alkenyl group capable of hydrosilylation reaction into the obtained vinyl polymer include a method of directly introducing an alkenyl group capable of hydrosilylation reaction in the polymerization reaction system, and a vinyl polymer having a specific functional group. And a method in which a specific functional group is converted into an alkenyl group capable of hydrosilylation reaction in one step or several steps.

  Each of these synthesis methods will be described in detail below.

The synthesis method of the vinyl polymer having a functional group by radical polymerization radical polymerization method can be classified into “general radical polymerization method” and “controlled radical polymerization method”.
The “general radical polymerization method” means a vinyl monomer having a specific functional group (hereinafter referred to as “functional monomer”) and other vinyl using a polymerization initiator such as an azo compound or a peroxide. This is a method of simply copolymerizing with a monomer.
On the other hand, the “controlled radical polymerization method” is a method capable of introducing a specific functional group at a controlled position such as a terminal.

General radical polymerization “General radical polymerization method” is a simple method and can also be used in the present invention. However, since it is a copolymerization, a specific functional group is only probable in the polymer. Not introduced. Therefore, in order to obtain a polymer having a high functionalization rate, it is necessary to use a large amount of the functional monomer. There is a problem of becoming larger. Further, since it is free radical polymerization, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

Controlled radical polymerization “Controlled radical polymerization method” can be classified into “chain transfer agent method” and “living radical polymerization method”.
The “chain transfer agent method” is characterized in that polymerization is performed using a chain transfer agent having a specific functional group, and a vinyl polymer having a functional group at the terminal is obtained. On the other hand, the “living radical polymerization method” is characterized in that a polymer growth terminal is grown without causing a side reaction such as a termination reaction by using a special polymerization system. As a result, in the “living radical polymerization method”, a polymer having a molecular weight almost as designed is obtained.

The chain transfer agent method “chain transfer agent method” can be used in the present invention because a functional group can be introduced quantitatively at the polymer terminal as compared with “general radical polymerization method”. However, a considerably large amount of a chain transfer agent having a specific functional group with respect to the initiator is required, and there is a problem in terms of economy including processing such as recovery of the chain transfer agent. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that a polymer having a wide molecular weight distribution and a high viscosity is obtained due to free radical polymerization.

  Although it does not specifically limit as radical polymerization using a chain transfer agent (telomer), The following two methods are illustrated as a method of obtaining the vinyl polymer which has the terminal structure suitable for this invention. JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Living radical polymerization Radical polymerization is generally considered difficult to control because it has a high polymerization rate and tends to cause a termination reaction due to coupling between radicals. However, the “living radical polymerization method” differs from the above-described polymerization method in that it is a radical polymerization, but a side reaction such as a termination reaction hardly occurs and a molecular weight distribution is narrow (Mw / Mn is about 1.1 to 1.5). And the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

  Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

  In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The living polymerization in the present invention corresponds to the latter.

  The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown, for example, in Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943; Macromolecules (Macromolecules), using a radical capping agent such as a nitroxide compound as shown in 1994, Vol. 27, p. 7228; “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the characteristics of `` legal method '', it has a halogen which is relatively advantageous for functional group conversion reaction at the end, and has a great degree of freedom in designing initiators and catalysts. It is further preferable as a manufacturing method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614; Macromolecules 1995, Science, 1996, 272, 866; WO 96/30421; WO 97/18247; WO 98/01480; WO 98/40415; Sawamoto et al., Macromolecules. (Macromolecules) 1995, 28, 1721; JP-A-9-208616; JP-A-8-41117.

  The atom transfer radical polymerization in the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, peroxidation with respect to Cu (II ′) when Cu (I) is used as a catalyst. In this method, a general radical initiator such as a compound is allowed to act, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).

  In the present invention, there is no particular restriction as to which of these living radical polymerization methods is used, but an atom transfer radical polymerization method is preferred.

  The living radical polymerization method will be described below.

  First, a method using a radical capping agent such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such nitroxy free radical-containing compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyl. Nitroxy free radicals from cyclic hydroxyamines such as oxy radicals are preferred. Here, the term “substituted” means “substituent”, and as the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

  The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of radical initiator is appropriate for 1 mol of radical capping agent.

  Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis There are peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide. As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, an alkoxyamine compound represented by the following formula may be used as an initiator.

開始剤として上式で示されているような水酸基等の官能基を有するアルコキシアミン化合物を用いると、末端に官能基を有する重合体が得られる。これを本発明の方法に利用すると、末端に官能基を有する重合体が得られる。

When an alkoxyamine compound having a functional group such as a hydroxyl group as represented by the above formula is used as an initiator, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at the terminal can be obtained.

  In the polymerization method using a radical capping agent such as the above nitroxide compound, polymerization conditions such as a monomer, a solvent, and a polymerization temperature used are not limited, but may be the same as the polymerization conditions in atom transfer radical polymerization described below.

Atom Transfer Radical Polymerization In the present invention, it is more preferable to produce the main chain of the vinyl polymer (I) by an atom transfer radical polymerization method as living radical polymerization. This will be described below.

In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator.
For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{R 3 -C (H) (X} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4,
(Wherein R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
R ³ —C ₆ H ₄ —SO ₂ X
(In the above formulas, R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
Etc.

By performing atom transfer radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide as an initiator, a vinyl polymer having a terminal structure represented by the general formula (1) is obtained.
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ¹ and R ² represent a group bonded to the ethylenically unsaturated group of the vinyl monomer described above. X represents chlorine, bromine or iodine.)
As an initiator used in atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a specific functional group that does not start polymerization together with a functional group that starts polymerization can be used. In such a case, a vinyl polymer having a specific functional group at one main chain terminal and a terminal structure represented by the general formula (1) at the other main chain terminal is obtained. Examples of such specific functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

It does not limit as an organic halide which has an alkenyl group as a specific functional group, For example, what has a structure shown in General formula (2) is illustrated.
R ⁶ R ⁷ C (X) —R ⁸ —R ⁹ —C (R ⁵ ) ═CH ₂ (2)
(Wherein R ⁵ is hydrogen or a methyl group, R ⁶ and R ⁷ are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or interconnected at the other end. things, R ⁸ is, -C (O) O- (ester group), - C (O) - ( keto group), or o-, m-, p-phenylene, R ⁹ is a direct bond or carbon atoms 1 to 20 divalent organic groups which may contain one or more ether bonds, X is chlorine, bromine or iodine)
Specific examples of the substituents R ⁶ and R ^{7 in} the general formula (2) include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.
Specific examples of the organic halide having an alkenyl group represented by the general formula (2) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n CH = CH 2, (H 3 C) 2 C (X ) C (O) O (CH 2) n CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O (CH 2) n CH = CH 2,

（上記の各式において、Ｘは塩素、臭素、又はヨウ素、ｎは０〜２０の整数）
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、

(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m CH = _{CH 2, (H 3 C)} 2 C (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O _{(CH 2) n O (CH} 2) m CH = CH 2,

（上記の各式において、Ｘは塩素、臭素、又はヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、又はヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_mＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、又はヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、又はヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、又はヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）等が挙げられる。

(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) _{n -CH = CH 2, o,} m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) -C _{6 H 4 - (CH 2)} n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) _{n -O- (CH 2) m CH} = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- _{(CH 2) n -CH = CH} 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) —C ₆ H ₄ —O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ , o, m, p—CH ₃ CH ₂ C (H) (X) —C ₆ H ₄ — O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ ,
(In the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20).

Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (3).
^{_{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (3)
Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group Or represents an o-, m-, p-phenylene group)
R ⁹ in the general formula (3) is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). When R ⁹ is a direct bond, it is a halogenated allylic compound in which a vinyl group is bonded to a carbon to which a halogen is bonded. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group or a phenylene group as R ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound of general formula (3) is specifically illustrated,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X, CH 2 = CHC (H) (X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3, CH ₂ = CHC (X) (CH ₃ ) ₂ , CH ₂ = CHC (H) (X) C ₂ H ₅ , CH ₂ = CHC (H) (X) CH (CH ₃ ) ₂ , CH ₂ = CHC ( _{H) (X) C 6 H} 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5, CH 2 = CHCH 2 C (H) (X) -CO 2 R, CH 2 = CH (CH _{2) 2 C (H) (} X) -CO 2 R, CH 2 = CH (CH 2) 3 C (H) (X) -CO 2 R, CH 2 = CH (CH 2) 8 C (H) ( _{X) -CO 2 R, CH 2} = CHCH 2 C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 2 C (H) (X) -C 6 H 5, CH 2 = _{CH (CH 2) 3 C (} H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X, o-, m-, p-CH 2 = CH- (CH 2) n -O-C ₆ H ₄ —SO ₂ X,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
Etc.

It does not specifically limit as an organic halide which has a crosslinkable silyl group as a specific functional group, For example, what has a structure shown in General formula (4) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (4)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, and when two or more R ¹¹ or R ¹² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, they may be the same or different, a is 0, 1, 2, or 3, and b is 0, 1, or 2. m is an integer from 0 to 19. (Provided that a + mb ≧ 1)
If the compound of general formula (4) is specifically illustrated,
_{XCH 2 C (O) O (} CH 2) n Si (OCH 3) 3, CH 3 C (H) (X) C (O) O (CH 2) n Si (OCH 3) 3, (CH 3) 2 C (X) C (O) O (CH 2) n Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n Si (CH 3) (OCH 3) 2, CH 3 C (H) (X) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2, (CH 3) 2 C (X) C (O) O (CH 2) n Si (CH 3) (OCH ₃ ) ₂ ,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m Si (OCH ₃ ) ₃ , (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OCH ₃ ) ₃ , CH ₃ CH ₂ C (H) (X ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n O (CH 2) m Si (CH 3) (OCH 3 ) ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m —Si (CH ₃ ) (OCH ₃ ) ₂ , (H ₃ C) ₂ C (X) _{C (O) O (CH 2} ) n O (CH 2) m -Si (CH 3) (OCH 3) 2, CH 3 CH 2 C (H) (X) C (O) O (CH 2) n O _{(CH 2) m -Si (CH} 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2 _{) 2 Si (OCH 3) 3} , o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p- _{XCH 2 -C 6 H 4 - (} CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3 _{) 3, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H _{4 - (CH 2) 2 -O-} (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 2 -O _{- (CH 2) 3 Si (} OCH 3) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H _{4 - (CH 2) 2 -O-} (CH 2) 3 Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3, _{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) ( _{X) -C 6 H 4 -O- (} CH 2) 3 -Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H 4 -O- (CH 2) 2 -O- (CH 2 _{) 3 -Si (OCH 3) 3} , o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3 _{) 3, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.

Examples of the organic halide having a crosslinkable silyl group as a specific functional group further include those having a structure represented by the general formula (5).
^{_{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (5)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, m, X, Y are the same as above)
If such a compound is specifically illustrated,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5, (CH 3 O) 2 (CH 3) SiCH 2 CH 2 C (H) (X) C 6 H 5, (CH _{3 O) 3 Si (CH 2} ) 2 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 2 C (H) (X) -CO 2 R, _{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 3 C (H) (X) -CO 2 _{R, (CH 3 O) 3} Si (CH 2) 4 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 4 C (H) (X) - _{CO 2 R, (CH 3 O} ) 3 Si (CH 2) 9 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 9 C (H) (X _{) -CO 2 R, (CH 3} O) 3 Si (CH 2) 3 C (H) (X) -C 6 H 5, (C _{3 O) 2 (CH 3)} Si (CH 2) 3 C (H) (X) -C 6 H 5, (CH 3 O) 3 Si (CH 2) 4 C (H) (X) -C 6 H _{5, (CH 3 O) 2} (CH 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

It does not specifically limit as an organic halide which has a hydroxyl group as a specific functional group, or a halogenated sulfonyl compound, The following are illustrated.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
It does not specifically limit as an organic halide which has an amino group as a specific functional group, or a halogenated sulfonyl compound, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
It does not specifically limit as an organic halide which has an epoxy group as a specific functional group, or a halogenated sulfonyl compound, The following are illustrated.

（上記の各式において、Ｘは塩素、臭素、又はヨウ素、Ｒは水素原子又は炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
本発明の末端構造を１分子内に２つ以上有する重合体を得るためには、２つ以上の開始点を持つ有機ハロゲン化物、又はハロゲン化スルホニル化合物を開始剤として用いるのが好ましい。具体的に例示するならば、

(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
In order to obtain a polymer having two or more terminal structures of the present invention in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator. For example,

等が挙げられる。

Etc.

  There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated can be used suitably.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferable examples include transition metal complexes having zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal. Of these, a copper complex is preferable. Specific examples of the monovalent copper compound used to form a copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. When using a copper compound, 2,2′-bipyridyl or its derivative, 1,10-phenanthroline or its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine These polyamines are added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. The type of solvent is not particularly limited. For example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated carbonization such as methylene chloride, chloroform and chlorobenzene Hydrogen solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; acetonitrile, propionitrile, benzonitrile, etc. Nitrile solvents; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; N, N-dimethylformamide, N Amide solvents such as N- dimethylacetamide. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.
Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

<Alkenyl group capable of hydrosilylation reaction>
The hydrosilylatable alkenyl groups vinyl polymer used in the hydrosilylatable alkenyl group present invention (I) contains, but not limited to, those represented by the general formula (6) It is preferable.
H ₂ C═C (R ¹³ ) − (6)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms.)
In General formula (6), R < ¹³ > is hydrogen or a C1-C20 organic group.

Although it does not specifically limit as a C1-C20 organic group, A C1-C20 alkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group is mentioned preferably, Specifically, The following groups are exemplified.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 4 (CH 3)} , - C 6 H 3 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 4 (CH 3), - ( _{CH 2) n -C 6 H 3} (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
Among these, from the viewpoint of the activity of the hydrosilylation reaction, R ¹³ is more preferably hydrogen or a methyl group.

  Further, although not limited, the alkenyl group capable of hydrosilylation reaction of the vinyl polymer (I) is not activated by a carbonyl group, an alkenyl group or an aromatic ring conjugated with the carbon-carbon double bond. Is preferred.

  The bond form of the alkenyl group capable of hydrosilylation reaction and the main chain of the vinyl polymer (I) is not particularly limited, but via a carbon-carbon bond, ester bond, ether bond, carbonate bond, amide bond, urethane bond, etc. Are preferably combined.

The vinyl polymer (I) has at least one alkenyl group capable of hydrosilylation reaction, and preferably has 1.5 or more from the viewpoint of mechanical properties of the cured product. Although not specifically limited, specifically, the average value obtained by ¹ H-NMR analysis of the number of alkenyl groups capable of hydrosilylation introduced per molecule of the vinyl polymer is 1.5 or more. And more preferably 1.8 or more.

Position of alkenyl group capable of hydrosilylation reaction When a rubber property is particularly required for the cured product obtained from the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be obtained. It is preferable that at least one of the alkenyl groups capable of hydrosilylation is at the end of the molecular chain. More preferably, all alkenyl groups capable of hydrosilylation reaction are present at the molecular chain ends.

  A method for producing a vinyl polymer having at least one alkenyl group capable of hydrosilylation reaction at the molecular end, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068 and Japanese Patent Publication No. 4-55444. Japanese Laid-Open Patent Publication No. 6-221922 and the like. However, since these methods are free radical polymerization methods using the above-mentioned “chain transfer agent method”, the resulting polymer has a relatively high proportion of alkenyl groups capable of hydrosilylation reaction at the molecular chain ends. The molecular weight distribution (Mw / Mn) is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having an alkenyl group capable of hydrosilylation reaction at the molecular chain terminal at a high ratio, the above-mentioned “living radical polymerization method” is used. Is preferably used.

<Method of introducing alkenyl group capable of hydrosilylation reaction>
Hereinafter, a method for introducing an alkenyl group capable of hydrosilylation reaction into a vinyl polymer will be described, but the method is not limited thereto.

Method for introducing alkenyl group capable of hydrosilylation reaction (Aa) When a vinyl polymer is synthesized by radical polymerization, preferably living radical polymerization, for example, in one molecule as shown in the following general formula (7) And reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group as the second monomer.
^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (7)
(Wherein R ¹⁴ represents hydrogen or a methyl group, R ¹⁵ represents —C (O) O—, or o-, m-, p-phenylene group, and R ¹⁶ represents a direct bond, 20 represents a divalent organic group of 20 and may contain one or more ether bonds. R ¹⁷ represents hydrogen or an organic group having 1 to 20 carbon atoms)
In the general formula (7), R ¹⁷ is hydrogen or an organic group having 1 to 20 carbon atoms. Although it does not specifically limit as a C1-C20 organic group, A C1-C20 alkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group is preferable, Specifically, the following Such groups are exemplified.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 4 (CH 3)} , - C 6 H 3 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 4 (CH 3), - ( _{CH 2) n -C 6 H 3} (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
Of these, R ¹⁷ is more preferably hydrogen or a methyl group.
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. However, if the resulting cured product is expected to have rubber-like properties, a living radical can be used. In the polymerization, it is preferable to react the above compound as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer.
(Ab) When a vinyl polymer is synthesized by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9- A method of reacting a compound having at least two alkenyl groups having low polymerizability such as decadiene.
(Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.
(Ad) A method of substituting a halogen by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in the general formula (8). .
^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (8)
(Wherein, R ¹⁷ is the same .R ^18, R ¹⁹ together carbanion C ^- a is an electron withdrawing group stabilizing or one of the other hydrogen or a 1 to 10 carbon atoms in the electron-withdrawing group Represents an alkyl group or a phenyl group, R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds, M ⁺ represents an alkali metal ion, Or a quaternary ammonium ion.)
As the electron withdrawing group for R ¹⁸ and R ^{19 in} the general formula (8), —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), -COSR (thioester group), - CN (nitrile group), - NO ₂ is (nitro group), and the _{like, -CO 2 R, -C (O} ) R and -CN are particularly preferable. Here, the substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. is there.
(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group .
(Af) An oxyanion or carboxylate anion having an alkenyl group represented by the following general formula (9) or (10), for example, in a vinyl polymer having at least one highly reactive carbon-halogen bond To replace halogen by reaction.
^{_{H 2 C = C (R 17}} ) -R 21 -O - M + (9)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²¹ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
^{_{H 2 C = C (R 17}} ) -R 22 -C (O) O - M + (10)
(In the formula, R ¹⁷ and M ⁺ are the same as described above. R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
In the present invention, when halogen is not directly involved in the method of introducing an alkenyl group such as (Aa) and (Ab), a living radical polymerization method is preferred as a method for synthesizing a vinyl polymer, and atom transfer A radical polymerization method is more preferable.

  In the method using a vinyl polymer having at least one highly reactive carbon-halogen bond as listed in (Ac) to (Af), at least a highly reactive carbon-halogen bond is present. As a method for synthesizing one vinyl polymer, a chain transfer polymerization method using a halide as a chain transfer agent or an atom transfer radical polymerization method using an organic halide or a sulfonyl halide as an initiator is preferable. A radical polymerization method is more preferable.

  Among the methods (Aa) to (Af), the method (Ab) is preferable because the control is easier. The method for introducing (Ab) will be described in detail below.

Diene compound addition method [(A-b) method]
In the (Ab) method, a vinyl polymer obtained by living radical polymerization of a vinyl monomer is reacted with a compound having at least two alkenyl groups having low polymerizability (hereinafter referred to as “diene compound”). It is characterized by.
At least two alkenyl groups of the diene compound may be the same or different from each other. The alkenyl group is a terminal alkenyl group [CH ₂ ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is an organic group having 1 to 20 carbon atoms, and R and R ′ May be bonded to each other to have a cyclic structure. Or an internal alkenyl group [R′—C (R) ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is an organic group having 1 to 20 carbon atoms; One R or two R ′ may be the same or different from each other. Any two of two R and two R ′ may be bonded to each other to have a cyclic structure. ], But a terminal alkenyl group is more preferable. R is hydrogen or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. The aralkyl group is preferably. Among these, as R, hydrogen or a methyl group is particularly preferable.

  Of the alkenyl groups of the diene compound, at least two alkenyl groups may be conjugated.

  Specific examples of the diene compound include isoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, etc. 5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

  A vinyl radical having an alkenyl group at the target terminal is obtained by conducting a living radical polymerization of a vinyl monomer and isolating the resulting polymer from the polymerization system and then subjecting the isolated polymer and the diene compound to a radical reaction. Although it is possible to obtain a polymer, a method of adding a diene compound to the polymerization reaction system at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer is more preferable because it is simple.

  The addition amount of the diene compound needs to be adjusted by the radical reactivity of the alkenyl group of the diene compound. When there is a large difference in the reactivity of the two alkenyl groups, the diene compound may be in an equivalent amount or a small excess amount relative to the polymerization growth terminal, but when the reactivity of the two alkenyl groups is equal or not significantly different, Since both alkenyl groups react and the polymerization ends are coupled to each other, the addition amount of the diene compound is preferably an excess amount relative to the polymer growth end, preferably 1.5 times or more, more preferably It is 3 times or more, particularly preferably 5 times or more.

Method for Converting Hydroxyl Group to Alkenyl Group The vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule is a vinyl polymer containing at least one hydroxyl group in the molecule. The methods exemplified below can be used, but are not limited thereto.

In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ag) a method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride;
(Ah) a method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate,
(Ai) a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine,
(Aj) A method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst, and the like.
(Ak) A method of reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound and reacting a compound having an alkenyl group and a hydroxyl group with the remaining isocyanate group is also mentioned.

  The compound having both an alkenyl group and a hydroxyl group is not particularly limited, and examples thereof include alkenyl alcohols such as 10-undecenol, 7-octenol, 5-hexenol and allyl alcohol.

  The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1 , 5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and the like. These can be used alone or in combination of two or more. Moreover, you may use block isocyanate.

  In order to make better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

Examples of the method for producing a vinyl polymer containing at least one hydroxyl group in the molecule used in the methods (Ag) to (Ak) for synthesizing a vinyl polymer having a hydroxyl group include the following methods. However, it is not limited to these methods.
(Ba) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (11) is used as the second monomer. How to react as.
^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -OH (11)
(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above)
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, when the obtained cured product is expected to have rubber-like properties, the polymerization reaction is performed in living radical polymerization. It is preferable to react the above compound as the second monomer at the end of the reaction or after completion of the reaction of the predetermined monomer.
(Bb) When a vinyl polymer is synthesized by living radical polymerization, for example, 10-undecenol, 7-octenol, 5-hexenol, allyl alcohol, etc. at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer A method of reacting alkenyl alcohol.
(Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide disclosed in JP-A-5-262808.
(Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.
(Be) A method of radical polymerization of a vinyl monomer using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.
(Bf) Hydrolysis of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method such as disclosed in, for example, JP-A-4-132706 To introduce a hydroxyl group into the terminal.
(Bg) A method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as listed in the general formula (12) to substitute a halogen.
M ⁺ C ⁻ (R ¹⁸ ) (R ¹⁹ ) —R ²⁰ —OH (12)
(Wherein R ¹⁸ , R ¹⁹ , R ²⁰ and M ⁺ are the same as above)
In general formula (12), as the electron withdrawing group of R ¹⁸ and R ¹⁹ , —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), -COSR (thioester group), - CN (nitrile group), - NO ₂ is (nitro group), and the _{like, -CO 2 R, -C (O} ) R and -CN are particularly preferable. Here, the substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. is there.
(Bh) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound, and then aldehydes. Or a method of reacting ketones.
(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula (13) or (14). To replace the halogen.
HO—R ²¹ —O ⁻ M ⁺ (13)
(Wherein R ²¹ and M ⁺ are the same as above)
HO—R ²² —C (O) O ⁻ M ⁺ (14)
(Wherein R ²² and M ⁺ are the same as above)
As M ⁺ , reaction conditions, solvents, etc., all described in the description of (A−f) can be preferably used.
(Bj) When synthesizing a vinyl polymer by living radical polymerization, as the second monomer after the end of the polymerization reaction or after the completion of the reaction of the predetermined monomer, an alkenyl group and a hydroxyl group having low polymerizability in one molecule A method of reacting a compound having
Although it does not specifically limit as a compound which has a low polymerizability alkenyl group and hydroxyl group in 1 molecule, The compound etc. which are shown by General formula (15) are mentioned.
^{_{H 2 C = C (R 14}} ) -R 21 -OH (15)
(Wherein R ¹⁴ and R ²¹ are the same as described above.)
Although it does not specifically limit as a compound shown by the said General formula (15), From an easy acquisition, alkenyl alcohol like 10-undecenol, 7-octenol, 5-hexenol, and allyl alcohol is preferable.

  In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a living radical polymerization method is used as a vinyl polymer synthesis method. Are preferred, and the atom transfer radical polymerization method is more preferred.

  In the method using a vinyl polymer having at least one highly reactive carbon-halogen bond as listed in (Bf) to (Bi), at least a highly reactive carbon-halogen bond is present. As a method for synthesizing one vinyl polymer, a chain transfer polymerization method using a halide as a chain transfer agent or an atom transfer radical polymerization method using an organic halide or a sulfonyl halide as an initiator is preferable. A polymerization method is more preferable.

  Among the synthesis methods (Ba) to (Bj), the methods (Bb) and (Bi) are preferable because they are easier to control.

  As mentioned above, although the manufacturing method of (A) component was demonstrated, it is preferable to obtain (A) component by the following methods especially.

One of them is
(1a) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the following general formula (1)
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
A vinyl polymer having a terminal structure represented by
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation reaction;
It is a method.

The other is
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two alkenyl groups having low polymerizability;
It is a method.
<< (B) Hydrosilyl group-containing compound (II) >>
The hydrosilyl group-containing compound (II) as the component (B) is a hydrosilyl group which can be cured by crosslinking with the vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction as the component (A). There are no particular limitations as long as it is a contained compound, and various compounds can be used, but organohydrogenpolysiloxane is preferred.

Examples of the hydrosilyl group-containing compound (II) include chain polysiloxanes represented by general formulas (16) and (17);
_{^{R 23 3 SiO- [Si (R}} 23) 2 O] a - [Si (H) (R 24) O] b - [Si (R 24) (R 25) O] c -SiR 23 3 (16)
_{^{HR 23 2 SiO- [Si (R}} 23) 2 O] a - [Si (H) (R 24) O] b - [Si (R 24) (R 25) O] c -SiR 23 2 H (17)
(Wherein, R ²³ and R ²⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ²⁵ is an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group. More R ^23, R ²⁴ and R ²⁵ may be the same or different, a is an integer satisfying 0 ≦ a ≦ 100, b is 2 ≦ b ≦ 100, and c is an integer satisfying 0 ≦ c ≦ 100.
A cyclic siloxane represented by the general formula (18);

（式中、Ｒ²⁶及びＲ²⁷は炭素数１〜６のアルキル基、又は、フェニル基、Ｒ²⁸は炭素数１〜１０のアルキル基、アリール基又はアラルキル基を示す。複数のＲ²⁶、Ｒ²⁷、Ｒ²⁸は同一でも異なっていてもよい。ｄは０≦ｄ≦８、ｅは２≦ｅ≦１０、ｆは０≦ｆ≦８の整数を表し、かつ３≦ｄ＋ｅ＋ｆ≦１０を満たす。）、
等の化合物を用いることができる。

(Wherein, R ²⁶ and R ²⁷ an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ²⁸ is an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group. More R ^26, R ²⁷ and R ²⁸ may be the same or different, d represents an integer of 0 ≦ d ≦ 8, e represents an integer of 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and satisfies 3 ≦ d + e + f ≦ 10. ),
Etc. can be used.

  These may be used alone or in combination of two or more.

Among these siloxanes, from the viewpoint of compatibility with vinyl polymers, chain siloxanes represented by the following general formulas (19) and (20) having a phenyl group, and general formulas (21) and (22) The cyclic siloxane represented is preferred.
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (19)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (CH 3) {CH 2 C (H) (R 30) C 6 H 5} O] h -Si (CH 3 ₃ (20)
(In the formula, R ³⁰ represents hydrogen or a methyl group. G represents an integer of 2 ≦ g ≦ 100 and h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group.)

（式中、Ｒ²⁹は水素、又はメチル基を示す。ｉは２≦ｉ≦１０、ｊは０≦ｊ≦８、かつ３≦ｉ＋ｊ≦１０を満たす整数を示す。Ｃ₆Ｈ₅はフェニル基を示す。）
（Ｂ）成分のヒドロシリル基含有化合物（ＩＩ）としては、さらに、分子中に２個以上のアルケニル基を有する低分子化合物に対し、一般式（１６）から（２２）で表されるヒドロシリル基含有化合物を、反応後にも一部のヒドロシリル基が残るようにして付加反応させて得られる化合物を用いることもできる。

(Wherein R ²⁹ represents hydrogen or a methyl group. I represents an integer satisfying 2 ≦ i ≦ 10, j represents 0 ≦ j ≦ 8, and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. Is shown.)
As the hydrosilyl group-containing compound (II) as the component (B), the hydrosilyl group-containing compound represented by the general formulas (16) to (22) is further used for a low molecular compound having two or more alkenyl groups in the molecule. It is also possible to use a compound obtained by subjecting a compound to an addition reaction such that a part of the hydrosilyl group remains after the reaction.

  Various compounds can be used as the low molecular compound having two or more alkenyl groups in the molecule. Illustrative examples include aliphatic hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene; , O′-diallyl bisphenol A, 3,3′-diallyl bisphenol A and other ether compounds; diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate and other ester compounds; diethylene glycol diallyl carbonate, etc. Carbonate compounds; isocyanurate compounds such as triallyl isocyanurate; aromatic hydrocarbon compounds such as divinylbenzene, divinylbiphenyl, and trivinylcyclohexane.

  A low molecular weight compound having two or more alkenyl groups in the above-listed molecule in the presence of a hydrosilylation catalyst described later with respect to the excessive amount of the hydrosilyl group-containing compound represented by the general formulas (16) to (22). Is slowly added dropwise to obtain the hydrosilyl group-containing compound (II). Among these compounds, considering the availability of raw materials, ease of removal of excessively used hydrosilyl group-containing compounds, and compatibility with the vinyl polymer (I), Preferably mentioned.

（Ｂ）成分の配合量としては特に限定されないが、硬化性の面から、（Ａ）成分中のヒドロシリル化反応可能なアルケニル基と（Ｂ）成分中のＳｉＨ（ヒドロシリル）基のモル比（（Ｂ）／（Ａ））が５〜０．２の範囲にあることが好ましく、２．５〜０．４であることが特に好ましい。モル比が５より大きいと、硬化後も硬化物中に活性なヒドロシリル基が多く残るので、クラック、ボイドが発生し、均一で強度のある硬化物が得られにくくなる傾向があり、０．２より小さいと、硬化が不十分で強度の小さい硬化物が得られ易くなる傾向がある。

The blending amount of component (B) is not particularly limited, but from the viewpoint of curability, the molar ratio of alkenyl groups capable of hydrosilylation reaction in component (A) and SiH (hydrosilyl) groups in component (B) (( B) / (A)) is preferably in the range of 5 to 0.2, particularly preferably 2.5 to 0.4. If the molar ratio is larger than 5, a large number of active hydrosilyl groups remain in the cured product even after curing, so that cracks and voids are generated, and it is difficult to obtain a uniform and strong cured product. If it is smaller, a cured product with insufficient strength and low strength tends to be obtained.

<< (C) Hydrosilylation Catalyst >>
There is no restriction | limiting in particular about the hydrosilylation catalyst which is (C) component in this invention, Arbitrary things can be used. Specific examples include hydrosilylation catalysts described in JP-A-2005-232419, page 36, paragraph [0137]. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

Although there is no restriction | limiting in particular as the usage-amount of a hydrosilylation catalyst, It is preferable to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to ¹ mol of alkenyl groups which can be hydrosilylated in (A) component. More preferably, it is the range of 10 ^<-2 > ^{-10 < -6>} mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and may generate a large amount of hydrogen gas to foam the cured product. Therefore, it is better not to use more than 10 ⁻¹ mol.

<< (D) Coal ash >>
There is no restriction | limiting in particular about the coal ash used by this invention, What remains after burning coal with a boiler in a thermal power plant etc. can be used. In particular, fly ash collected with a dust collector or clinker ash obtained by pulverizing welded coal ash collected at the bottom of the boiler is preferably used. Is particularly preferred. As the fly ash, those of I type to IV type defined in JIS A 6201 can be used. Although there is no restriction | limiting in particular as addition amount of this coal ash, Preferably it is 10-300 weight part with respect to 100 weight part of (A) component, More preferably, it is 30-200 weight part, More preferably, it is 50-150 weight part It is. When the blending amount is less than 10 parts by weight, sufficient compression set characteristics may not be obtained. When the blending amount exceeds 300 parts by weight, the workability of the curable composition may be reduced, Mechanical properties may deteriorate. The coal ash used for the improvement is generally very inexpensive, and the use of more coal ash not only improves productivity but also has a great effect from the viewpoint of economy. Moreover, the said coal ash (D) may be used independently and may be used together 2 or more types.

<< (E) Reinforcing Silica >>
The curable composition used in the present invention may further contain (E) reinforcing silica as necessary.

Examples of the reinforcing silica of component (E) include fumed silica and wet method silica. Among these, particles having a particle diameter of 50 μm or less and a specific surface area (by BET method (low temperature and low humidity physical adsorption of inert gas)) of 80 m ² / g or more are preferable from the effect of reinforcement. Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it easily exhibits fluidity suitable for molding. More specific examples of the reinforcing silica include, but are not limited to, Nippon Aerosil Co., Ltd., which is one of fumed silicas, Leoro Seal, Tokuyama Co., and Nippon Sil, Tosoh Silica Co., Ltd., which is one of wet-type silicas. , Fuji Silysia's Silicia, Silo Hobic, Tokuyama's Toxeal, Fine Seal, Degussa's Carplex, Sipernat, Mizusawa Chemical's Mizusukasil.

  Although there is no restriction | limiting in particular as addition amount of this reinforcing silica, Preferably it is 0.1-100 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.5-80 weight part, More preferably 1 to 50 parts by weight. When the blending amount is less than 0.1 parts by weight, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts by weight, the workability of the curable composition may be deteriorated. Moreover, the said reinforcing silica (E) may be used independently and may be used together 2 or more types.

<< Curable composition >>
The curable composition used in the present invention contains the components (A), (B), (C), and (D) and (E) as necessary, but adjusts the physical properties. In addition, various additives such as curing modifiers, metal soaps, fillers, fine hollow particles, plasticizers, adhesion promoters, solvents, flame retardants, antioxidants, light stabilizers, UV absorbers, Physical properties modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, photocurable resins, etc. Good. These various additives may be used alone or in combination of two or more.

<Curing modifier>
The curable composition used in the present invention may further contain a curing regulator as necessary in order to achieve both the storage stability and the curability balance.
There is no restriction | limiting in particular as a hardening regulator, Although arbitrary things can be used, It is preferable that it is a compound containing an aliphatic unsaturated bond.

  As a compound containing an aliphatic unsaturated bond, for example,

（式中、Ｒ^a、Ｒ^bは、同一又は異なって、水素原子、炭素数１〜１０のアルキル基、又は、炭素数６〜１０のアリール基を表し、両者は相互に連結していてもよい。）で示されるアセチレンアルコール類が例示される。特に、これらアセチレンアルコール類においては、Ｒ^aあるいはＲ^bのかさ高さが貯蔵安定性に大きく関与しており、Ｒ^aあるいはＲ^bがかさ高いものが高温での貯蔵安定性に優れることから好ましい。しかし、かさ高いものになりすぎると、貯蔵安定性には優れるものの、硬化性が悪くなるという欠点があり、貯蔵安定性と硬化性のバランスのとれたアセチレンアルコールを選ぶことが重要である。

(In the formula, R ^a and R ^b are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and both may be connected to each other. Acetylene alcohols represented by the following formula: In particular, in these acetylene alcohols, the bulkiness of R ^a or R ^b is greatly involved in storage stability, and those having a high R ^a or R ^b are preferred because they are excellent in storage stability at high temperatures. . However, if it becomes too bulky, the storage stability is excellent, but there is a drawback that the curability is deteriorated, and it is important to select an acetylene alcohol having a balance between the storage stability and the curability.

  Examples of acetylene alcohols having a good balance between storage stability and curability include acetylene alcohols described in JP-A-2005-232419, page 38, paragraph [0143]. Among these, 1-ethynyl-1-cyclohexanol and 3,5-dimethyl-1-hexyn-3-ol are more preferable from the viewpoint of availability.

  Examples of the compound containing an aliphatic unsaturated bond that improves storage stability at high temperatures other than acetylene alcohols include compounds described in JP 2005-232419 A, page 38, paragraph [0143] to page 39, paragraph [0152]. Can be mentioned.

The amount of the curing regulator used can be selected almost arbitrarily as long as it is uniformly dispersed in the component (A) and the component (B). It is preferably used in the range of 10,000 molar equivalents. More preferably, it is the range of 5-1000 molar equivalent. When it is less than 2 molar equivalents, the storage stability may be insufficient, and when it exceeds 10,000 molar equivalents, curing tends to be slow.
Moreover, a hardening regulator may be used independently and may use 2 or more types together.

<Metal soap>
The curable composition used in the present invention may further contain a metal soap as necessary in order to enhance mold releasability.

  There is no restriction | limiting in particular about metal soap, Arbitrary things can be used. Metal soap is generally a combination of long-chain fatty acids and metal ions, and has a nonpolar or low polarity part based on fatty acids and a polar part based on the part bound to metal in one molecule. Can be used.

  Examples of the long chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, a saturated fatty acid having 1 to 18 carbon atoms is preferable from the viewpoint of availability, and a saturated fatty acid having 6 to 18 carbon atoms is particularly preferable from the viewpoint of the releasability effect.

  Examples of the metal ions include alkali metals (lithium, sodium, potassium), alkaline earth metals (magnesium, calcium, barium), zinc, lead, cobalt, aluminum, manganese, strontium, and the like.

  If a metal soap is illustrated more concretely, the metal soap of Unexamined-Japanese-Patent No. 2005-232419 page 40 paragraph [0155] will be mentioned.

  Among these metal soaps, metal stearates are preferable from the viewpoint of availability and safety, and particularly from the viewpoint of economy, one or more selected from the group consisting of calcium stearate, magnesium stearate, and zinc stearate. Is most preferred.

  Although there is no restriction | limiting in particular as addition amount of this metal soap, It is preferable to use normally in the range of 0.025-5 weight part with respect to 100 weight part of (A) component, and 0.05-4 weight part is used. Is more preferable. If the blending amount is more than 5 parts by weight, the physical properties of the cured product tend to decrease, and if it is less than 0.025 part by weight, mold releasability tends to be difficult to obtain.

<Filler>
In the curable composition used in the present invention, various fillers may be used as needed in addition to the reinforcing silica as the component (D).

  Although it does not specifically limit as a filler, The filler of Unexamined-Japanese-Patent No. 2005-232419 page 40 paragraph [0158] is mentioned.

  Of these fillers, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

In particular, when it is desired to obtain a cured product having high strength with these fillers, mainly crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activity A filler selected from zinc oxide and the like can be added. Among them, the specific surface area (according to BET adsorption method) of 50 m ² / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface has been previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganopolysiloxane, etc. is more preferred.

  Moreover, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength and breaking elongation of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the breaking strength and breaking elongation of the cured product.

  Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved and the storage stability effect of the curable composition is further improved as compared with the case where calcium carbonate that is not surface-treated is used. I think that.

  Examples of the surface treatment agent include the surface treatment agent described in JP-A-2005-232419, page 41, paragraph [0161].

  The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability improvement effect may not be sufficient, and when it exceeds 20% by weight, the storage stability of the curable composition may be lowered.

  Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is preferably used when the effect of improving the thixotropy of the blend, the breaking strength of the cured product, the elongation at break and the like is particularly expected.

  On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, use the following as necessary. be able to.

Heavy calcium carbonate is obtained by mechanically crushing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for the pulverization method, but the wet pulverized product may reduce the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes a product having various average particle diameters by classification. Although not particularly limited, when the effect of improving the breaking strength and breaking elongation of the cured product is expected, the value of the specific surface area of heavy calcium carbonate is preferably 1.5 m ² / g to 50 m ² / g, and preferably 2 m ^2. / G or more and 50 m ² / g or less is more preferred, 2.4 m ² / g or more and 50 m ² / g or less is more preferred, and 3 m ² / g or more and 50 m ² / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply lowered or only for the purpose of increasing the viscosity.

Although not particularly limited, for example, when heavy calcium carbonate and colloidal calcium carbonate having a specific surface area value of 1.5 m ² / g or more are combined as needed, the increase in viscosity of the formulation is moderately suppressed, The effect of improving the breaking strength and breaking elongation of the cured product can be greatly expected.

  The value of the specific surface area is a value measured by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

  The said filler may be used independently according to the objective and necessity, and may use 2 or more types together. When the filler is used, it is preferable that the filler is used in the range of 5 to 1000 parts by weight with respect to 100 parts by weight of the vinyl polymer (I), and is used in the range of 20 to 500 parts by weight. It is more preferable to use in the range of 40 to 300 parts by weight. If the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts by weight, the work of the curable composition May decrease.

<Micro hollow particles>
For the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles can be added in combination with these reinforcing fillers.

Such fine hollow particles (hereinafter sometimes referred to as “balloons”) are not particularly limited, but have a diameter as described in “Latest Technology for Functional Fillers” (CMC). Examples thereof include hollow bodies (inorganic balloons and organic balloons) made of inorganic or organic materials of 1 mm or less, preferably 500 μm or less, more preferably 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and it is more preferable to use a micro hollow body having a true specific gravity of 0.5 g / cm ³ or less.

  As the inorganic balloon and the organic balloon, balloons described in JP-A-2005-232419, page 42, paragraph [0168] to page 43, paragraph [0170] can be used.

  The balloons may be used alone or in combination of two or more. Furthermore, the surface of these balloons is made of fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. to improve dispersibility and workability of the compound. Those processed in the above can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

  The addition amount of the balloon is not particularly limited, but is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). . If the amount is less than 0.1 parts by weight, the effect of reducing the weight is small. If the amount is more than 50 parts by weight, a decrease in tensile strength may be observed among the mechanical properties when the compound is cured. Moreover, when the specific gravity of a balloon is 0.1 or more, the addition amount is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

<Plasticizer>
A plasticizer can be mix | blended with the curable composition used by this invention as needed.

  Although it does not specifically limit as a plasticizer, For example, the plasticizer of Unexamined-Japanese-Patent No. 2005-232419 page 43 paragraph [0173] is mentioned by the objectives, such as adjustment of a physical property and adjustment of a property.

  Among them, a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000 is added, so that the viscosity of the curable composition and the tensile strength and elongation of the cured product obtained by curing the composition are increased. Compared with the case where a low molecular plasticizer which is a plasticizer which does not contain a polymer component in the molecule can be adjusted, the initial physical properties can be maintained over a long period of time. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the said polymeric plasticizer was described as 500-15000, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer may flow out over time due to heat or rain, and the initial physical properties may not be maintained for a long time. Moreover, when molecular weight is too high, a viscosity will become high and there exists a tendency for workability | operativity to fall.

  Among these polymer plasticizers, those compatible with the vinyl polymer (I) are preferable. Of these, vinyl polymers are preferred from the viewpoints of compatibility, weather resistance, and heat aging resistance. Among the vinyl polymers, (meth) acrylic polymers are preferable, and acrylic polymers are more preferable. Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer does not use a solvent or a chain transfer agent, and is a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-331522, USP 5010166). It is more preferable for the purpose of the present invention. Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.

  These plasticizers can also be blended at the time of polymer production.

  Although the usage-amount in the case of using a plasticizer is not limited, Preferably it is 1-100 weight part with respect to 100 weight part of vinyl-type polymer (I), More preferably, it is 5-50 weight part. If the amount is less than 1 part by weight, the effect as a plasticizer tends to be hardly exhibited, and if it exceeds 100 parts by weight, the mechanical strength of the cured product tends to be insufficient.

  In addition to the plasticizer, a reactive diluent described below may be used in the present invention.

  Examples of the reactive diluent include organic compounds having at least one alkenyl group or alkynyl group capable of undergoing hydrosilylation reaction in the molecule. This organic compound lowers the viscosity of the composition before curing, and bonds with the SiH group of the hydrosilyl group-containing compound (II) by a hydrosilylation reaction during the curing reaction, and is eventually taken into the network structure.

  Therefore, in the present invention, there is no particular limitation as long as it is an organic compound having at least one alkenyl group or alkynyl group capable of hydrosilylation reaction in the molecule, but the phase with the vinyl polymer (I) of the present invention is not limited. From the viewpoint of good solubility, a compound having a polar group such as an ester group is preferred. Further, the lower the molecular weight, the better the compatibility, but it is preferable. However, the molecular weight may be high to some extent as long as it is sufficiently compatible. In addition, from the viewpoint of heat aging resistance, weather resistance, etc., which are characteristics of the cured product obtained from the curable composition of the present invention, this reactive diluent has a carbon-carbon unsaturated bond having low activity against hydrosilylation. More preferably, it is not present.

  In addition, when using a low-boiling compound that can volatilize during curing and curing as a reactive diluent, it may cause a shape change before and after curing, or may adversely affect the environment due to volatiles. An organic compound having a boiling point at room temperature of 100 ° C. or higher is particularly preferable.

  Specific examples of the reactive diluent include 1-octene, 4-vinylcyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, 8-acetoxy-1,6-octadiene and the like. However, it is not limited to these.

  The amount of the reactive diluent added is not particularly limited as long as it does not interfere with the formation of a three-dimensional crosslinked structure by the hydrosilylation reaction between the vinyl polymer (I) and the hydrosilyl group-containing compound (II). . When the addition amount of the reactive diluent is excessive, the SiH group of the hydrosilyl group-containing compound (II) is consumed by the hydrosilylation reaction with the unsaturated group of the reactive diluent, and the vinyl polymer (I ) May cause insufficient formation of a three-dimensional crosslinked structure.

  The addition amount of the reactive diluent is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and further preferably 1 to 50 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). Part.

<Solvent>
A solvent can be mix | blended with the curable composition used by this invention as needed.

Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone A solvent etc. are mentioned. These solvents may be used during production of the polymer.
<Adhesive agent>
When the curable composition of the present invention is used alone as a molding rubber, it is not particularly necessary to add an adhesion-imparting agent. However, when it is used for two-color molding with a different base material, a vinyl-based polymer is used. It is possible to add an adhesion-imparting agent to such an extent that the crosslinking reaction between the compound (I) and the hydrosilyl group-containing compound (II) is not significantly inhibited and the physical properties of the resulting cured product are not significantly affected.
The adhesiveness imparting agent that can be blended is not particularly limited as long as it imparts adhesiveness to the curable composition, but is preferably a crosslinkable silyl group-containing compound, and more preferably a silane coupling agent.
Specific examples thereof include the adhesion-imparting agent described in JP-A-2005-232419, page 45, paragraph [0184].
In addition, in the range not inhibiting the hydrosilylation reaction, carbon atoms such as epoxy groups, isocyanate groups, isocyanurate groups, carbamate groups, amino groups, mercapto groups, carboxyl groups, halogen groups, (meth) acryl groups and the like in the molecule A silane coupling agent having both an organic group having an atom other than a hydrogen atom and a crosslinkable silyl group can be used.
Specific examples thereof include a silane coupling agent having both an organic group having an atom other than a carbon atom and a hydrogen atom described in JP-A-2005-232419, page 45, paragraph [0185] and a crosslinkable silyl group.
Among these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness.
These may be used alone or in combination of two or more.
Specific examples of the adhesion-imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.
Moreover, in order to further improve adhesiveness, a crosslinkable silyl group condensation catalyst can be used in combination with the above-mentioned adhesiveness-imparting agent. Examples of the crosslinkable silyl group condensation catalyst include those described in Japanese Patent Application Laid-Open No. 2005-232419, page 46, paragraph [0187].
The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the vinyl polymer (I). If the amount is less than 0.01 part by weight, the effect of improving the adhesiveness is small, and if it exceeds 20 parts by weight, the physical properties of the cured product tend to decrease. Preferably it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.
The adhesiveness-imparting agent may be used alone or in combination of two or more.
<< Method for producing cured product >>
The hardened | cured material obtained from the said curable composition of this invention is demonstrated below.
In the present invention, the curable composition is cured by the addition reaction of the SiH group to the alkenyl group using the hydrosilylation catalyst, so that the curing rate is very fast, which is advantageous for line production. In particular, the temperature for thermosetting is preferably in the range of 100 ° C to 180 ° C. Since the curable composition of the present invention is excellent in storage stability, the curing reaction hardly proceeds at a temperature lower than 100 ° C. However, when the temperature is about 100 ° C. or higher, the hydrosilylation reaction proceeds rapidly and takes a short time. A cured product can be obtained.
Since the curable composition of the present invention is excellent in storage stability even at a relatively high temperature, the composition can be handled with a lower viscosity and is suitable for liquid injection molding at a high temperature.
In the present invention, when the curable composition is flowed, it is preferably performed at a temperature of 20 ° C. or higher and lower than 100 ° C., but is more preferably flowed at a temperature of 40 ° C. or higher and lower than 80 ° C.
Moreover, in this invention, while making a curable composition flow at the temperature of 20 degreeC or more and less than 100 degreeC, hardening reaction can be performed, further making it flow at 20 degreeC or more. That is, the curable composition of the present invention can be used as a resin for liquid injection molding (LIM or the like).

The curable composition used in the present invention may be prepared as a one-component type in which all the ingredients are pre-blended and stored and heated by curing at the time of curing, to ensure long-term storage stability. May be prepared in the form of two liquids or three liquids or more and mixed before curing.
In the case of preparing as a two-part form, there is no particular limitation on how to divide the ingredients, but when long-term storage stability is required, (B) a hydrosilyl group-containing compound and (C) hydrosilylation The catalyst is divided, and one compounded liquid (referred to as liquid a) is blended with the vinyl polymer (I) as component (A) and the hydrosilylation catalyst as component (C), and the other compounded liquid (liquid b). It is desirable to blend the vinyl polymer (I) as the component (A) and the hydrosilyl group-containing compound as the component (B). The filler containing the coal ash (D) and the reinforcing silica (E), the curing modifier, the metal soap, the plasticizer, the anti-aging agent, etc. may be blended in either the liquid a or liquid b. In consideration of the stability of each component, it may be better to mix a curing regulator and metal soap in the liquid b. Since the workability at the time of mixing is improved, it is preferable to adjust the compounding materials of each liquid so that the liquids a and b may be mixed in an equivalent amount, and the viscosity of both liquids should be adjusted to the same level. Is more preferable.
<< Molding method >>
The molding method when the curable composition of the present invention is used as a molded body is not particularly limited, and various commonly used molding methods can be used. Examples thereof include cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, and thermoforming. In particular, an injection molding method is preferable from the viewpoint that automation and continuation are possible and productivity is excellent.

<< Usage >>
The curable composition of the present invention is not particularly limited, but it is not limited to automobile materials, electrical / electronic component materials, electrical insulation materials such as electric wire / cable insulation coating materials, coating materials, foams, electrical and electronic potting materials, It can be used for various applications such as films, gaskets, casting materials, and various molding materials.

  Furthermore, the molded body showing rubber elasticity obtained from the curable composition of the present invention can be applied to sealing materials mainly for gaskets and packings.

For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, particularly engine mount rubbers. Engine parts include hoses for cooling, fuel supply and exhaust control, gaskets for engine cam covers and oil pans, gaskets for oil pumps, gaskets for power steering vane pumps, gaskets for intake manifolds, gaskets for throttle bodies, compressors Gaskets, gaskets such as gaskets for timing belt covers, seal washers, oil receivers, plug tube seals, injection pipe seals, brake drum seals, connector seals for wire harnesses, oil level gauges, breathers, valves, diaphragms, etc. Rubber parts, fuel injection device, fuel heating device, air damper, pressure detection device, oil cooler for resin tank for heat exchanger, variable compression ratio engine, cylinder device, compression Gas regulators, pressure vessels, fuel injection systems for in-cylinder direct injection internal combustion engines or O-rings for high-pressure pumps, bottling materials for igniter HICs or hybrid ICs for automobiles, coating materials for engine control boards, moldings, heads It can be used as an adhesive for lamp lenses, sunroof seals or mirrors. It can also be used for exhaust gas cleaning device parts and brake parts.
In the electric field, it can be used for coating, potting, packing, O-rings, belts and the like. Specifically, high-voltage thick film resistors, hybrid IC circuit elements, HICs, electrical insulation components, semiconductive components, conductive components, modules, printed circuits, ceramic substrates, diodes, transistors or buffer materials for bonding wires, Semiconductive element, coating material such as optical fiber for optical communication, transformer high voltage circuit, printed circuit board, high voltage transformer with variable resistance, electrical insulation component, semiconductive component, conductive component, solar cell or TV flyback Potting materials such as transformers, heavy electrical components, weak electrical components, back sealing of solar cells, sealing materials for circuits and boards of electrical and electronic equipment, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect protection Packing, anti-vibration / sound absorption and air sealant for cleaner, drip-proof cover for electric water heater, waterproof packing Heater packing, electrode packing, safety valve diaphragm, hose for sake can, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt , Heat insulation heater packing, steam outlet seal, etc., combustion equipment oil packing, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, Rubber parts such as oil supply pipes, diaphragm valves, air supply pipes, speaker gaskets for audio equipment, speaker edges, turntable seats, belts, pulleys, and the like. Also used for cathode ray tube wedges, necks, electrical insulation parts, adhesives for semiconductive parts or conductive parts, wire covering repair materials, insulation joints for wire joint parts, rolls for OA equipment, vibration absorbers, gels, etc. it can.

  In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like.

  In the sports field, it can be used for all-weather pavement materials and gymnasium floors as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls as ball for ball games.

  In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

  In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Measurement of molecular weight distribution)
The number average molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko) and chloroform as a GPC solvent were used.
(Synthesis Example 1)
N-butyl acrylate 16.3 parts, ethyl acrylate 3.3 parts, 2-methoxyethyl acrylate 0.42 parts, copper (I) bromide 0.88 parts, acetonitrile 8.7 parts under nitrogen stream 1.8 parts of diethyl 2,5-dibromoadipate were charged and stirred at 80 ° C. To this was added 0.018 part of pentamethyldiethylenetriamine (hereinafter referred to as triamine) to initiate the reaction. On the way, a mixture of 65 parts of n-butyl acrylate, 13 parts of ethyl acrylate, 1.7 parts of 2-methoxyethyl acrylate was intermittently added, and the temperature of the reaction solution was increased from 80 ° C. while adding triamine as appropriate. Heating and stirring were continued to reach 90 ° C. After the reaction rate of butyl acrylate reached 95%, the inside of the reaction vessel was depressurized to remove volatile components.

  To this, 34.9 parts of acetonitrile and 22.5 parts of 1,7-octadiene were added, triamine was further added, and the mixture was heated and stirred at 80 ° C. Thereafter, the pressure inside the reaction vessel was reduced to remove volatile components.

This was diluted with toluene, synthetic hydrotalcite, aluminum silicate and filter aid were added, and the mixture was heated and stirred in an oxygen / nitrogen mixed gas atmosphere. After removing solids, the solution was concentrated. Synthetic hydrotalcite and aluminum silicate were added, and the mixture was heated and stirred under reduced pressure. This was diluted with toluene, and further synthetic hydrotalcite and aluminum silicate were added and heated and stirred. After removing the solid content, the solution was concentrated to obtain an alkenyl-terminated copolymer [P1].
The number average molecular weight of the alkenyl-terminated copolymer [P1] is 25000, the molecular weight distribution is 1.3, the number of average alkenyl groups introduced into one molecule of the polymer is analyzed by concentration analysis by ¹ H-NMR analysis, and by GPC The number average molecular weight calculated was 1.8.
(Synthesis Example 2)
In Synthesis Example 1,
N-butyl acrylate total 27.7 parts ethyl acrylate total 39.8 parts 2-methoxyethyl acrylate total 32.6 parts copper (I) bromide 0.93 parts acetonitrile total 33.4 parts 1,7-octadiene An alkenyl-terminated copolymer [P2] was obtained in the same manner as in Synthesis Example 1 except that 23.8 parts were used.
The number average molecular weight of the alkenyl-terminated copolymer [P2] is 24,000, the molecular weight distribution is 1.2, the number of average alkenyl groups introduced into one molecule of the polymer is analyzed by concentration analysis by ¹ H-NMR analysis, and by GPC The number average molecular weight calculated was 2.0.

(Synthesis Example 3)
Into a 5 L two-necked flask, 1200 g of toluene and 760 g of trimethylsilyl group-terminated polymethylhydrosiloxane having an average molecular weight of 760 (containing 10 SiH groups on average in one molecule) are placed, heated and stirred under nitrogen in an 80 ° C. oil bath did. To this solution, a mixed solution of 710 g of α-methylstyrene, 700 g of toluene and 144 μl of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 60 minutes. The resulting solution was heated and stirred as it was for 6 hours. Unreacted α-methylstyrene and toluene were distilled off under reduced pressure to obtain a hydrosilyl group-containing compound [B1].
^{From the 1} H-NMR analysis, it was found that the hydrosilyl group-containing compound [B1] was a linear methylpolysiloxane containing an average of 5 hydrosilyl groups and an average of 5 α-methylphenethyl groups in the molecule ( The hydrosilyl group-containing compound [B1] is a mixture, but contains a linear methylpolysiloxane containing an average of 5 hydrosilyl groups and an average of 5 α-methylphenethyl groups in one molecule.

(Synthesis Example 4)
1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 5 L two-necked flask, and the mixture was heated and stirred under nitrogen in an oil bath at 120 ° C. To this solution, a mixed liquid of 200 g of triallyl isocyanurate, 200 g of toluene and 144 μl of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours. After adding 2.95 mg of 1-ethynyl-1-cyclohexanol, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a hydrosilyl group-containing compound [B2]. .
^{From 1} H-NMR analysis, it was found that the hydrosilyl group-containing compound [B2] was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate. (The hydrosilyl group-containing compound [B2] is a mixture, but contains the following compound having 9 SiH groups in one molecule as a main component).

（実施例１）
合成例１で得られた共重合体［Ｐ１］１００部に、石炭灰としてフライアッシュＪＩＳＩ種（商品名：ファイナッシュＩ種、四電ビジネス製）１００部、酸化防止剤として、４，４’−ビス（α，α−ジメチルベンジル）ジフェニルアミン（商品名：ナウガード４４５、白石カルシウム製）を２部配合し、プラネタリーミキサーを用いて充分混合した。その後、アルケニル末端共重合体［Ｐ１］に対して、ヒドロシリル基含有化合物〔Ｂ１〕を、［Ｂ１］のＳｉＨ基がアルケニル末端共重合体［Ｐ１］のアルケニル基の２．２モル当量分となる量を添加し、０価白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体のイソプロパノール溶液（白金として３ｗｔ％含有）を白金換算でアルケニル末端共重合体［Ｐ１］のアルケニル基の５×１０^-4モル当量添加し、硬化調整剤として３，５−ジメチル−１−へキシン−３−オール（商品名：サーフィノール６１、日信化学製）を、白金触媒に対し１５０モル当量添加し、更に均一に混合し硬化性組成物を得た。
得られた硬化性組成物を１８０℃で１０分間プレス成形し、ＪＩＳ Ｋ ６２６２に準じて圧縮永久ひずみ試験測定用大型試験片を作製した。得られた試験片群を二つに分け、一方には１８０℃２２時間の二次加硫を行い、他方は二次加硫を行なわずに二種類の試験片を調製した。得られた二種類の試験片を、ＪＩＳ Ｋ ６２６２に準じて１５０℃で７０時間の圧縮永久ひずみ試験を行なった。結果を表１に示す。
（実施例２）
ヒドロシリル基含有化合物（ＩＩ）として、ヒドロシリル基含有化合物〔Ｂ１〕の代わりに合成例４で得られたヒドロシリル基含有化合物〔Ｂ２〕を２．２モル当量用いた以外は実施例１と同様にして硬化性組成物を得た後、二次加硫ありなしの二種類の試験片を作製し、圧縮永久ひずみ試験を行なった。結果を表１に示す。

(Example 1)
100 parts of the copolymer [P1] obtained in Synthesis Example 1 is mixed with 100 parts of fly ash JISI type (trade name: Finalash I type, manufactured by Yoden Business) as coal ash, and 4,4 ′ as an antioxidant. -Two parts of bis (α, α-dimethylbenzyl) diphenylamine (trade name: Naugard 445, manufactured by Shiraishi Calcium) were blended and mixed thoroughly using a planetary mixer. Thereafter, with respect to the alkenyl-terminated copolymer [P1], the hydrosilyl group-containing compound [B1] is such that the SiH group of [B1] is 2.2 molar equivalents of the alkenyl group of the alkenyl-terminated copolymer [P1]. An alkenyl-terminated copolymer [P1] with an isopropanol solution (containing 3 wt% as platinum) of a 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum in terms of platinum 5 × 10 ⁻⁴ molar equivalent of the alkenyl group of 3,5-dimethyl-1-hexyn-3-ol (trade name: Surfynol 61, manufactured by Nissin Chemical) as a platinum catalyst 150 mol equivalent was added, and it mixed further uniformly, and obtained the curable composition.
The obtained curable composition was press-molded at 180 ° C. for 10 minutes to prepare a large test piece for compression set test measurement according to JIS K 6262. The obtained test piece group was divided into two, one was subjected to secondary vulcanization at 180 ° C. for 22 hours, and the other was prepared two types of test pieces without performing secondary vulcanization. The two types of obtained test pieces were subjected to a compression set test at 150 ° C. for 70 hours in accordance with JIS K 6262. The results are shown in Table 1.
(Example 2)
As hydrosilyl group-containing compound (II), in the same manner as in Example 1, except that 2.2 mol equivalent of hydrosilyl group-containing compound [B2] obtained in Synthesis Example 4 was used instead of hydrosilyl group-containing compound [B1]. After obtaining the curable composition, two types of test pieces with and without secondary vulcanization were prepared and subjected to a compression set test. The results are shown in Table 1.

(Example 3)
As hydrosilyl group-containing compound (II), in the same manner as in Example 1, except that 1.8 mol equivalent of hydrosilyl group-containing compound [B2] obtained in Synthesis Example 4 was used instead of hydrosilyl group-containing compound [B1]. After obtaining the curable composition, two types of test pieces with and without secondary vulcanization were prepared and subjected to a compression set test. The results are shown in Table 1.

Example 4
A curable composition was obtained in the same manner as in Example 1 except that fly ash type II (trade name: fly ash type II, manufactured by Kanden Powertech Co., Ltd.) was used as coal ash. Various types of test pieces were prepared and subjected to a compression set test. The results are shown in Table 1.

(Example 5)
Curability as in Example 1 except that 100 parts of the alkenyl-terminated copolymer [P2] obtained in Synthesis Example 2 was used as the vinyl polymer (I) instead of the alkenyl-terminated copolymer [P1]. After obtaining the composition, two types of test pieces with and without secondary vulcanization were prepared and subjected to a compression set test. The results are shown in Table 1.

(Comparative Example 1)
Example 1 was used except that 30 parts of silica (trade name: Nipseal LP, manufactured by Tosoh Silica) was used instead of coal ash, and 1.8 molar equivalents of the hydrosilyl group-containing compound [B2] was used. Then, after obtaining a curable composition, two types of test pieces with and without secondary vulcanization were prepared and subjected to a compression set test. The results are shown in Table 1.

(Comparative Example 2)
There was secondary vulcanization after obtaining a curable composition in the same manner as in Example 2 except that 30 parts of silica (trade name: Nipseal LP, manufactured by Tosoh Silica) was used as a filler instead of coal ash. Two types of test pieces without the above were prepared and subjected to a compression set test. The results are shown in Table 1.

(Comparative Example 3)
Example except that 30 parts of silica (trade name: Nipseal LP, manufactured by Tosoh Silica) and 70 parts of soft silica (trade name: IMSIL A-25, manufactured by Tatsumori) were used as fillers instead of coal ash After obtaining the curable composition in the same manner as in No. 2, two types of test pieces with and without secondary vulcanization were prepared and subjected to a compression set test. The results are shown in Table 1.

(Comparative Example 4)
A curable composition was obtained in the same manner as in Example 2 except that 100 parts of kaolin clay (trade name: ASP-170, manufactured by Tsuchiya Kaolin Kogyo) was used as a filler instead of coal ash. Two kinds of test pieces with and without sulfur were prepared and subjected to a compression set test. The results are shown in Table 1.

(Comparative Example 5)
After obtaining a curable composition in the same manner as in Example 2 except that 100 parts of calcium carbonate (trade name: white gloss CCR, manufactured by Shiroishi Kogyo Co., Ltd.) was used as a filler instead of coal ash, a secondary additive was obtained. Two kinds of test pieces with and without sulfur were prepared and subjected to a compression set test. The results are shown in Table 1.

表１の結果から、充填剤として石炭灰を用いた場合、二次加硫を行なわなくとも充分な圧縮永久ひずみを示すことが明らかである。

From the results in Table 1, it is clear that when coal ash is used as the filler, sufficient compression set is exhibited even without secondary vulcanization.

The curable composition of the present invention is a curable composition containing a vinyl polymer that gives a cured product exhibiting good mechanical properties, oil resistance, heat resistance, etc., and can be cured by a hydrosilylation reaction. It has the property that vulcanization can be omitted.

Claims (19)

(A) a vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule;
(B) Hydrosilyl group-containing compound (II),
(C) a hydrosilylation catalyst, and
(D) A curable composition containing coal ash. The curable composition of Claim 1 whose molecular weight distribution of the said vinyl polymer (I) is less than 1.8. The main chain of the vinyl polymer (I) is at least one selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. The curable composition according to claim 1 or 2, which is produced mainly by polymerization. The curable composition according to any one of claims 1 to 3, wherein the vinyl polymer (I) is a (meth) acrylic polymer. The curable composition according to any one of claims 1 to 4, wherein the vinyl polymer (I) is an acrylic polymer. The curable composition according to any one of claims 1 to 5, wherein the vinyl polymer (I) is an acrylate polymer. The vinyl polymer (I) is at least one selected from the group consisting of ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, 2-methoxybutyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate. The curable composition according to any one of claims 1 to 6, wherein the curable composition is produced by mainly polymerizing the saponification. The curable composition according to any one of claims 1 to 7, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. The curable composition according to claim 8, wherein the living radical polymerization is atom transfer radical polymerization. The atom transfer radical polymerization is performed using a complex selected from the group consisting of transition metal complexes having a central metal of Group 7, 8, 9, 10, or 11 of the periodic table as a catalyst. The curable composition according to claim 9, wherein The curable composition according to claim 10, wherein the transition metal complex is selected from the group consisting of complexes having copper, nickel, ruthenium or iron as a central metal. The curable composition according to claim 11, wherein the transition metal complex is a copper complex. The vinyl polymer (I) has the following steps:
(1a) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the general formula (1)
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
A vinyl polymer having a terminal structure represented by
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation reaction;
The curable composition as described in any one of Claims 1-12 obtained by these. The vinyl polymer (I) has the following steps:
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two alkenyl groups having low polymerizability;
The curable composition as described in any one of Claims 1-12 obtained by these. The curable composition according to any one of claims 1 to 14, wherein the vinyl polymer (I) has an alkenyl group capable of hydrosilylation reaction at its terminal. The curable composition according to any one of claims 1 to 15, wherein the (B) hydrosilyl group-containing compound (II) is an organohydrogenpolysiloxane. The curable composition according to any one of claims 1 to 16, wherein the (D) coal ash is fly ash. (E) The curable composition according to any one of claims 1 to 17, further comprising reinforcing silica. Hardened | cured material obtained from the curable composition as described in any one of Claims 1-18.