JP4455900B2 - Curable composition with improved compatibility with curing agent - Google Patents

Description

The present invention relates to a curable composition having improved compatibility. More specifically, molding curable resins having improved compatibility between an alkenyl group-containing vinyl polymer and a hydrosilyl group-containing compound, comprising an alkenyl group-containing vinyl polymer, a hydrosilyl group-containing compound, and a hydrosilylation catalyst as essential components. Relates to the composition.

A molded body mainly composed of a vinyl polymer or a (meth) acrylic polymer can be obtained by kneading and molding a high molecular weight polymer together with various additives in a heated state using a roll or a mill. . A molded product of acrylic rubber containing a (meth) acrylic polymer as a main component can be obtained by kneading a compound such as a filler and a vulcanizing agent into an unvulcanized rubber, followed by heat vulcanization molding. There are problems with workability such as adhesion to the roll during kneading and difficulty in smoothing during sheeting, poor workability such as non-flowability during molding, and curing such as low vulcanization speed but easy scorch. There is also a problem with inferiority (see Non-Patent Document 1, for example).

In order to solve these problems, if a (meth) acrylic polymer having a highly reactive functional group at the molecular end can be obtained by a simple method, a crosslinkable group in the side chain as in the case of conventional acrylic rubber. It is possible to reduce the molecular weight of the main chain itself, because it is possible to obtain a cured product having excellent cured product properties, as well as to effectively obtain the molecular weight between cross-linking points, A curable composition having excellent fluidity can be obtained. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially.
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 has been disclosed (for example, see Patent Document 1). Since it is not easy to introduce the copolymer and the resulting copolymer is a latex, it is necessary to remove moisture when used for moldings. In addition, a (meth) acrylic polymer having hydroxyl groups at both ends was synthesized using disulfides having hydroxyl groups, and (meth) acrylic having alkenyl groups at both ends using the reactivity of hydroxyl groups. Although a method for synthesizing a polymer is disclosed (for example, see Patent Document 2), it is not easy to reliably introduce an alkenyl group at both ends even by this method. There are issues such as the need for time post-cure.

In order to solve these problems, a curable composition containing a vinyl polymer containing an alkenyl group at a terminal and a hydrosilyl group-containing compound and capable of being cured by a hydrosilylation reaction is disclosed (for example, Patent Documents). 3 and 4). Examples of the hydrosilyl group-containing compound used in such a curable composition include a chain polysiloxane having a hydrosilyl group or a cyclic siloxane, and among them, a phenyl group has a phenyl group from the viewpoint of compatibility with a vinyl polymer. It has been proposed that chain siloxanes are preferred. Also exemplified are compounds obtained by adding a hydrosilyl group-containing compound to a low molecular weight compound having two or more alkenyl groups in the molecule so that a part of the hydrosilyl group remains after the reaction. Low molecular weight compounds having two or more alkenyl groups in the molecule are considered hydrocarbons in consideration of the availability of siloxane, ease of removal of excess siloxane, and compatibility with vinyl polymers. As the hydrosilyl group-containing compound, a cyclic siloxane compound is mentioned as a preferred compound, such as a series compound, O, O′-diallyl bisphenol A, diallyl isophthalate, and diethylene glycol diallyl carbonate.

However, even when such a hydrosilyl group-containing compound is used, the compatibility with the vinyl polymer is insufficient, and when a vinyl polymer obtained by polymerizing a highly polar monomer is used, or a hydrosilyl group-containing compound When a large amount of is used, there are problems such as turbidity in the curable composition and separation of the hydrosilyl group-containing compound during storage of the curable composition.

Japanese Patent Laid-Open No. 5-255415 JP-A-5-262808 JP-A-9-272714 JP 2000-154255 A Journal of the Japan Rubber Association, Vol. 73, No. 10, 555 (2000)

An object of the present invention is to provide 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, weather resistance and the like. An object of the present invention is to provide a curable composition having excellent compatibility between a vinyl polymer and a hydrosilyl group-containing compound.

In the present invention, as a result of intensive studies in view of the above-described present situation, as a hydrosilyl group-containing compound, the following general formula (1)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by hydrosilylation reaction, and at least two SiH in one molecule. A hydrosilyl group-containing compound (II) characterized by having a group, and / or the following general formula (2)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by a hydrosilylation reaction, and at least two SiH in one molecule. A hydrosilyl group-containing compound (III) characterized by having a group;
The present inventors have found that the above-mentioned problems can be solved by using.

That is, the present invention comprises the following three components:
(A) a vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule;
(B) The following general formula (1)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by hydrosilylation reaction, and at least two SiH in one molecule. A hydrosilyl group-containing compound (II) characterized by having a group, and / or the following general formula (2)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by a hydrosilylation reaction, and at least two SiH in one molecule. A hydrosilyl group-containing compound (III) characterized by having a group;
(C) a hydrosilylation catalyst,
The present invention relates to a curable composition comprising as an essential component.

The curable composition of this invention is explained in full detail below.
<< Vinyl polymer (I) >>
<Main chain>
It does not specifically limit as a vinyl-type monomer which comprises the principal chain of vinyl-type polymer (I) of this invention, Various things 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.

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, preferably 70 mol% or more of the monomer units constituting the vinyl polymer (I) are the above monomers.

Of these, aromatic vinyl monomers and (meth) acrylic acid monomers are preferred from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferable monomers are preferably contained in a weight ratio of 40% by weight. .
In the above expression format, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

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, 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 Yes, most preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is usually 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) in the present invention can be obtained by various polymerization methods, and the method is not particularly limited, but the radical polymerization method is preferable from the viewpoint of versatility of the monomer and ease of control. Among radical polymerizations, controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable.
The alkenyl group can be introduced by directly introducing an alkenyl group in the polymerization reaction system, or by synthesizing a vinyl polymer having a specific functional group, and then reacting the specific functional group in one step or several steps. The method etc. which convert into an alkenyl group are mentioned.
These synthesis methods are described in detail below.

Radical polymerization Synthetic methods of vinyl polymers having functional groups by radical polymerization can be classified into "general radical polymerization" and "controlled radical polymerization".
The “general radical polymerization method” is a vinyl monomer having a specific functional group (hereinafter referred to as “functional monomer”) using a polymerization initiator such as an azo compound or a peroxide and another vinyl type. 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 a functional monomer, and conversely, if a small amount is used, the proportion of the polymer in which this specific functional group is not introduced increases. is there. Moreover, 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 into the polymer terminal relatively quantitatively 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 using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl group-terminated polymer 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 definition in the present invention is also 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 in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943; (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” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a 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 of 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 polymerizations is used, but an atom transfer radical polymerization method is preferred.

Below, living radical polymerization is demonstrated.
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. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical, 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the like. Nitroxy free radicals from cyclic hydroxyamines are preferred. 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.

When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above formula, 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.

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

Atom transfer radical polymerization Next, an atom transfer radical polymerization method more preferable as the living radical polymerization in the present invention will be described.
In this 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 halogenated compound. A sulfonyl compound or the like is 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 6 -C (H) (X}} ) -CO 2 R 7, R 6 -C (CH 3) (X) -CO 2 R 7, R 6 -C (H) (X), - C (O) R ⁷ , R ⁶ -C (CH ₃ ) (X) -C (O) R ⁷ ,
(Wherein R ⁶ and R ⁷ 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 6 -C 6 H 4 -SO 2}} X
(In the above formulas, R ⁶ 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 compound as an initiator, a vinyl polymer having a terminal structure represented by the general formula (3) is obtained.
^{-C (R 2) (R 3} ) (X) (3)
(In the formula, R ² and R ³ represent a group bonded to the ethylenically unsaturated group of the vinyl monomer described above. X represents chlorine, bromine or iodine.)

As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a specific functional group that does not initiate polymerization together with a functional group that initiates polymerization can also 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 (3) 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, For example, what has a structure shown in General formula (5) is illustrated.
^{R 9 R 10 C (X)} -R 11 -R 12 -C (R 8) = CH 2 (5)
(Wherein R ⁸ is hydrogen or a methyl group, R ⁹ and R ¹⁰ 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 11} is, -C (O) O- (ester group), - C (O) - ( keto group), or o-, m-, p-phenylene ^{group, R 12} 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 ⁹ and R ¹⁰ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁹ and R ¹⁰ 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 (5) 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,

(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,

(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)
_{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 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 (6).
_{^{H 2 C = C (R 8}} ) -R 12 -C (R 9) (X) -R 13 -R 10 (6)
(Wherein R ⁸ , R ⁹ , R ¹⁰ , R ¹² and X are the same as above, R ¹³ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or represents an o-, m-, p-phenylene group)

R ¹² is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), but in the case of a direct bond, carbon to which halogen is bonded. Is a halogenated allylic compound. 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 ¹³ , and a direct bond may be used. In the case where R ¹² is not a direct bond, R ¹³ 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 (6) is illustrated specifically,
_{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 each of 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 said organic halide which has a crosslinkable silyl group, For example, what has a structure shown to General formula (7) is illustrated.
^{R 9 R 10 C (X)} -R 11 -R 12 -C (H) (R 8) CH 2 - [Si (R 14) 2-b (Y) b O] m -Si (R 15) 3- _a (Y) _a (7)
(In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and X are the same as above, and R ¹⁴ and R ¹⁵ 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). An organosiloxy group, when two or more R ¹⁴ or R ¹⁵ 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 represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer from 0 to 19. (Provided that a + mb ≧ 1)

If the compound of the general formula (7) is specifically exemplified,
_{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 1-20, m is an integer of 0-20)
_{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 each of the above formulas, X is chlorine, bromine, or iodine)
Etc.

Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula (8).
_{^{(R 15) 3-a (}} Y) a Si- [OSi (R 14) 2-b (Y) b] m -CH 2 -C (H) (R 8) -R 12 -C (R 9) ( X) -R < ¹³ > -R < ¹⁰ > (8)
(Wherein R ⁸ , R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , 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, (CH 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 each of 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.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{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)

The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{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)
The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

(In each of 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,

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. Further preferred are complexes having zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel as the central metal. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity 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. Furthermore, 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 not limited, the polymerization can be performed in the range of 0 to 200 ° C, and preferably in the range of room temperature to 150 ° C.

<Alkenyl group capable of hydrosilylation reaction>
Alkenyl group The alkenyl group capable of hydrosilylation reaction contained in the vinyl polymer (I) in the present invention is not limited, but is preferably one represented by the general formula (9).
H ₂ C═C (R ¹⁶ ) − (9)
(In the formula, R ¹⁶ represents hydrogen or an organic group having 1 to 20 carbon atoms.)

In the general formula (9), R ¹⁶ 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 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, hydrogen or a methyl group is more preferable as R ¹⁶ from the viewpoint of the activity of the hydrosilylation reaction.

Further, although not limited, it is preferable that the alkenyl group 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.
The bond form of the alkenyl group and the main chain of the vinyl polymer (I) is not particularly limited, but is bonded through a carbon-carbon bond, an ester bond, an ether bond, a carbonate bond, an amide bond, a urethane bond, or the like. It is preferable.

Position of alkenyl group When the rubber property is particularly required for the cured product of the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. Preferably at least one of is at the end of the molecular chain. More preferably, it has all alkenyl groups at the molecular chain ends.

A method for producing a vinyl polymer having at least one alkenyl group at the molecular end, in particular a (meth) acrylic polymer, is disclosed in JP-B-3-14068, JP-B-4-55444, No. 211922 and the like. However, since these methods are free radical polymerization methods using the “chain transfer agent method”, the resulting polymer has a relatively high proportion of alkenyl groups at the molecular chain ends, while Mw / Mn The expressed molecular weight distribution value 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 a high proportion of alkenyl groups at the molecular chain ends, the above “living radical polymerization method” should be used. preferable.

<Alkenyl group introduction method>
The method for introducing an alkenyl group into a vinyl polymer will be described below, but is not limited thereto.

Method of introducing alkenyl group (Aa) When synthesizing a vinyl polymer by radical polymerization, preferably living radical polymerization, for example, polymerizable alkenyl in one molecule as shown in the following general formula (10) A method in which a compound having both a group and a low polymerizable alkenyl group is reacted as the second monomer.
_{^{H 2 C = C (R 17}} ) -R 18 -R 19 -C (R 20) = CH 2 (10)
(In the formula, R ¹⁷ represents hydrogen or a methyl group, R ¹⁸ represents —C (O) O—, or o-, m-, p-phenylene group, R ¹⁹ represents a direct bond, 20 represents a divalent organic group having ^{20 and} may contain one or more ether bonds. R ²⁰ represents hydrogen or an organic group having 1 to 20 carbon atoms)

In the general formula (10), R ²⁰ is hydrogen or an organic group having 1 to 20 carbon atoms. The organic group having 1 to 20 carbon atoms is not particularly limited, but an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are preferable. 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)
Of these, R ²⁰ 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. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.

(Ab) When synthesizing a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability such as

(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 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 (11). .
^{M + C - (R 21)} (R 22) -R 23 -C (R 20) = CH 2 (11)
^{(Wherein, R 20} is the same ^{.R 21, R 22} 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 ²³ 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 ²¹ and R ²² , —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. 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. .

(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 (12) or (13), for example, on a vinyl polymer having at least one highly reactive carbon-halogen bond To replace halogens.
_{^{H 2 C = C (R 20}} ) -R 24 -O - M + (12)
(In the formula, R ²⁰ and M ⁺ are the same as above. R ²⁴ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
_{^{H 2 C = C (R 20}} ) -R 25 -C (O) O - M + (13)
(In the formula, R ²⁰ and M ⁺ are the same as above. R ²⁵ 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 a 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]
The method (Ab) is characterized by reacting a vinyl polymer obtained by living radical polymerization of a vinyl monomer with a compound having at least two alkenyl groups having low polymerizability (hereinafter referred to as a diene compound). To do.

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 7 carbon atoms. Twenty aralkyl groups are preferred. 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 of the 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 3 times Above, especially preferably 5 times or more.

Method for converting hydroxyl group to alkenyl group A vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below are used. Yes, but you are not limited to these.
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, hexamethyl 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 use of 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 having at least one hydroxyl group used in the methods (Ag) to (Ak) for synthesizing a vinyl polymer having a hydroxyl group include the following methods. 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 (14) is used as the second monomer. How to react as.
_{^{H 2 C = C (R 17}} ) -R 18 -R 19 -OH (14)
(Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ are the same as above)
There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second 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 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 shown in the general formula (15) to substitute a halogen.
^{M + C - (R 21)} (R 22) -R 23 -OH (15)
(Wherein R ²¹ , R ²² and R ²³ are the same as above)
As the electron withdrawing group for R ²¹ and R ²² , —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. 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. .

(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 (16) or (17). To replace the halogen.
^{HO-R 24 -O - M +} (16)
(Wherein R ²⁴ and M ⁺ are the same as above)
^{HO-R 25 -C (O)} O - M + (17)
(Wherein R ²⁵ 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 such a compound, The compound etc. which are shown by General formula (18) are mentioned.
_{^{H 2 C = C (R 17}} ) -R 24 -OH (18)
(In the formula, R ¹⁷ and R ²⁴ are the same as those described above.)
The compound represented by the general formula (18) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 7-octenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

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-based 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. Legal is more preferred.
Among the synthesis methods (Ba) to (Bj), the methods (Bb) and (Bi) are preferred 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
(1) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the following general formula (3)
^{-C (R 2) (R 3} ) (X) (3)
(In the formula, R ² and R ³ 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
(2) 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
(1) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2) Subsequently, this is reacted with a compound having at least two alkenyl groups having low polymerizability.
It is a method.

<< Hydrosilyl group-containing compound (II), (III) >>
As the hydrosilyl group-containing compound of component (B), the following general formula (1)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by hydrosilylation reaction, and at least two SiH in one molecule. A hydrosilyl group-containing compound (II) characterized by having a group, and / or the following general formula (2)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by a hydrosilylation reaction, and at least two SiH in one molecule. Any hydrosilyl group-containing compound (III) characterized by having a group can be used without particular limitation.

<(Α1) component>
The component (α1) is represented by the following general formula (1)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same). Any organic compound can be used without particular limitation.
As R ^{1 in the} general formula (1), at least one R ¹ is represented by the following general formula (4) from the viewpoint of easy availability and compatibility with the vinyl polymer (I).

(In the formula, R ⁴ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁵ represents a hydrogen atom or a methyl group. When a plurality of R ⁴ and R ⁵ are present, they are different from each other. Are preferably the same, and more preferably a monovalent organic group having 1 to 20 carbon atoms; a monovalent organic group having 1 to 10 carbon atoms; More preferably, it is particularly preferably a monovalent organic group having 1 to 4 carbon atoms.
Examples of these preferable R ¹ are vinyl group, allyl group,

Etc.
From the viewpoint of improving the reactivity with the (β1) component, at least two of the three R ¹ are ones having 1 to 20 carbon atoms including one or more groups represented by H ₂ C═CH—. A valent organic group is preferred.
Furthermore, it is preferable that at least two of the three R ¹ are allyl groups.

Preferred specific examples of the organic compound represented by the general formula (1) as described above include triallyl isocyanurate,

Etc. Among these, triallyl isocyanurate is preferable from the viewpoint of availability. The organic compound represented by the general formula (1) can be used alone or in combination of two or more.

<(Β1) component>
The polyorganosiloxane having at least two SiH groups in one molecule, which is the (β1) component of the present invention, is not particularly limited, and is represented by, for example, the general formula (19) or (20) Chain polysiloxane;
^{_{R 26 3 SiO- [Si (R}} 26) 2 O] a - [Si (H) (R 27) O] b - [Si (R 27) (R 28) O] c -SiR 26 3 (19)
^{_{HR 26 2 SiO- [Si (R}} 26) 2 O] a - [Si (H) (R 27) O] b - [Si (R 27) (R 28) O] c -SiR 26 2 H (20)
(In the formula, R ²⁶ and R ²⁷ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ²⁸ represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. A is 0 ≦ a ≦. 100 and b are integers satisfying 2 ≦ b ≦ 100 and c is an integer satisfying 0 ≦ c ≦ 100, and a plurality of R ²⁶ , R ²⁷ and R ²⁸ may be the same or different.
A cyclic siloxane represented by the general formula (21);

(Wherein R ²⁹ and R ³⁰ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group. D represents 0 ≦ d ≦ 8, e represents an integer of 2 ≦ e ≦ 10, and f represents an integer of 0 ≦ f ≦ 8, and satisfies 3 ≦ d + e + f ≦ 10, and a plurality of R ²⁹ , R ³⁰ , and R ³¹ may be the same or different. .)
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 the (α1) component and reactivity, chain siloxanes represented by the following general formulas (22), (23), and (24), and general formulas (25), ( The cyclic siloxane represented by 26) and (27) is preferred.
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g -Si (CH 3) 3 (22)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (23)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (CH 3) {CH 2 C (H) (R 32) C 6 H 5} O] h -Si (CH 3 ₃ (24)
(In the formula, R ³² 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.)

(In the formula, R ³² 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.)
Among these siloxanes, 1,3,5,7-tetramethylcyclotetrasiloxane is more preferable from the viewpoint of availability.
Various (β1) components as described above can be used alone or in admixture of two or more.

<Reaction of (α1) component and (β1) component>
As the catalyst for the hydrosilylation reaction between the (α1) component and the (β1) component, the following can be used. Specifically, chloroplatinic acid; platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; platinum-vinylsiloxane complex {eg, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) n, Pt [(MeViSiO) ₄ ] _m }; platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ } (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer); chloroplatinic acid And a complex of alcohol, aldehyde, ketone, etc .; platinum-olefin complex (for example, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); Pt (acac) ₂ (wherein acac represents acetylacetonate); dicarbonyldichloroplatinum; Karlstedt catalyst; platinum described in U.S. Pat. -Hydrocarbon complexes; platinum alcohol catalysts described in US Pat. No. 3,220,972 to Lamoreaux et al. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl _{4 and the} like.
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 catalyst, In order to have sufficient reactivity and to keep the cost of a curable composition comparatively low, it is 10 < ^- > with respect to 1 mol of SiH groups of ((beta) 1) component. The range of ¹ to 10 ⁻⁸ mol is preferable, and the range of 10 ⁻³ to 10 ⁻⁷ mol is more preferable.

The hydrosilylation reaction of the (α1) component and the (β1) component is performed while slowly adding the (α1) component to the excess amount of the (β1) component in the presence of a hydrosilylation catalyst. A hydrosilyl group-containing compound (II) having at least two SiH groups in one molecule is obtained by removing excess (β1) component from the reaction system after the hydrosilylation reaction. Can do.
The mixing ratio of the (α1) component and the (β1) component used in the reaction is not particularly limited, but in consideration of the physical properties of the cured product obtained by hydrosilylation of the obtained (II) component and the vinyl polymer (I) component Since it is preferable that the component (II) has a large amount of SiH groups, an excess amount of the component (β1) is used. In general, the ratio of the number of alkenyl groups capable of hydrosilylation reaction in the component (α1) (X) to the number of SiH groups in the component (β1) (Y) is 30 ≧ Y / X ≧ 1. More preferably, 15 ≧ Y / X ≧ 2 is more preferable from the viewpoint of economy.

<(Α2) component>
The component (α2) has the following general formula (2)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 1 to 50 carbon atoms, and each R ¹ may be different or the same). Any organic compound can be used without particular limitation.
As R ¹ of the general formula (2), at least one R ¹ is represented by the following general formula (4) from the viewpoint of easy availability and compatibility with the vinyl polymer (I).

(In the formula, R ⁴ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁵ represents a hydrogen atom or a methyl group. When a plurality of R ⁴ and R ⁵ are present, they are different from each other. Are preferably the same, and more preferably a monovalent organic group having 1 to 20 carbon atoms; a monovalent organic group having 1 to 10 carbon atoms; More preferably, it is particularly preferably a monovalent organic group having 1 to 4 carbon atoms.
Examples of these preferable R ¹ are vinyl group, allyl group,

Etc.
From the viewpoint of improving the reactivity with the (β1) component, R ¹ is a monovalent organic group having 1 to 20 carbon atoms containing one or more groups represented by H ₂ C═CH—. It is preferable.

Preferable specific examples of the organic compound represented by the general formula (2) as described above include m-divinylbenzene, p-divinylbenzene and the like. The organic compound represented by the general formula (2) can be used alone or in combination of two or more.

<Reaction of (α2) component and (β1) component>
Examples of the catalyst for the hydrosilylation reaction of the (α2) component and the (β1) component include the hydrosilylation catalyst used in the hydrosilylation reaction of the above (α1) component and the (β1) component. 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 catalyst, In order to have sufficient reactivity and to keep the cost of a curable composition comparatively low, it is 10 < ^- > with respect to 1 mol of SiH groups of ((beta) 1) component. The range of ¹ to 10 ⁻⁸ mol is preferable, and the range of 10 ⁻³ to 10 ⁻⁷ mol is more preferable.

The hydrosilylation reaction of the (α2) component and the (β1) component is performed while slowly adding the (α2) component to the excess amount of the (β1) component in the presence of a hydrosilylation catalyst. A hydrosilyl group-containing compound (III) having at least two SiH groups in one molecule is obtained by removing the excess (β1) component from the reaction system after the hydrosilylation reaction. Can do.
The mixing ratio of the (α2) component and the (β1) component used in the reaction is not particularly limited, but in consideration of the physical properties of the cured product obtained by hydrosilylation of the obtained (III) component and the vinyl polymer (I) component Since it is preferable that the component (III) has more SiH groups, an excess amount of the component (β1) is used. In general, the ratio of the number (Z) of alkenyl groups capable of hydrosilylation reaction in the component (α2) to the number of SiH groups (Y) in the component (β1) is 20 ≧ Y / Z ≧ 1. More preferably, 10 ≧ Y / Z ≧ 2 is more preferable from the viewpoint of economy.

The component (B) includes at least one organic compound selected from the group consisting of triallyl isocyanurate, p-divinylbenzene and m-divinylbenzene, and a polyorgano having at least two SiH groups in one molecule. Particularly preferred is a hydrosilyl group-containing compound (II) or (III) characterized by having at least two SiH groups in one molecule, which can be obtained by hydrosilylation reaction of siloxane (β1). .

Although it does not specifically limit as a compounding quantity of (B) component, From the sclerosing | hardenable surface, the molar ratio ((B) / (A) of the alkenyl group in (A) component and SiH (hydrosilyl) group in (B) component. )) Is preferably in the range of 5 to 0.2, particularly preferably 2.5 to 0.4.

<< (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. Specifically, chloroplatinic acid; platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; platinum-vinylsiloxane complex {eg, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) n, Pt [(MeViSiO) ₄ ] _m }; platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ } (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer); chloroplatinic acid And a complex of alcohol, aldehyde, ketone, etc .; platinum-olefin complex (for example, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); Pt (acac) ₂ (wherein acac represents acetylacetonate); dicarbonyldichloroplatinum; Karlstedt catalyst; platinum described in U.S. Pat. -Hydrocarbon complexes; platinum alcohol catalysts described in US Pat. No. 3,220,972 to Lamoreaux et al. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl _{4 and the} like.
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 catalyst, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to ¹ mol of alkenyl groups in (A) component. It is preferable to use in the range of 10 ⁻² to 10 ⁻⁶ mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas is generated and the cured product may foam, so it is better not to use more than 10 ⁻¹ mol.

<< (D) Reinforcing Silica >>
In addition to the components (A), (B), and (C), the curable composition of the present invention can further contain reinforcing silica as the component (D) as necessary.
Examples of the reinforcing silica of component (D) include fumed silica and precipitated silica. Among these, those having a particle diameter of 50 μm or less and a specific surface area of 80 m ² / g or more are preferable from the viewpoint of reinforcing effect. 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 reinforcing silica include, but are not limited to, Nippon Aerosil Co., Ltd., which is one of fumed silicas, and Nippon Sil, Ltd., Nippon Silica Co., Ltd., which is one of precipitated silicas. .
In addition, the measurement of a specific surface area says the measured value by BET method (low-temperature low-humidity physical adsorption of an inert gas).

Although there is no restriction | limiting in particular as addition amount of this reinforcing silica, 0.1-100 weight part with respect to 100 weight part of (A) component, Preferably it is 0.5-80 weight part, Especially 1-50 weight. It is preferable to use parts. 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 (D) may be used independently and may be used together 2 or more types.

<< (E) Curing modifier >>
The curable composition of the present invention may further contain a (E) component curing modifier as necessary.
(E) As a hardening regulator of a component, the compound etc. which contain an aliphatic unsaturated bond are mentioned. For example,

(In formula, R ^<a> , R ^<b> is the same or different, represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group, and even if both are connected mutually. 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 with a good balance between storage stability and curability include 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyne-3 -Ol, 3-methyl-1-hexyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol Etc. Among these, 1-ethynyl-1-cyclohexanol and 3,5-dimethyl-1-hexyn-3-ol are more preferable from the viewpoint of availability.

As compounds containing aliphatic unsaturated bonds that improve storage stability at high temperatures other than acetylene alcohols,

(Wherein R ^c , R ^d , and R ^e are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and the total number of carbon atoms of R ^c , R ^d , and R ^e is 2 to 2) However, when R ^c and R ^d , or R ^d and R ^e are hydrocarbon groups, they may be linked to each other.)

(Wherein R ^f , R ^g and R ^h are the same or different and are each a hydrocarbon group having 1 to 10 carbon atoms, provided that R ^g and R ^h may be linked to each other). Silane compounds shown,

(In the formula, each R ⁱ may be the same or different, but at least one of them is a hydrocarbon group having 1 to 10 carbon atoms having an acetylenically unsaturated bond. N is 1 to 10) A polysiloxane compound represented by:

(Wherein R ^j may be the same or different and each represents a hydrogen atom, a halogen, or a monovalent hydrocarbon group having 1 to 10 carbon atoms. X is a halogen group such as chlorine or bromine; Or an alkoxy group).
Aliphatic carboxylic acid esters of olefinic alcohols such as vinyl acetate, tetravinylsiloxane cyclics, nitriles containing aliphatic unsaturated bonds such as 2-pentenenitrile, alkyl acetylenedicarboxylates, diallyl maleate, dimethyl maleate, Examples thereof include maleic esters such as diethyl maleate, diorgano fumarate and the like.

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. A hardening regulator may be used independently and may use 2 or more types together.

<< (F) Metal Soap >>
The curable composition of the present invention may further contain (F) component metal soap as necessary.
There is no restriction | limiting in particular about the metal soap which is (F) component, 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 binding part with metal in one molecule. Can be used.
Examples of long chain fatty acids include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. In these, a C1-C18 saturated fatty acid is preferable from the point of availability, and a C6-C18 saturated fatty acid is especially preferable from the point of the mold release effect.
Examples of metal ions include alkali metals (lithium, sodium, potassium), alkaline earth metals (magnesium, calcium, barium), zinc, lead, cobalt, aluminum, manganese, strontium, and the like.

Specific examples of metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, barium ricinoleate, zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate, Examples include zinc 2-ethylhexanoate, lead stearate, lead 12-hydroxystearate, cobalt stearate, aluminum stearate, manganese oleate and the like.
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.

<< Curable composition >>
The curable composition of the present invention has various additives for adjusting physical properties, such as flame retardants, anti-aging agents, fillers, plasticizers, physical property modifiers, adhesion promoters, storage stability improvers. A solvent, a radical inhibitor, a metal deactivator, an ozone degradation inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, a foaming agent, a photocurable resin, and the like may be appropriately blended as necessary. These various additives may be used alone or in combination of two or more.
In addition, since the vinyl polymer is originally a polymer having excellent durability, an anti-aging agent is not always necessary, but conventionally known antioxidants, ultraviolet absorbers, light stabilizers and the like may be appropriately used. it can.

<Filler>
In the curable composition of the present invention, various fillers may be used as necessary in addition to the reinforcing silica as the component (D).
The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, graphite, clay, silica (crystalline silica, fused silica, dolomite, silicic anhydride, water content Reinforcing fillers such as silicic acid, carbon black, etc .; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, bengara , Aluminum fine powder, Flint powder, Zinc oxide, Active zinc white, Zinc powder, Zinc carbonate, Shirasu balloon and other fillers; Asbestos, Glass fiber, Glass filament, Carbon fiber, Kevlar fiber, Polyethylene fiber, etc. Etc.
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.
As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. Salts of these fatty acids such as sodium and potassium; alkyl esters of these fatty acids. Specific examples of surfactants include polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, and sulfate-type anionic surfactants such as sodium salts and potassium salts thereof; alkylbenzene sulfonic acids and alkylnaphthalene sulfones. Examples thereof include acids, paraffin sulfonic acids, α-olefin sulfonic acids, alkyl sulfosuccinic acids, and the like, and sulfonic acid type anionic surfactants such as sodium salts and potassium salts thereof.
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 a dry method and a wet method 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 products having various average particle sizes by classification. Although not particularly limited, the specific surface area value is preferably 1.5 m ² / g or more and 50 m ² / g or less, when the effect of improving the breaking strength and breaking elongation of the cured product is expected, and is preferably 2 m ² / g or more and 50 m ^2. / G or less is more preferable, 2.4 m ² / g or more and 50 m ² / g or less is more preferable, and 3 m ² / g or more and 50 m ² / g or less is particularly preferable. 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 when the purpose is to increase the viscosity only.

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, an increase in the 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.

In addition, the value of a specific surface area means the measured value by the air permeation method (method which calculates | requires a specific surface area from the permeability | transmittance of the air with respect to a powder filling layer) performed according to JISK5101 as a measuring 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>
Furthermore, for the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles may be used in combination with these reinforcing fillers.
Such fine hollow particles (hereinafter referred to as balloons) are not particularly limited, but, as described in “The latest technology of functional filler” (CMC), the diameter is 1 mm or less, preferably 500 μm or less, and more preferably Is a hollow body made of an inorganic or organic material of 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 more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

Examples of the inorganic balloon include silicate balloons and non-silicate balloons. Silicate balloons include shirasu balloons, perlite, glass balloons, silica balloons, fly ash balloons, etc., and non-silicate balloons include alumina. Examples include balloons, zirconia balloons, and carbon balloons.
Specific examples of these inorganic balloons include Shirasu balloons made by Idichi Kasei Co., Ltd., Sankilite made by Sanki Kogyo Co., Ltd., Nihon Sheet Glass Karun as glass balloons, Cellstar Z-28 made by Sumitomo 3M, MICRO made by EMERSON & CUMING. BALLON, PELTSBURGE CORNING's CELAMIC GLASSMMODULES, 3M's GLASS BUBBLES, Asahi Glass's Q-CEL, Taiheiyo Cement's E-SPHERES, Fly Ash Balloon's, PERAMARKET's CEROSPHERES S. FILLITE manufactured by A, BW manufactured by Showa Denko as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA as a zirconia balloon, clecas sphere manufactured by Kureha Chemical Co., Ltd. and boss sphere manufactured by GENERAL TECHNOLOGIES as a carbon balloon are commercially available.

Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon. The thermosetting balloon is a phenol balloon, an epoxy balloon, and a urea balloon, and the thermoplastic balloon is a saran balloon, a polystyrene balloon, Examples include methacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons. A crosslinked thermoplastic balloon can also be used. The balloon here may be a balloon after foaming, or a balloon containing a foaming agent may be foamed after blending.

Specific examples of these organic balloons include UCAR and PHENOLIC MICROBALLONONS made by Union Carbide as phenolic balloons, ECCOSPHERES made by EMERSON & CUMING as epoxy balloons, ECCOSPHERES VF-O made by EMERSON & CUMING, and DOWEMIC PHALS made by Saran Balloon by Saran Balloon. EXPANSEL manufactured by Nippon Filament, Matsumoto Microsphere manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Bridge-type styrene - SX863 is acrylic acid balloon made by Japan Synthetic Rubber (P) are commercially available.

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.

Although content of a balloon is not specifically limited, Preferably it is 0.1-50 weight part with respect to 100 weight part of vinyl-type polymer (I), More preferably, it can be used in 0.1-30 weight part. . 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. When the specific gravity of the balloon is 0.1 or more, the content 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 of this invention as needed.
Although it does not specifically limit as a plasticizer, According to the objectives, such as adjustment of a physical property and adjustment of properties, phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; Dioctyl adipate , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinolinate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Polyalkylene glycol esters such as erythritol ester; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; polystyrene, poly-α-methylstyrene Polystyrene, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene glycol, polypropylene glycol, polytetra Polyether polyols such as methylene glycol and polyethers such as derivatives obtained by converting hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; sebacic acid, Dibasic alcohols such as adipic acid, azelaic acid and phthalic acid, and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol Polyester plasticizers obtained from a resin; vinyl polymers obtained by polymerizing vinyl monomers including acrylic plasticizers by various methods, and the like.

Among them, the polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000 is added, such as the viscosity of the curable composition and the tensile strength and elongation of the cured product obtained by curing the composition. The mechanical properties can be adjusted, and the initial physical properties can be maintained for a long time as compared with the case where a low molecular plasticizer which is a plasticizer not containing a polymer component in the molecule is used. Although not limited, the polymer plasticizer may or may not have a functional group.

Although the number average molecular weight of the polymer plasticizer was described as 500-15000 above, 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 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.

The amount of the plasticizer used is not limited, but is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). is there. If it is less than 5 parts by weight, the effect as a plasticizer tends to be difficult to develop, and if it exceeds 150 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 compound lowers the viscosity of the composition before curing, and bonds with the SiH group of the hydrosilyl group-containing compound (II) and / or (III) by the hydrosilylation reaction during the curing reaction, and is eventually incorporated into the network structure. It is.
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. A compound having a polar group such as an ester group is preferred from the viewpoint of good solubility. Further, the lower the molecular weight, the better the compatibility, but it is preferable that the molecular weight is sufficiently high as long as it is sufficiently compatible. Further, from the viewpoint of heat resistance, weather resistance, etc., which are the characteristics of the composition of the present invention, it is more preferable that this reactive diluent does not have a carbon-carbon unsaturated bond having low activity against hydrosilylation. .
In addition, when a low boiling point compound that can volatilize during curing curing is used as a reactive diluent, it may cause a shape change before and after curing, or it 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.

On the other hand, the addition amount of the reactive diluent is within a range that does not hinder the formation of a three-dimensional crosslinked structure by the hydrosilylation reaction between the vinyl polymer (I) and the hydrosilyl group-containing compound (II) and / or (III). If so, there is no particular limitation. That is, when the addition amount of the reactive diluent becomes excessive, the SiH group of the hydrosilyl group-containing compound (II) and / or (III) is consumed by the hydrosilylation reaction with the unsaturated group of the reactive diluent. Therefore, the formation of the three-dimensional crosslinked structure by the vinyl polymer (I) may be insufficient.
The reactive diluent is used in an amount of 0.1 to 100 parts by weight, preferably 0.5 to 70 parts by weight, particularly 1 to 50 parts by weight, based on 100 parts by weight of the vinyl polymer (I).

<Solvent>
A solvent can be mix | blended with the curable composition of 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; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone Is 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, if necessary, such as two-color molding with a dissimilar substrate, The mold release which is the effect of the present invention does not significantly inhibit the crosslinking reaction between the compound (I) and the hydrosilyl group-containing compound (II) and / or (III), and does not significantly affect the physical properties of the resulting cured product. It is possible to add an adhesion-imparting agent to the extent that it does not affect moldability.
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 alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkyls such as dimethyldiisopropenoxysilane and methyltriisopropenoxysilane. Isopropenoxysilane; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; Silicone varnishes; polysiloxanes and the like.

In addition, as long as the hydrosilylation reaction is not inhibited, 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.
Specifically, alkoxysilanes having an epoxy group include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- Epoxysilanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; having an isocyanate group Alkoxysilanes include isocyanates such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane. Group-containing silanes; as alkoxysilanes having an isocyanurate group, isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; as alkoxysilanes having an amino group, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)- γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane N-phenyl-γ-amino Amino group-containing silanes such as propyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; alkoxysilanes having a mercapto group include γ-mercapto Mercapto group-containing silanes such as propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane; as alkoxysilanes having a carboxyl group, β-carboxyl Carboxysilanes such as ethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; Examples of alkoxysilanes having a gen group include halogen-containing silanes such as γ-chloropropyltrimethoxysilane; examples of alkoxysilanes having a (meth) acryl group include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxy. Propyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane And (meth) acrylic group-containing silanes.
In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. .

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 dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimethoxide, tin octylate and the like; organoaluminum compounds such as aluminum acetylacetonate; tetraisopropoxytitanium, tetrabutoxytitanium And organic titanium compounds.

The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight with respect to 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 be lowered. 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.
The vinyl polymer (I) and the hydrosilyl group-containing compound (II) and / or (III) can be mixed at an arbitrary ratio, but from the viewpoint of curability, the alkenyl group in the component (A) ( The molar ratio ((B) / (A)) of SiH (hydrosilyl) groups in component B) is preferably in the range of 5 to 0.2, particularly preferably 2.5 to 0.4. If the molar ratio is greater than 5, curing tends to be insufficient and a cured product having a low strength tends to be obtained, and if it is less than 0.2, many active hydrosilyl groups remain in the cured product even after curing. , Cracks and voids tend to be produced, and it is difficult to obtain a uniform and strong cured product.

In the present invention, the curable composition is cured by the addition reaction of the SiH group to the alkenyl group using a 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. At a temperature lower than 100 ° C., the composition is excellent in storage stability, so the curing reaction hardly proceeds. However, when the temperature is about 100 ° C. or higher, the hydrosilylation reaction proceeds rapidly, and a cured product is obtained in a short time. be able to.

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 30 ° C. or more and less than 100 ° C., but more preferably 40 ° C. or more and less than 80 ° C.

Moreover, in this invention, while making a curable composition flow at the temperature of 30 degreeC or more and less than 100 degreeC, hardening reaction can be performed, further making it flow at 30 degreeC or more. That is, the curable composition of the present invention can be used as a resin for injection molding (RIM, LIM, etc.).

The curable composition of the present invention may be prepared as a one-component type that is pre-blended and stored with all compounding components and cured by heating at the time of curing. When ensuring long-term storage stability, It 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-component form, there is no particular limitation on how to divide the compounding components, but when longer-term storage stability is required, the hydrosilyl group-containing compound and the hydrosilylation catalyst are divided. In the blended liquid (referred to as liquid A), the vinyl polymer (I) as component (A) and the hydrosilylation catalyst as component (C) were blended, and the other blended liquid (referred to as 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). (D) Filler containing reinforcing silica of component, (E) component curing regulator, (F) component metal soap, plasticizer, anti-aging agent, etc. may be blended in either A liquid or B liquid Good. In consideration of the stability of each component, it may be better to blend the (E) component curing regulator and the (F) component metal soap in the B liquid. 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, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.

<< Usage >>
The curable composition of the present invention is not particularly limited, but is an electric / electronic component material such as a solar cell back surface sealing material, an electric insulating material such as an electric wire / cable insulating coating material, a coating material, a foam, and an electric / electronic material. Can be used for various applications such as potting materials, films, gaskets, casting materials, artificial marble, various molding materials, and rust-proof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts). is there.

Furthermore, the molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used 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, especially engine mount rubbers. Engine parts can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts.
In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts 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 Oil packing for combustion equipment, such as heater packing, steam outlet seal, etc., O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube Speaker gaskets, speaker edges, turntables for sound equipment such as diaphragm valves and air pipes Over door, belts, pulleys, and the like.

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, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. 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.
In the marine and civil engineering field, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave extinguishing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc.
In addition, it can be used for sheet rubber, mats, foam boards and the like.

Since the curable composition of the present invention has excellent compatibility between the vinyl polymer and the hydrosilyl group-containing compound, the curable composition becomes cloudy or the hydrosilyl group-containing compound is separated during storage of the curable composition. There is no problem, and it is excellent in the compression set of the cured product.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.
In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
In the following examples, “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)
A 500 mL flask was charged with 1.80 g (12.6 mmol) of copper (I) bromide and 21 mL of acetonitrile, and heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. To this, 5.05 g (14.0 mmol) of diethyl 2,5-dibromoadipate, 60 mL (0.418 mol) of butyl acrylate, 84 mL (0.775 mol) of ethyl acrylate, 63 mL (0.489 mol) of 2-methoxyethyl acrylate ), And the mixture was further heated and stirred at 80 ° C. for 20 minutes. To this was added 0.262 mL (1.26 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) to initiate the reaction. Further, 0.087 mL (0.42 mmol) of triamine was added. Stirring was continued at 80 ° C., during which time 0.087 mL (0.42 mmol) of triamine was added. 180 minutes after the start of the reaction, the inside of the reaction vessel was depressurized to remove volatile components. 240 minutes after the start of the reaction, 62 mL of acetonitrile, 62 mL (0.42 mol) of 1,7-octadiene, and 0.87 mL (4.18 mmol) of triamine were added, followed by continued heating and stirring at 80 ° C., and heating after 620 minutes from the start of the reaction. Stopped. The reaction solution was heated under reduced pressure to remove volatile components, diluted with toluene and filtered, and the filtrate was concentrated to obtain a polymer.

The obtained polymer, Kyoward 500SH (inorganic synthetic adsorbent, manufactured by Kyowa Chemical Co., Ltd .: 2 parts by weight with respect to 100 parts by weight of polymer), Kyoward 700SL (inorganic synthetic adsorbent, manufactured by Kyowa Chemical Co., Ltd .: polymer) 2 parts by weight with respect to 100 parts by weight) was mixed with xylene (100 parts by weight with respect to 100 parts by weight of the polymer) and stirred at 130 ° C. After 3 hours, aluminum silicate was filtered, and the volatile matter in the filtrate was distilled off by heating under reduced pressure. The polymer was devolatilized by heating at 180 ° C. for 12 hours (the degree of vacuum was 10 torr or less), thereby removing the Br group from the copolymer. Kyoward 500SH (manufactured by Kyowa Chemical Co., Ltd .: 3 parts by weight with respect to 100 parts by weight of the polymer) and Kyoward 700SL (manufactured by Kyowa Chemical Co., Ltd .: 3 parts by weight with respect to 100 parts by weight of the polymer) xylene (polymer 100) 100 parts by weight with respect to parts by weight) and stirred at 130 ° C. After 5 hours, aluminum silicate was filtered, and the volatile content of the filtrate was distilled off by heating under reduced pressure to obtain an alkenyl-terminated copolymer [P1].
The number average molecular weight of the copolymer [P1] was 18000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.1. The number of alkenyl groups introduced per molecule of the copolymer was determined by ¹ H-NMR analysis and found to be 1.9 on average.

(Synthesis Example 2)
A copolymer [P2] was obtained in the same manner as in Synthesis Example 1 except for the following compound amounts.
-Butyl acrylate: 120 mL (0.84 mol)
-Ethyl acrylate: 5.4 mL (0.06 mol)
-2-methoxyethyl acrylate: 115 mL (0.90 mol)
Copper bromide (I): 1.93 g (13.4 mmol)
・ Diethyl 2,5-dibromoadipate: 3.59 g (9.96 mmol)
Triamine: 1.29 mL (4.93 mmol)
Acetonitrile: 97 mL (1.85 mol)
・ 1,7-octadiene: 44 mL (0.30 mol)
The obtained copolymer [P2] had a number average molecular weight of 27,000 and a molecular weight distribution of 1.2. The average number of alkenyl groups introduced per molecule of the copolymer was determined by ¹ H-NMR analysis and found to be 2.0 on average.

(Synthesis Example 3)
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 a 120 ° C. oil bath. To this solution, a mixed solution 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 [C1]. .
^{By 1} H-NMR analysis, it was found that the hydrosilyl group-containing compound [C1] was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate. (The hydrosilyl group-containing compound [C1] is a mixture, but contains the following compounds having 9 SiH groups in one molecule as a main component).

(Synthesis Example 4)
1800 g of toluene, 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane and xylene of bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex in a 5 L two-necked flask 125 μl of a solution (containing 3 wt% as platinum) was added, and the mixture was heated and stirred at 50 ° C. under nitrogen in an oil bath. To this solution, a mixed solution of 156 g of divinylbenzene (DVB960 manufactured by Nippon Steel Chemical Co., Ltd.) and 433 g of toluene was dropped over 25 minutes. The resulting solution was heated and stirred for 1 hour. After adding 275 mg of benzothiazole, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a hydrosilyl group-containing compound [C2].
^{According to 1} H-NMR analysis, the hydrosilyl group-containing compound [C2] was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with divinylbenzene (hydrosilyl group-containing compound [C2] Is a mixture but contains the following compound having 6 SiH groups in one molecule as a main component).

(Comparative Synthesis Example 1)
Toluene 600 g, 1,3,5,7-tetramethylcyclotetrasiloxane 600 g, and xylene of bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex in a 2 L two-necked flask 52 μl of a solution (containing 3 wt% as platinum) was added, and the mixture was heated and stirred at 80 ° C. under nitrogen in an oil bath. To this solution, a mixed liquid of 28.7 g of 1,9-decadiene and 58 g of toluene was added dropwise over 1 hour. The resulting solution was allowed to warm and stir for 2 hours. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a hydrosilyl group-containing compound [C3].
^{According to 1} H-NMR analysis, the hydrosilyl group-containing compound [C3] was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with 1,9-decadiene (hydrosilyl group-containing compound). It was found that [C3] is a mixture but contains the following compound having 6 SiH groups in one molecule as a main component).

(Examples 1-4, Comparative Examples 1-6)
As shown in Table 1, 100 parts by weight of each vinyl polymer, 10 parts by weight of each hydrosilyl group-containing compound, and 1,1,3,3-tetramethyl-1,3 of zero-valent platinum as a hydrosilylation catalyst. -A curable composition was obtained by mixing 0.04 parts by weight of an isopropanol solution of divinyldisiloxane complex (containing 3 wt% as platinum).
The curable composition was put in a glass bottle and sealed, and allowed to stand at room temperature (15 to 23 ° C.) for one day, and then the state was visually observed to evaluate the compatibility. A sample having no turbidity was indicated by ○, and a sample having white turbidity or layer separation was indicated by ×. The results are shown in Table 1.
In addition, hydrosilyl group containing compound [C4] shows the chain | strand-shaped methylpolysiloxane which contains an average of five hydrosilyl groups and an average of five (alpha) -methylstyrene groups in a molecule | numerator. The hydrosilyl group-containing compound [C5] represents a chain methylpolysiloxane containing an average of 6 hydrosilyl groups and an average of 1.5 α-methylstyrene groups in the molecule.

As is apparent from Table 1, when the conventional hydrosilyl group-containing compound was used, it was inferior in compatibility with the vinyl polymer and became cloudy or separated into layers, whereas the hydrosilyl group-containing compound in the present invention was used. In Examples 1 to 4, all were uniformly compatible.

(Example 5)
To 100 parts of the copolymer [P1] obtained in Synthesis Example 1, 20 parts of Aerosil R974 (average diameter of primary particles 12 nm: manufactured by Nippon Aerosil) as reinforcing silica, calcium stearate (trade name SC-100, 1 part of Sakai Chemical Co., Ltd.) and 1 part of a hindered phenolic antioxidant (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals) as an antioxidant were blended and further mixed thoroughly using three paint rolls. Thereafter, the hydrosilyl group-containing compound [C1] is added to the copolymer [P1] in such an amount that the SiH group of [C1] becomes 1.0 molar equivalent of the alkenyl group of the copolymer [P1]. A xylene solution of a 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (containing 3 wt% as platinum) is 5 × 10 5 of the alkenyl group of the copolymer [P1] in terms of platinum. ^-4 molar equivalent, 3,5-dimethyl-1-hexyn-3-ol (trade name Surfynol 61, manufactured by Nissin Chemical) as a curing regulator is added in a molar ratio of 150 to the platinum catalyst, and The mixture was uniformly mixed to obtain a curable composition.
The curable composition thus obtained was sufficiently degassed in a 50 ° C. vacuum oven, and then poured into a compression permanent sample preparation mold based on JIS K 6262, and pressed at a temperature of 180 ° C. Vulcanization was performed for 10 minutes, and then post-vulcanization was performed in an oven at 180 ° C. for 22 hours to obtain a rubber-like cured product.

(Examples 6-11, Comparative Examples 7-13)
In the same manner as in Example 5, each component was blended at the blending ratio shown in Table 2 to obtain a rubber-like cured product.

(Evaluation 1) Compression set at 150 ° C. for 70 hours was measured according to JIS K 6262 for the compression set for compression set obtained in Examples 5 to 11 and Comparative Examples 7 to 13. . The results are shown in Table 2.

As is apparent from Table 2, in Examples 5 to 11 using a compatible hydrosilyl group-containing compound, all have good compression set as compared with the case of using the same mole of a conventional hydrosilyl group-containing compound. showed that.

Since the curable composition of the present invention has excellent compatibility between the vinyl polymer and the hydrosilyl group-containing compound, turbidity of the curable composition, separation of the hydrosilyl group-containing compound during storage of the curable composition, etc. There is no problem, and it is excellent in compression set of the cured product.

Claims (16)

The following three components:
(A) Acrylic ester polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule and having a main chain produced by a living radical polymerization method,
(B) The following general formula (1)

(In the formula, R ¹ represents a monovalent organic group having an alkenyl group having 2 to 50 carbon atoms capable of hydrosilylation reaction, and each R ¹ may be different or the same.)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by a hydrosilylation reaction, and at least two SiH in one molecule. A hydrosilyl group-containing compound (II) characterized by having a group;
And / or the following general formula (2)

(Wherein R ¹ represents a monovalent organic group having an alkenyl group capable of hydrosilylation reaction having 2 to 50 carbon atoms, and each R ¹ may be different or the same)
And a polyorganosiloxane (β1) having at least two SiH groups in one molecule can be obtained by a hydrosilylation reaction, and at least two SiH in one molecule. A hydrosilyl group-containing compound (III) characterized by having a group;
(C) a hydrosilylation catalyst,
Is a curable composition that gives a rubber-like molded product comprising as an essential component,
The molar ratio of the alkenyl group of component (A) to the SiH group of component (B) ((B) / (A)) is set to 5 to 0.2, and (C) with respect to 1 mole of alkenyl group in component (A) ) The curable composition characterized by using 10 ^{< -1} > ^-10 <^-8> mol component. The curable composition according to claim 1, wherein the molecular weight distribution of the vinyl polymer (I) is less than 1.8. The curable composition according to claim 1, wherein the living radical polymerization is atom transfer radical polymerization. The atom transfer radical polymerization is carried out using a metal complex selected from transition metal complexes having a central metal of Group 7, Group 8, Group 9, Group 10, or Group 11 of the Periodic Table as a catalyst. 3. The curable composition according to 3 . 5. The curable composition according to claim 4 , wherein the metal complex used as a catalyst is a complex having copper, nickel, ruthenium, or iron as a central metal. 6. The curable composition according to claim 5 , wherein the metal complex used as a catalyst is a copper complex. (A) component is the following processes:
(1) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the following general formula (3)
^{-C (R 2) (R 3} ) (X) (3)
(In the formula, R ² and R ³ 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
(2) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation;
The curable composition according to any one of claims 1 to 6 , wherein the curable composition is a vinyl polymer obtained by the following process. (A) component is the following processes:
(1) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2) Subsequently, this is reacted with a compound having at least two alkenyl groups having low polymerizability;
The curable composition according to any one of claims 1 to 7 , which is a vinyl polymer obtained by the following. The curable composition according to any one of claims 1 to 8 , wherein an alkenyl group capable of hydrosilylation reaction is contained in the terminal of the polymer in the vinyl polymer (I). (B) At least one R ¹ in the general formula (1) or (2) representing the organic compound (α1) or (α2) in the component is represented by the following general formula (4)

(Wherein R ⁴ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁵ represents a hydrogen atom or a methyl group. When a plurality of R ⁴ and R ⁵ are present, they are different from each other. May be the same.)
The curable composition according to any one of claims 1-9 in a group represented by. (B) an organic compound of component ([alpha] 1) at least two of the three R ¹ in the general formula (1) representing the curable composition according to any one of claims 1 to 10 which is an allyl group. (B) the component is at least one organic compound selected from the group consisting of triallyl isocyanurate, p-divinylbenzene and m-divinylbenzene, and a polyorganosiloxane having at least two SiH groups in one molecule ( the .beta.1), it can be obtained by hydrosilylation reaction, hydrosilyl group-containing compound characterized by having at least two SiH groups in each molecule (II) or of claim 1-9 which is (III) The curable composition as described in any one. A curable composition comprising the curable composition according to any one of claims 1 to 12 and further containing reinforcing silica as a component (D). A curable composition comprising the curable composition according to any one of claims 1 to 13 and further containing a curing regulator as a component (E). Claim 1 The curable composition according to any one of 14, further (F) curable composition containing a metal soap as a component. Hardened | cured material obtained from the curable composition as described in any one of Claims 1-15 .