JP2007182523A - Method for bonding cured material and metal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for bonding a curable composition containing a vinyl polymer giving a cured material generally having good mechanical properties, oil resistance, heat-resistance, etc., and curable by hydrosilylation reaction to a surface of a metal. <P>SOLUTION: The method for bonding a cured material and a metal is characterized by the contact of a curable composition containing (A) a vinyl polymer (I) containing at least one alkenyl group having hydrosilylation reactivity in the molecule, (B) a compound (II) containing a hydrosilyl group and (C) a hydrosilylation catalyst with the surface of a metal having a primer coated or applied to the surface to effect the curing of the curable composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a method of bonding a cured product and a metal and a composite obtained by the method. More specifically, the present invention relates to a method for bonding a cured product obtained by curing a curable composition comprising an alkenyl group-containing vinyl polymer capable of hydrosilylation reaction, a hydrosilyl group-containing compound and a hydrosilylation catalyst, and a metal. .

A molded body containing a vinyl polymer as a main component can be obtained by kneading a high molecular weight polymer together with various additives in a heated state using a roll, a mill, or the like and molding the polymer. Among them, a molded product of acrylic rubber mainly composed of (meth) acrylic polymer is heat vulcanized after kneading compounding agents such as filler and vulcanizing agent with unvulcanized rubber (acrylic rubber). Can be obtained. However, it is inferior in workability, such as sticking to the roll during kneading and being difficult to smooth during sheeting, and poor workability such as non-fluidity during molding and low vulcanization speed, and easy scorching There is a problem of poor curability (Non-patent Document 1).
As a method for solving these problems, it is conceivable to use a (meth) acrylic polymer having a reactive functional group at the molecular end. When a (meth) acrylic polymer having a reactive functional group at the molecular end is used, the molecular weight between the crosslinking points can be effectively obtained, and the molecular weight of the main chain itself can be reduced. As a result, it is expected that processability will be improved. In addition, since it has a reactive functional group at the molecular end, a cured product with a high molecular weight between cross-linking points can be obtained. It is expected to obtain an excellent cured product. Therefore, many researchers are studying an industrial production method of a (meth) acrylic polymer having a reactive functional group at the molecular end. For example, there is a method for synthesizing a (meth) acrylic polymer having an alkenyl group at both ends using an alkenyl group-containing disulfide as a chain transfer agent (Patent Document 1). However, it is difficult to reliably introduce alkenyl groups at both ends, and since the resulting copolymer is a latex, a complicated operation of removing moisture is required when used for molded products. There is a problem such as. In addition, 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. There is a method of synthesizing a polymer (Patent Document 2). This method also has a problem that it is difficult to reliably introduce alkenyl groups at both ends, and that complicated work such as long-time post-curing is required for curing with peroxide. is there.
Therefore, in order to solve such a problem, the present inventors have obtained a (meth) acrylic compound having a specific terminal structure obtained by a polymerization method using an organic halide or the like as an initiator and a transition metal complex as a catalyst. Developed a method (Patent Document 3) for producing a (meth) acrylic polymer having an alkenyl group at its terminal by converting the halogen of the polymer into an alkenyl group-containing substituent, enabling production on a factory scale. ing. Moreover, the molded object (patent document 4) which hardens the curable composition containing the vinyl polymer containing an alkenyl group at the terminal, and a hydrosilyl group containing compound is proposed. The hydrosilylation reaction used for curing a curable composition containing a vinyl polymer containing an alkenyl group at the terminal and a hydrosilyl group-containing compound is very slow or does not proceed substantially at low temperatures. , It has a feature with excellent thermal potential that the reaction is completed quickly by heating. Therefore, this curable composition has an advantage that a cured product can be obtained quickly without scorching during molding.
A curable composition containing a (meth) acrylic polymer having an alkenyl group at the terminal obtained by the above method (Patent Document 3), a vinyl polymer containing an alkenyl group at the terminal, and a hydrosilyl group-containing compound. When using the curable composition containing (Patent Document 4) for two-color molding or insert molding with a different base material, an adhesiveness imparting agent is added to improve the adhesion to the different base material. However, the addition of these adhesion-imparting agents is not sufficient in the effect of adhesion, and there are problems such as a decrease in mechanical properties and a delay in the curing rate. Further, when an adhesion imparting agent is added in order to impart adhesion to the metal surface, there is a problem that it is difficult to release from the mold surface.
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)

The object of the present invention is to cure a curable composition that contains a vinyl polymer and can be cured by a hydrosilylation reaction, which gives a cured product that generally exhibits good mechanical properties, oil resistance, heat resistance, and the like. It is to provide a method capable of providing a composite in which a cured product and a metal are firmly bonded.

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

That is, the present invention
(A) Vinyl-based polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule, (B) Hydrosilyl group-containing compound (II), and (C) Curing containing hydrosilylation catalyst The adhesive composition is a method of adhering a cured product to a metal (hereinafter sometimes simply referred to as “adhesion method”), characterized in that the adhesive composition is cured by contacting the metal surface to which the primer is applied or attached. is there.

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

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

  The vinyl polymer (I) is preferably a (meth) acrylic polymer, more preferably an acrylic polymer, and even more preferably an acrylic ester polymer.

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

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

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

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

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

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

  The primer is preferably an aqueous primer composition, and more preferably water.

  The curable composition may further contain (D) reinforcing silica and / or (E) a curable modifier.

  The composite of the present invention can be obtained by the above bonding method.

  According to the bonding method of the present invention, curing is performed by curing a curable composition containing a vinyl polymer exhibiting good mechanical properties, oil resistance, heat resistance, etc. without using an adhesion promoter. An object can be firmly adhered to a metal surface.

  Below, the adhesion method of this invention and the composite obtained by the method are explained in full detail.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(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 each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20).

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

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

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

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

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

It does not specifically limit as an organic halide which has a hydroxyl group as a specific functional group, or a halogenated sulfonyl compound, The following are illustrated.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(In 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)
It does not specifically limit as an organic halide which has an amino group as a specific functional group, or a halogenated sulfonyl compound, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(In 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)
It does not specifically limit as an organic halide which has an epoxy group as a specific functional group, or a halogenated sulfonyl compound, The following are illustrated.

(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 in one molecule of the present invention, it is preferable to use an organic halide having two or more initiation 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. More preferable examples include transition metal complexes having zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal. Of these, a copper complex is preferable. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. 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. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

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

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

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

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

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

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

When the rubber-like properties are especially required in the cured product obtained from the curable composition of the positions invention hydrosilylatable alkenyl group, the molecular weight between crosslinking sites, which has a great influence on the rubber elasticity, can be increased It is preferable that at least one of the alkenyl groups capable of hydrosilylation is at the end of the molecular chain. More preferably, all alkenyl groups capable of hydrosilylation reaction are present at the molecular chain ends.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The other is
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two low-polymerizable alkenyl groups;
It is a method.

<< (B) Hydrosilyl group-containing compound (II) >>
The hydrosilyl group-containing compound (II) as the component (B) is a hydrosilyl group which can be cured by crosslinking with the vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction as the component (A). There are no particular limitations as long as it is a contained compound, and various compounds can be used, but organohydrogenpolysiloxane is preferred.

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

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

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

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

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

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

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

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

<< (C) Hydrosilylation Catalyst >>
There is no restriction | limiting in particular about the hydrosilylation catalyst which is (C) component in this invention, Arbitrary things can be used. 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 Complexes with alcohols, aldehydes, ketones, etc .; platinum-olefin complexes (eg Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); Pt (acac) ₂ (Eq. , Acac represents acetylacetonate); dicarbonyldichloroplatinum; Karlstedt catalyst; platinum-hydrocarbon complexes described in Ashby et al. US Pat. Nos. 3,159,601 and 3,159,662; Examples thereof include platinum alcoholate catalysts described in the specification of No. 3220972. 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 hydrosilylation catalyst, It is preferable to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to ¹ mol of alkenyl groups which can be hydrosilylated in (A) component. More preferably, it is the range of 10 ^<-2 > ^{-10 < -6>} mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and may generate a large amount of hydrogen gas to foam the cured product, so it is better not to use more than 10 ⁻¹ mol.

<< Primer >>
The primer used in the present invention is a primer that is applied or adhered in advance to the metal surface in order to improve the adhesion of the cured product obtained by curing the curable composition to the metal. The primer in the present invention can be used without particular limitation as long as it is a primer for improving adhesiveness, but it is liquid at room temperature such as an organic solvent, water, etc. Hereinafter, those having a main component of a solvent) are preferably used. Examples of preferable organic solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, ether solvents such as ethyl ether, isopropyl ether, and tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. Ketone solvents, ester solvents such as ethyl acetate and butyl acetate, hydrocarbon solvents such as pentane, hexane, heptane and octane, aromatic solvents such as benzene, toluene and xylene, methylene chloride, chloroform, trichloroethylene, park Halogen solvents such as lorethylene and 1,1.1-trichloroethane may be used alone or in combination of two or more. Water is preferably used as the solvent from the viewpoints of cost, environmental burden, and worker safety.

  When water is used as the primer used in the present invention, the pH of the water is preferably 5-10. When the pH is less than 5, problems such as oxidation of the applied metal surface may occur. When the pH is more than 10, the alkalinity is high and handling is required.

  To the primer used in the present invention, a solid or liquid film-forming substance and / or an adhesion-imparting substance may be added as a component for improving adhesion. The film-forming substance and / or the adhesion-imparting substance is dissolved or dispersed in a solvent and used as a liquid (solution or dispersion). However, it may be used as it is at room temperature, but it is preferable to dilute and apply or adhere from the viewpoint of cost and workability.

  The addition amount of the film-forming substance and / or the adhesion-imparting substance is preferably 0 to 50 parts with respect to 100 parts of the solvent, and preferably 0 to 30 parts from the viewpoint of cost.

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

Examples of the reinforcing silica as component (D) include fumed silica and wet process 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 the reinforcing silica include, but are not limited to, Nippon Aerosil Co., Ltd., which is one of fumed silicas, Leoroseal Co., Ltd., Tokuyama Co., and Nippon Sil, Tosoh Silica Co., Ltd., which is one of wet-type silicas. , Fuji Silysia's Silicia, Silo Hobic, Tokuyama's Toxeal, Fine Seal, Degussa's Carplex, Sipernat, Mizusawa Chemical's Mizusukasil.

  In addition, the said specific surface area value 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, Preferably it is 0.1-100 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.5-80 weight part, More preferably 1 to 50 parts by weight. When the blending amount is less than 0.1 parts by weight, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts by weight, the workability of the curable composition may be deteriorated. Moreover, the said reinforcing silica (D) may be used independently and may be used together 2 or more types.

<(E) Curing modifier>
There is no restriction | limiting in particular as a hardening regulator which is (E) component contained in the curable composition used by this invention, Although arbitrary things can be used, It is a compound containing an aliphatic unsaturated bond. preferable.

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

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

  Examples of acetylene alcohols having a 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-pentyne-3- Examples include oars. 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, 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 having 1 to 10 carbon atoms).
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 modifier (E) 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 2 to 10,000 molar equivalents. More preferably, it is the range of 5-1000 molar equivalent. When it is less than 2 molar equivalents, the storage stability may be insufficient, and when it exceeds 10,000 molar equivalents, curing tends to be slow.
Moreover, a hardening regulator may be used independently and may use 2 or more types together.

<< Curable composition >>
The curable composition used in the present invention contains the components (A), (B) and (C), and if necessary, the components (D) and / or (E), but the physical properties are adjusted. In addition, various additives such as metal soap, fillers, fine hollow particles, plasticizers, solvents, flame retardants, antioxidants, light stabilizers, ultraviolet absorbers, physical property modifiers, radical inhibitors, 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.

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

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

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

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

  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.

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

  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 white 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 or the like is more preferable.

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

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

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

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

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

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

  Examples of the inorganic balloons 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., Nippon Glass Co., Ltd. Caloon, Sumitomo 3M Cellstar Z-28, EMERSON & CUMING MICRO 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, and CARBOS 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, DYLITE EXPANDABLE POLYSTYRENE manufactured by ARCO POLYMERS as polystyrene balloon, EXPANDABLE POLYSTYRENE BEADS manufactured by BASF WYANDOTE, 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.

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

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

  Although it does not specifically limit as a plasticizer, Depending on the objectives, such as adjustment of a physical property, adjustment of a property, phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; , 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 acids such as adipic acid, azelaic acid, phthalic acid, and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-buta And polyester plasticizers obtained from dihydric alcohols such as vinyl diol; vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone A solvent etc. are mentioned. These solvents may be used during production of the polymer.

  Since the curable composition used in the present invention is excellent in storage stability even at a relatively high temperature, the composition can be handled with a lower viscosity, and is suitable for liquid injection molding at a high temperature.

  In the present invention, when the curable composition is flowed, it is preferably performed at a temperature of 20 ° C. or higher and lower than 100 ° C., but more preferably 40 ° C. or higher and lower than 80 ° C.

  Moreover, in this invention, while making a curable composition flow at the temperature of 20 degreeC or more and less than 100 degreeC, hardening reaction can be performed, further making it flow at 20 degreeC or more. That is, the curable composition of the present invention can be used as a resin for liquid injection molding (LIM or the like).

The curable composition used in the present invention may be prepared as a one-component type in which all the ingredients are pre-blended and stored and heated by curing at the time of curing, to ensure long-term storage stability. May be prepared in the form of two liquids or three liquids or more and mixed before curing.
In the case of preparing as a two-part form, there is no particular limitation on how to divide the ingredients, but when long-term storage stability is required, (B) a hydrosilyl group-containing compound and (C) hydrosilylation The catalyst is divided, and one compounded liquid (referred to as liquid a) is blended with the vinyl polymer (I) as component (A) and the hydrosilylation catalyst as component (C), and the other compounded liquid (liquid b). It is desirable to blend the vinyl polymer (I) as the component (A) and the hydrosilyl group-containing compound as the component (B). The filler containing reinforcing silica as component (D), the curing modifier as component (E), metal soap, plasticizer, anti-aging agent, etc. may be added to either liquid a or liquid b. In consideration of the stability of each component, it may be better to mix the curing regulator of component (E) and metal soap in the liquid b. Since the workability at the time of mixing is improved, it is preferable to adjust the compounding materials of each liquid so that the liquids a and b may be mixed in an equivalent amount, and the viscosity of both liquids should be adjusted to the same level. Is more preferable.

<< Adhesion method >>
In the bonding method of the present invention, the curable composition containing the components (A) to (C) is brought into contact with various metal substrates treated with a primer, and then the curable composition is heated and cured. Features. By this method, excellent adhesion between the cured product and the metal is exhibited, and a composite in which the cured product and the metal are firmly bonded can be easily manufactured.

  In this invention, before making a curable composition contact the metal surface which is a base material, a primer is apply | coated or adhered to a metal surface (primer process). In order to ensure sufficient adhesive strength, the metal surface to be contacted with the curable composition before the primer treatment is subjected to a normal metal surface treatment method, that is, degreasing, sandpapering, various blasting, or various chemical treatments. It is preferable to keep it.

  The method for applying or adhering the primer to the metal surface is not particularly limited as long as the primer film can be formed on the metal surface by an ordinary method such as brush coating, spraying, dipping, roll coating, or pouring.

  In the present invention, after the metal surface is primed as described above, the curable composition is brought into contact with the primer-treated metal surface and cured. Although there is no particular limitation, when the primer contains a solvent, it is preferable that no excess solvent remains on the metal surface with which the curable composition is contacted. After applying to the surface of the substrate, air-dry for 1 minute or longer and then contact the curable composition with this metal surface. After applying the primer to the metal surface, wipe off any excess primer on the surface with a cloth. The method of making a curable composition contact is mentioned.

  The curable composition used in the adhesion method of the present invention is cured by the addition reaction of SiH groups to alkenyl groups capable of hydrosilylation reaction using a hydrosilylation catalyst. Is convenient. The temperature for thermosetting is preferably in the range of 100 ° C to 200 ° C. Since the curable composition of the present invention is excellent in storage stability, the curing reaction hardly proceeds at a temperature lower than 100 ° C. However, when the temperature is about 100 ° C. or higher, the hydrosilylation reaction proceeds rapidly and takes a short time. A cured product can be obtained.

  Various conditions such as the curing time can be appropriately set depending on the amount of the curable composition to be contacted. Moreover, what is necessary is just to use what is normally used in hydrosilylation hardening also about a heating apparatus, a method, etc.

  By the bonding method of the present invention, the curable composition of the present invention hardens and adheres firmly to the surfaces of various metals such as iron, stainless steel, aluminum, nickel, zinc, copper and alloys thereof.

  The bonding method of the present invention can also be used for various molding methods that are generally used to produce a curable composition and a metal as an integrally molded body. 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 composite of the cured product obtained by curing the curable composition obtained by the adhesion method of the present invention and the production method of the present invention and a metal is not particularly limited, but it is an automobile material, an electric / electronic component material. It can be used for various applications such as electrical insulation materials such as insulation coating materials for electric wires and cables, coating materials, foams, potting materials for electrical and electronic use, films, gaskets, casting materials, and various molding materials.

  Furthermore, the bonding method of the present invention can be applied to sealing materials, mainly gaskets and packings.

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

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

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

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

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

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

(Measurement of molecular weight distribution)
The number average molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko) and chloroform as a GPC solvent were used.

(Synthesis Example 1)
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. After 240 minutes from the start of the reaction, 62 mL of acetonitrile, 62 mL of 1,7-octadiene (0.42 mol) and 0.87 mL (4.18 mmol) of triamine were added, followed by continued heating and stirring at 80 ° C., and 620 minutes after the start of the reaction. Heating was 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 copolymer.
The obtained copolymer, Kyoward 500SH (synthetic hydrotalcite, manufactured by Kyowa Chemical Co., Ltd .: 2 parts by weight per 100 parts by weight of the polymer) and Kyoward 700SL (synthetic aluminum silicate, Kyowa) as inorganic synthetic adsorbents. Chemical: 2 parts by weight with respect to 100 parts by weight of the polymer 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, the inorganic synthetic adsorbent was filtered, and the volatile matter in the filtrate was distilled off by heating under reduced pressure. The copolymer was heated and devolatilized at 180 ° C. for 12 hours (decompression degree: 10 torr or less) to desorb Br groups from the copolymer. Kyoward 500SH (synthetic hydrotalcite, manufactured by Kyowa Chemical Co., Ltd .: 3 parts by weight relative to 100 parts by weight of the polymer) and Kyoward 700SL (synthetic aluminum silicate, manufactured by Kyowa Chemical Co., Ltd.) as an inorganic synthetic adsorbent 3 parts by weight with respect to 100 parts by weight of the polymer) was mixed with xylene (100 parts by weight with respect to 100 parts by weight of the polymer) and stirred at 130 ° C. After 5 hours, the inorganic synthetic adsorbent was filtered, and the volatile matter in 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. Moreover, when the number of alkenyl groups introduced per molecule of the copolymer was determined by ¹ H-NMR analysis (Gemini 300, manufactured by Varian Japan), it was 1.9 on average.

(Synthesis Example 2)
A polymer [P2] was obtained in the same manner as in Synthesis Example 1 except for the following compound amounts.
-Butyl acrylate: 336 mL (2.34 mol)
Copper bromide (I): 2.52 g (17.6 mmol)
・ Diethyl 2,5-dibromoadipate: 5.27 g (14.6 mmol)
Triamine: 1.83 mL (8.85 mmol) in total
-Acetonitrile: 168 mL in total
・ 1,7-octadiene: 43 mL (0.29 mol)
The obtained polymer [P2] had a number average molecular weight of 24,000 and a molecular weight distribution of 1.2. The average number of alkenyl groups introduced per molecule of the polymer was determined by ¹ H-NMR analysis and found to be 1.9 on average.

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

(Synthesis Example 4)
1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 5 L two-necked flask, and the mixture was heated and stirred under nitrogen in an oil bath at 120 ° C. To this solution, a mixed 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 [B2]. .
^{From 1} H-NMR analysis, it was found that the hydrosilyl group-containing compound [B2] was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate. (The hydrosilyl group-containing compound [B2] is a mixture, but contains the following compounds having 9 SiH groups in one molecule as a main component).

Example 1
To 100 parts of the copolymer [P1] obtained in Synthesis Example 1, 30 parts of nip seal LP (wet silica, average particle size 9.0 μm, manufactured by Tosoh Silica) as reinforcing silica, tetrakis- [Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 1 part of methane (trade name IRGANOX 1010, manufactured by Ciba Specialty Chemicals) was blended and sufficiently mixed using a planetary mixer. Thereafter, the hydrosilyl group-containing compound [B1] containing an average of 5 hydrosilyl groups and an average of 5 α-methylphenethyl groups in the molecule as the hydrosilyl group-containing compound [B1] The amount of SiH group of the alkenyl group of the copolymer [P1] is 1.8 molar equivalent, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane of zero-valent platinum is added. An isopropanol solution of the complex (containing 3 wt% as platinum) was added in an amount of 5 × 10 ⁻⁴ molar equivalent of the alkenyl group of the copolymer [P1] in terms of platinum, and 3,5-dimethyl-1-hexyne- 150 mol equivalent of 3-ol (trade name Surfynol 61, manufactured by Nissin Chemical) was added to the platinum catalyst, and further uniformly mixed to obtain a curable composition. After the metal plate described in Table 1 was wiped with acetone, it was heated at 180 ° C. for 10 minutes to remove the solvent and moisture on the surface. After applying water as a primer, it was wiped off immediately, and the obtained curable composition was applied thereon, heat-cured at 180 ° C. for 10 minutes, and evaluated for adhesion to metal by manual peeling.

(Example 2)
The curable composition obtained in the same manner as in Example 1 except that 100 parts of the polymer [P2] obtained in Synthesis Example 2 was used as the vinyl polymer (I) instead of the copolymer [P1]. Adhesion was evaluated.

(Example 3)
As hydrosilyl group-containing compound (II), in the same manner as in Example 1, except that 1.8 mol equivalent of hydrosilyl group-containing compound [B2] obtained in Synthesis Example 6 was used instead of hydrosilyl group-containing compound [B1]. The adhesiveness of the obtained curable composition was evaluated.

(Comparative Example 1)
The adhesiveness of the curable composition obtained in the same manner as in Example 1 was evaluated except that water was not applied as a primer to the metal plate.

The adhesiveness of the curable compositions obtained in the above examples and comparative examples was measured as described above. The results are shown in Table 1. The cured product cured on the metal plate is allowed to cool naturally to room temperature, and then the cured product is peeled off by hand. If the cured product is peeled off without remaining on the metal plate, AF (interfacial fracture) occurs. The adhesion was judged as CF (adhesion failure) when the cured product was broken without peeling off the metal plate and the cured product.

From the results of Table 1, it is clear that when the primer is not applied, adhesion to the metal cannot be obtained, but by applying the primer, strong adhesion to the metal plate can be obtained.

The present invention relates to a method for adhering a cured product obtained by curing a curable composition comprising an alkenyl group-containing vinyl polymer capable of hydrosilylation reaction, a hydrosilyl group-containing compound, and a hydrosilylation catalyst to a metal surface. It is.

Claims (20)

(A) a vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule,
(B) a hydrosilyl group-containing compound (II), and
(C) A method for adhering a cured product and a metal, comprising curing a curable composition containing a hydrosilylation catalyst by bringing the curable composition into contact with a metal surface to which a primer is applied or attached. The adhesion method according to claim 1, wherein the molecular weight distribution of the vinyl polymer (I) is less than 1.8. The main chain of the vinyl polymer (I) is mainly a monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. The bonding method according to claim 1, wherein the bonding method is manufactured. The adhesion method according to any one of claims 1 to 3, wherein the vinyl polymer (I) is a (meth) acrylic polymer. The adhesion method according to any one of claims 1 to 4, wherein the vinyl polymer (I) is an acrylic polymer. The adhesion method according to any one of claims 1 to 5, wherein the vinyl polymer (I) is an acrylate polymer. The adhesion method according to any one of claims 1 to 6, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. The adhesion method according to claim 7, wherein the living radical polymerization is atom transfer radical polymerization. The atom transfer radical polymerization is performed using, as a catalyst, a complex selected from the group consisting of transition metal complexes having a central metal of Group 7, Group 8, Group 9, Group 10, or Group 11 of the periodic table, The bonding method according to claim 8. The adhesion method according to claim 9, wherein the transition metal complex is selected from the group consisting of a complex of copper, nickel, ruthenium, or iron. The adhesion method according to claim 10, wherein the transition metal complex is a copper complex. The vinyl polymer (I) has the following steps:
(1a) By polymerizing a vinyl monomer by an atom transfer radical polymerization method, the general formula (1)
-C (R ¹ ) (R ² ) (X) (1)
(Wherein R ¹ and R ² represent a group bonded to an ethylenically unsaturated group of a vinyl monomer; X represents chlorine, bromine or iodine), to produce a vinyl polymer having a terminal structure ,
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group capable of hydrosilylation reaction;
The adhesion method according to any one of claims 1 to 11, which is obtained by the following. The vinyl polymer (I) has the following steps:
(1b) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two alkenyl groups having low polymerizability;
The adhesion method according to any one of claims 1 to 11, which is obtained by the following. The adhesion method according to any one of claims 1 to 13, wherein the vinyl polymer (I) has an alkenyl group capable of hydrosilylation reaction at its terminal. The adhesion method according to any one of claims 1 to 14, wherein the hydrosilyl group-containing compound (II) is an organohydrogenpolysiloxane. The adhesion method according to any one of claims 1 to 15, wherein the primer is an aqueous primer composition. The adhesion method according to any one of claims 1 to 16, wherein the primer is water. The adhesion method according to claim 1, wherein the curable composition further contains (D) reinforcing silica. The adhesion method according to any one of claims 1 to 18, wherein the curable composition further contains (E) a curable modifier. The composite obtained by the adhesion | attachment method as described in any one of Claims 1-19.