JP4800629B2 - Curable composition with improved heat aging resistance - Google Patents

Description

The present invention relates to a curable composition having improved heat aging resistance. More specifically, a (meth) acryloyloxy group-containing vinyl polymer, a polymerization initiator, a phenolic antioxidant, and a sulfur antioxidant are essential components, and heat aging of a cured product obtained from the curable composition. The present invention relates to a curable composition for molding having improved properties.

A molded body mainly composed of a vinyl polymer or a (meth) acrylic polymer can be obtained by kneading and molding a high molecular weight polymer together with various additives in a heated state using a roll or a mill. . A molded product of acrylic rubber containing a (meth) acrylic polymer as a main component can be obtained by kneading a compound such as a filler and a vulcanizing agent into an unvulcanized rubber, followed by heat vulcanization molding. There are problems in workability, such as adhesion to the roll during kneading and difficulty in smoothing during sheeting, poor workability such as non-fluidity during molding, and curing such as low vulcanization speed but easy scorch. There is also a problem with inferiority (Non-Patent Document 1).
In order to solve these problems, if a (meth) acrylic polymer having a highly reactive functional group at the molecular end can be obtained by a simple method, a crosslinkable group can be added to the side chain like conventional acrylic rubber. It is possible to reduce the molecular weight of the main chain itself, because it is possible to obtain a cured product having excellent cured product properties, as well as to effectively obtain the molecular weight between cross-linking points, A curable composition excellent in fluidity can be obtained. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially.

A method for synthesizing a (meth) acrylic polymer having an alkenyl group at both ends using an alkenyl group-containing disulfide as a chain transfer agent is disclosed (Patent Document 1), but the alkenyl group is reliably introduced at both ends. This is not easy, and since the resulting copolymer is latex, it is necessary to remove moisture when used for moldings. In addition, (meth) acrylic polymers having hydroxyl groups at both ends were synthesized using disulfides having hydroxyl groups, and (meth) acrylic having alkenyl groups at both ends using the reactivity of hydroxyl groups. Although a method for synthesizing a polymer is disclosed (Patent Document 2), it is not easy to reliably introduce an alkenyl group at both ends even by this method. There are issues such as the need for cure. In order to solve these problems, a curable composition containing a vinyl polymer containing an alkenyl group at a terminal and a hydrosilyl group-containing compound and curable by a hydrosilylation reaction is disclosed (Patent Document 3, 4). A cured product obtained from such a curable composition is known to have excellent heat aging resistance due to the fact that the main chain is a saturated hydrocarbon. Is not sufficient under actual use conditions, and in order to improve heat aging resistance, it is common to add a phenol-based antioxidant or an amine-based antioxidant (Non-patent Document 2). In particular, in the case of acrylic rubber using a (meth) acrylic polymer, the amine antioxidant p, p'-dicumyldiphenylamine is described as having an excellent effect. Since the agent is highly colored, there is a problem that it cannot be used in applications where white formulation or transparency is required. In addition, a phenolic antioxidant known as an antioxidant that is inferior in antioxidant effect to an amine antioxidant but suppresses coloring may be used for a vinyl polymer having functional groups at both ends. Although disclosed (Patent Document 5), the heat aging resistance is insufficient, and the effect of suppressing coloring is not sufficient.
Japanese Patent Laid-Open No. 5-255415 JP-A-5-262808 JP-A-9-272714 JP 2000-154255 A JP 2003-113324 A Journal of the Japan Rubber Association, Vol. 73, No. 10, 555 (2000) New edition of basic rubber technology, edited by Japan Rubber Association, page 156

The object of the present invention is to contain a vinyl polymer having a (meth) acryloyloxy group at the end, which gives a cured product generally showing good mechanical properties, oil resistance, weather resistance, etc. Another object of the present invention is to provide a curable composition having heat aging resistance that cannot be achieved by a conventional antioxidant in a curable composition that can be cured by heat.

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 solved by using a combination of a phenol-based antioxidant and a sulfur-based antioxidant, and have completed the present invention. .

That is, the present invention
(A) General formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.)
A vinyl polymer (I) having at least one group represented by the formula:
(B) Polymerization initiator (II)
(C) Phenolic antioxidant (D) It is related with the curable composition formed by containing sulfur type antioxidant.
The curable composition of this invention is explained in full detail below.

<< (A) Vinyl Polymer (I) >>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.)
Is a vinyl polymer (I) having at least one group represented by the formula ((meth) acryloyloxy group) per molecule.

The (meth) acryloyloxy group is present at the molecular terminal of the vinyl polymer from the viewpoint of obtaining rubber elasticity by uniformly and increasing the molecular weight between cross-linking points.

R ^a in the (meth) acryloyloxy group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the hydrocarbon 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, an aralkyl group having 7 to 20 carbon atoms, a nitrile group, and the like. And the like.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

Preferable specific examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , — CH ₂ OH, -CN and the like, and more preferably -H, a -CH _3.

<Main chain>
The vinyl polymer (I) in the present invention is a vinyl polymer having at least one (meth) acryloyloxy group per molecule at the molecular end, and the vinyl monomer constituting the main chain is as follows. It does not specifically limit and various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic monomers such as hexadecylethyl; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride Fluorine-containing vinyl monomers such as vinyl trimethoxysilane, vinyl triethoxysilane and other silicon-containing vinyl monomers; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl of fumaric acid Beauty treatment And maleic monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile -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 alone or a plurality of these 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 monomers are preferred from the physical properties of the product. An acrylate monomer and / or a methacrylic acid ester monomer is more preferable, and an acrylate monomer is more preferable. 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.
As a method for introducing a (meth) acryloyloxy group into the obtained vinyl polymer, a method in which an alkenyl group is directly introduced in a polymerization reaction system, a vinyl polymer having a specific functional group is synthesized and specified. And a method of converting the functional group of 1 into an alkenyl group by a one-step or several-step reaction.
Each of these synthesis methods will be described in detail below.

Radical polymerization Synthetic methods of vinyl polymers having functional groups by radical polymerization can be classified into "general radical polymerization" and "controlled radical polymerization".
The “general radical polymerization method” means a vinyl monomer having a specific functional group (hereinafter referred to as “functional monomer”) and another 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 The “general radical polymerization method” is a simple method and can 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. When a small amount of the functional monomer is used, the proportion of the polymer in which a specific functional group is not introduced There is a problem of becoming larger. Moreover, since it is free radical polymerization, there is also 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 carried out 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 the polymer growth terminal grows 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 is required with respect to the initiator, and there are problems 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 in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943; Macromolecules (Macromolecules), using a radical capping agent such as a nitroxide compound as shown in 1994, Vol. 27, p. 7228; “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the characteristics of `` legal method '', it has a halogen which is relatively advantageous for functional group conversion reaction at the end, and has a great degree of freedom in designing initiators and catalysts. It is further preferable as a manufacturing method.
As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614; Macromolecules 1995 28, 7901; 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 those 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 a 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, 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 (3) is obtained.
-C (R ¹ ) (R ² ) (X) (3)
(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 (3) at the other main chain terminal is obtained. Examples of such specific functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

It does not limit as an organic halide which has an alkenyl group as a specific functional group, For example, what has a structure shown in General formula (6) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (6)
(Wherein R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are a hydrogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or each other at the other end. Connected, R ⁸ is —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group, R ⁹ is a direct bond, or A divalent organic group having 1 to 20 carbon atoms, 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 (6) include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. 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 (6) 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 each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) _{n -CH = CH 2, o,} m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) -C _{6 H 4 - (CH 2)} n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) _{n -O- (CH 2) m CH} = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- _{(CH 2) n -CH = CH} 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) _{-C 6 H 4 -O- (CH 2} ) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ ,
(In the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20).

Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (7).
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (7)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , 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 (7) 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, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. In the case where 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 the general formula (7) is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X, CH 2 = CHC (H) (X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3, _{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5, CH 2 = CHC (H) (X) CH (CH 3) 2, CH 2 = CHC ( _{H) (X) C 6 H} 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5, CH 2 = CHCH 2 C (H) (X) -CO 2 R, CH 2 = CH (CH _{2) 2 C (H) (} X) -CO 2 R, CH 2 = CH (CH 2) 3 C (H) (X) -CO 2 R, CH 2 = CH (CH 2) 8 C (H) ( _{X) -CO 2 R, CH 2} = CHCH 2 C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 2 C (H) (X) -C 6 _{H 5, CH 2 = CH (} CH 2) 3 C (H) (X) -C 6 H 5,
(In each of the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

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

It does not specifically limit as an organic halide which has a crosslinkable silyl group as a specific functional group, For example, what has a structure shown to General formula (8) 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 (8)
(In the formula, 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). An organosiloxy group, 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 the general formula (8) is specifically exemplified,
_{XCH 2 C (O) O (} CH 2) n Si (OCH 3) 3, CH 3 C (H) (X) C (O) O (CH 2) n Si (OCH 3) 3, (CH 3) 2 _{C (X) C (O)} O (CH 2) n Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n Si (CH 3) (OCH 3) 2, CH 3 C (H) _{(X) C (O) O} (CH 2) n Si (CH 3) (OCH 3) 2, (CH 3) 2 C (X) C (O) O (CH 2) n Si (CH 3) (OCH ₃ ) ₂ ,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m Si (OCH ₃ ) ₃ , (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OCH ₃ ) ₃ , CH ₃ CH ₂ C (H) (X _{) C (O) O (CH} 2) n O (CH 2) m Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n O (CH 2) m Si (CH 3) (OCH 3 ) ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m —Si (CH ₃ ) (OCH ₃ ) ₂ , (H ₃ C) ₂ C (X) _{C (O) O (CH 2} ) n O (CH 2) m -Si (CH 3) (OCH 3) 2, CH 3 CH 2 C (H) (X) C (O) O (CH _{2) n O (CH 2)} m -Si (CH 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1 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 (9).
_{^{(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 (9)
(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, (CH 3 O) 2 (CH 3) Si (CH 2) 3 C (H _{) (X) -C 6 H 5} , (CH 3 O) 3 Si (CH 2) 4 C (H) (X) -C 6 H 5, (CH 3 O) 2 (CH 3) Si (CH 2) ₄ C (H) (X) -C ₆ H ₅ ,
(In each of the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

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 of the present invention in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator. For example,

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

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. Further preferred are 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. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

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

<Functional group introduction method>
The method for producing the component (A) is not particularly limited. For example, a vinyl polymer having a reactive functional group is produced by the above-described method, and the reactive functional group is a substituent having a (meth) acryloyloxy group. It can manufacture by converting into.
Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

The method for introducing the (meth) acryloyloxy group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.
(Introduction Method 1) Vinyl-based polymer having a halogen group at the terminal, and general formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The method by reaction with the compound shown by these.
As a vinyl polymer having a halogen group at the terminal, the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
Those having a terminal group represented by are preferred.

(Introduction method 2) A vinyl polymer having a hydroxyl group at the terminal, and the general formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The method by reaction with the compound shown by these.
(Introduction method 3) A vinyl-based polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and a general formula (5):
HO-R'- OC (O) C (R ^a ) ═CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The method by reaction with the compound shown by these.

Below, each said method is demonstrated in detail.
[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).
Although there is no limitation in particular in the vinyl polymer which has a halogen group at the terminal, What has a terminal group shown in General formula (3) is preferable.
Examples of the group bonded to the ethylenically unsaturated group of the vinyl monomer in R ¹ and R ² in the general formula (3) include a hydrogen atom, a methyl group, a carbonyl group, a carboxylate group, a toluyl group, a fluoro group, and a chloro group. , Trialkoxysilyl group, phenylsulfonic acid group, carboxylic acid imide group, cyano group and the like.
A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (3), is prepared by using the above-mentioned organic halide or sulfonyl halide compound as an initiator, and a transition metal complex. It is produced by a method of polymerizing a vinyl monomer as a catalyst or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, and the former is preferred.

There is no limitation in particular in the compound represented by General formula (2).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (2) are the same as those described above, and specific examples thereof are also the same as those described above.
M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples thereof include alkali metal ions and quaternary ammonium ions.
Examples of the alkali metal ions include lithium ions, sodium ions, and potassium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like. Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

The usage-amount of the compound shown by General formula (2) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (3), More preferably, it is 1.0-1.2 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).
There is no limitation in particular in the compound represented by General formula (4).
Examples of the organic group having 1 to 20 carbon atoms in ^Ra in General Formula (4) are the same as those described above, and specific examples thereof are also the same as those described above.
The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Although it is produced by a method of polymerizing a vinyl monomer, the former is preferred.

Although there is no limitation in particular in the method of manufacturing the vinyl polymer which has a hydroxyl group at the terminal, For example, the following methods are illustrated.
(A) When synthesizing a vinyl polymer by living radical polymerization, the general formula (10):
_{^{H 2 C = C (R 13}} ) -R 14 -R 15 -OH (10)
Wherein R ¹³ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹⁴ is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹⁵ is a direct bond. Or, it represents a C1-C20 divalent organic group that may contain one or more ether bonds)
A method of reacting a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

R ¹³ is preferably a hydrogen atom or a methyl group. Further, when R ¹⁴ is an ester group, it is a (meth) acrylate compound, and when R ¹⁵ is a phenylene group, it is a styrene compound.
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, it is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, it has a low polymerizable alkenyl group and hydroxyl group in the molecule as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.
Such a compound is not particularly limited. For example, the compound represented by the general formula (11):
_{^{H 2 C = C (R 13}} ) -R 16 -OH (11)
(In the formula, R ¹³ is the same as above, and R ¹⁶ represents a C 1-20 divalent organic group optionally having one or more ether bonds)
And the like.
The compound represented by the general formula (11) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

(C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolyzing or reacting a halogen atom with a hydroxyl group-containing compound.

(D) To a vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization, the general formula (12):
^{M + C - (R 17)} (R 18) -R 16 -OH (12)
(In the formula, R ¹⁶ and M ⁺ are the same as described above, and R ¹⁷ and R ¹⁸ are both an electron-withdrawing group for stabilizing carbanion C ⁻ or one is the electron-withdrawing group, the other is a hydrogen atom, and 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group of
A method in which a halogen is substituted by reacting a stabilized carbanion having a hydroxyl group represented by

Examples of the electron withdrawing group include —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group). ), —NO ₂ (nitro group) and the like, and —CO ₂ R, —C (O) R, and —CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3), preferably a halogen atom at the terminal of the polymer, represented by the general formula (13):
HO-R ^{< 16 >} -O ^- M ^<+> (13)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A hydroxyl group-containing compound represented by
General formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A method in which the halogen atom is substituted with a hydroxyl group-containing substituent by reacting the hydroxyl group-containing compound represented by formula (1).

In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.
In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. Amides, acetonitrile and the like are preferably used.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 3]
In the introduction method 3, a vinyl polymer having a hydroxyl group at a terminal is reacted with a diisocyanate compound, and a residual isocyanate group and a general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
It is the method by reaction with the compound shown by.

Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (5) are the same as those described above, and specific examples thereof are also the same as those described above.
Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And an arylene group having 7 to 20 carbon atoms.
Although there is no limitation in particular in the compound shown by General formula (5), As a particularly preferable compound, 2-hydroxypropyl methacrylate etc. are mentioned.
The vinyl polymer having a hydroxyl group at the terminal is as described above.

The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Examples thereof include xylylene diisocyanate and isophorone diisocyanate. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, with respect to the terminal hydroxyl group of the vinyl polymer.
The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.
The reaction solvent is not particularly limited, but an aprotic solvent is preferred.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

<< (B) Polymerization initiator (II) >>
The polymerization initiator (II) which is the component (B) in the present invention is not particularly limited, but when it is cured by an active energy ray such as UV or electron beam, a photopolymerization initiator is preferable and is cured by heat. In some cases, a thermal polymerization initiator is preferred.

<Photopolymerization initiator>
Although there is no restriction | limiting in particular as a photoinitiator, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is especially preferable.
Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4 -Chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin Tyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1, dibenzoyl and the like.
Examples of the photoanion initiator include 1,10-diaminodecane, 4,4′-trimethylenedipiperidine, carbamates and derivatives thereof, cobalt-amine complexes, aminooxyiminos, ammonium borates and the like. .

These initiators may be used alone, in combination of two or more, or in combination with other compounds. As a combination when used in combination with other compounds, specifically, a combination with an amine such as diethanolmethylamine, dimethylethanolamine, or triethanolamine, and further a combination with an iodonium salt such as diphenyliodonium chloride, Examples include a combination with a dye such as methylene blue and an amine.

In addition, when using the said photoinitiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, and para tertiary butyl catechol, can also be added as needed.

Moreover, you may use a near-infrared light absorptive cationic dye as a near-infrared photoinitiator. As the near-infrared light absorbing cationic dye, near-infrared light which is excited by light energy in the region of 650 to 1500 nm, for example, disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

The addition amount of the photopolymerization initiator is not particularly limited since it only needs to slightly functionalize the system, but is preferably 0 with respect to 100 parts by weight of the vinyl polymer (I) as the component (A). 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight.

<Thermal polymerization initiator>
Although it does not specifically limit as a thermal-polymerization initiator, An azo initiator, a peroxide initiator, a persulfate initiator, and a redox initiator are contained.
Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2, 2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis (2- Cyclopropylpropionitrile), 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries), etc. I can get lost.

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Examples thereof include oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), t-butyl peroxyisopropyl monocarbonate (trade name Perbutyl I, manufactured by NOF Corporation), and dicumyl peroxide.

Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.
Suitable redox (oxidation) initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; Examples include systems based on tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.
Other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.

Of the above thermal polymerization initiators, those selected from the group consisting of azo initiators and peroxide initiators are preferred. More preferred are 2,2'-azobis (methylisobutyrate), benzoyl peroxide, t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof. is there.

The thermal polymerization initiator used in the present invention is added in a catalytically effective amount, and although such amount is not limited, typically, the vinyl polymer (I) of the present invention and other When the total amount of the monomer and / or oligomer mixture described below that can be added is 100 parts by weight, it is preferably about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight. In addition, when the mixture of initiators is used, it is preferable that the total amount of the mixture of initiators exists in the said range.

<< (C) Phenolic Antioxidant >>
The phenolic antioxidant as component (C) in the present invention is not particularly limited, and any one can be used. However, from the viewpoint of heat aging resistance, a hindered phenol structure or a single hindered phenol structure is formed in the molecule. Preference is given to phenolic antioxidants.
Specific examples of these compounds include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α Methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tris -[N- (3,5-di-tert-butyl-4-hydroxybenzyl)] isocyanurate, 1,1,3-tris- (2-mes 4-hydroxy-5-tert-butylphenyl) butane, butylidene-1,1-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], octadecyl-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-bis- [ 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-to Methyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), benzenepropanoic acid, 3,5-bis (1,1- Dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] 1,3,5-triazine-2,4,6-trione, 2,4-bis- (n-octylthio) − -(4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxy Benzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) -ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,6- Bis [(octylthio) methyl] o-cresol, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like.

In terms of product names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330 (and above) All are manufactured by Asahi Denka Kogyo), IRGANOX-1010, IRGANOX-1035, IRGANOX-1076, IRGANOX-1098, IRGANOX-1135, IRGANOX-1330, IRGANOX-1520L, IRGANOX-2 5, IRGANOX-259, IRGANOX-3114, IRGANOX-3790, IRGANOX-565 (all of which are manufactured by Ciba Specialty Chemicals), Smizer BHT, Smizer S, Smizer BP-76, Smizer MDP-S, Smizer GM, Smizer GS, Smizer Examples thereof include, but are not limited to, BBM-S, Sumilyzer WX-R, Sumilyzer BP101, Sumilyzer GA-80 (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

These phenolic antioxidants may be used alone or in combination of two or more. Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, in which the molecular weight of the phenolic antioxidant is 600 or more from the viewpoint of further improving heat aging resistance, Tris- [N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl -4-hydroxybenzyl) benzene, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4 , 8,10-tetraoxaspiro [5,5] undecane is more preferred.
In addition, the said molecular weight can be measured using GC-MS or LC-MS.

Although there is no restriction | limiting in particular as a compounding quantity of a phenolic antioxidant, Preferably it is 0.1-10 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.5-5 weight part. When the blending amount is less than 0.1 parts by weight, the effect of improving the heat aging resistance may not be sufficient. When the blending amount exceeds 10 parts by weight, the cured product obtained from the curable composition may be markedly colored. is there.

<< (D) Sulfur-based antioxidant >>
There is no restriction | limiting in particular as a sulfur type antioxidant which is (D) component in this invention, Although arbitrary things can be used, since a thiol structure affects sclerosis | hardenability, it does not have a thiol structure, and is a thioether. A compound having a structure in the molecule is preferred.
Specific examples of the sulfur antioxidant include 4,4′-thiobis (3-methyl-6-tert-butylphenol), dilauryl-thiodipropionate, bis {2-methyl-4- [3- n- alkyl _{(C 12} or _{C 14)} thio propionyloxy] -5-tert-butylphenyl} sulfide, pentaerythrityl - tetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate , Distearyl-thiodipropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis [(octylthio) methyl] o-cresol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, dimyristyl-3,3'-thiodipropionate, di-butyl methylene - bis - thioglycolate, distearyl - thiodipropionate, and the like.

In terms of product names, Nocrack 300, Nocrack 400 (all of which are manufactured by Ouchi Shinsei Chemical Industry) ADK STAB AO-23, AO-412S, AO-503A (all of which are manufactured by Asahi Denka Kogyo Co., Ltd.), IRGANOX-PS800FL, IRGANOX -PS802FL, IRGANOX-1035, IRGANOX-1520L, IRGANOX-565 (all of which are manufactured by Ciba Specialty Chemicals), Sumilyzer TPL-R, Sumilyzer TPS, Sumilyzer TPM, Sumilyzer WX-R, Sumilyzer TP-D (all of which are Sumitomo Chemical) Industrial) and Vulcanol 88 (manufactured by Bayer) can be exemplified, but are not limited thereto.

These sulfur-based antioxidants may be used alone or in combination of two or more. From the viewpoint of further improving heat aging resistance, pentaerythrityl-tetrakis (3-laurylthiopropionate) in which the molecular weight of the sulfur-based antioxidant is 1000 or more is more preferable.
In addition, the measuring method of molecular weight is the same as what was described by the above-mentioned phenolic antioxidant.

Although there is no restriction | limiting in particular as a compounding quantity of a sulfur type antioxidant, Preferably it is 0.1-10 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.5-5 weight part. When the blending amount is less than 0.1 parts by weight, the effect of improving the heat aging resistance may not be sufficient, and when it exceeds 10 parts by weight, the curability may be affected.

Although there is no restriction | limiting in particular in the use ratio of the phenolic antioxidant which is (C) component, and the sulfur type antioxidant which is (D) component, From the point of improving heat aging resistance more effectively, phenolic oxidation The ratio of the inhibitor / sulfur antioxidant is preferably in the range of 0.1 to 10, particularly preferably 0.3 to 3.

As a preferred combination of the phenolic antioxidant as component (C) and the sulfurous antioxidant as component (D), tetrakis- [methylene-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate] methane and pentaerythrityl-tetrakis (3-laurylthiopropionate); tris- [N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate and penta Combination of erythrityl-tetrakis (3-laurylthiopropionate); 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and pentaerythrityl-tetrakis (3 A combination of laurylthiopropionate). This combination is extremely excellent in that it retains rubber elasticity for a long time even in a heat aging test at 175 ° C., and there is little or no coloring after the heat test.

<< (E) Reinforcing Silica >>
The curable composition of the present invention may further contain (E) reinforcing silica as necessary.
Examples of the reinforcing silica as the component (E) include fumed silica and precipitated silica. Among these, those having a particle diameter of 50 μm or less and a specific surface area of 80 m ² / g or more are preferable from the viewpoint of reinforcing effect.
Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it is easy to exhibit fluidity suitable for molding.
More specific examples of the reinforcing silica include, but are not particularly limited to, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Sil, Ltd., Japan Silica Industry Co., which is one of precipitated silicas. .
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 (E) may be used independently and may be used together 2 or more types.

<< Curable composition >>
In the curable composition of the present invention, various additives such as polymerizable monomers and / or oligomers, flame retardants, light stabilizers, ultraviolet absorbers, fillers, plasticizers, physical properties are used for adjusting physical properties. Conditioner, adhesion promoter, storage stability improver, solvent, radical inhibitor, metal deactivator, ozone degradation inhibitor, phosphorus peroxide decomposer, lubricant, pigment, foaming agent, photo-curing resin Etc. may be appropriately blended as necessary. These various additives may be used alone or in combination of two or more.

<Polymerizable monomer and / or oligomer>
The curable composition of the present invention is not limited, but for the purpose of improving surface curability, imparting toughness, improving workability by reducing viscosity, and the like, a polymerizable monomer and / or oligomer as necessary. Can further be contained.
As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferable.

Examples of radical polymerizable groups include acrylic functional groups such as (meth) acryloyl groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, and vinyl halides. Group, vinylidene halide group and the like. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.
Examples of the anionic polymerizable group include an acrylic functional group such as a (meth) acryloyl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, and a vinyl ketone group. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Specific examples of the above monomers include (meth) acrylate monomers, cyclic acrylates, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, halogenated Examples thereof include vinyl / vinylidene halide monomers and polyfunctional monomers.

(Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth ) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , Phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) acrylic Benzyl, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, ( Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meta ) 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate , Perfluoromethyl (meth) acrylate, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, Examples include (meth) acrylic acid 2-perfluorohexadecylethyl. Moreover, the compound etc. which are shown by the following Formula can also be mentioned. In the following formula, n represents an integer of 0-20.

Examples of the styrenic monomer include styrene and α-methylstyrene.
Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate.
Examples of the acrylamide monomer include acrylamide and N, N-dimethylacrylamide.
Examples of the conjugated diene monomer include butadiene and isoprene.
Examples of the vinyl ketone monomer include methyl vinyl ketone.
Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

Multifunctional monomers include trimethylolpropane triacrylate, neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexa Chlorate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1 , 3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetra Chi glycol diacrylate, 1,9-nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene diisocyanate A urethane resin obtained from a hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.)} Examples thereof include urethane acrylate resins obtained by reaction; resins in which (meth) acrylic groups are introduced into the above polyols through ester bonds; polyester acrylate resins and the like.

The number average molecular weight of the monomer and / or oligomer having an acrylic functional group is preferably 5000 or less. Further, in the case of using a monomer for improving the surface curability and reducing the viscosity for improving workability, it is more preferable that the molecular weight is 1000 or less because of good compatibility.
The amount of the polymerizable monomer and / or oligomer used is 100 parts by weight of component (A) from the viewpoints of viscosity reduction of the blend, curability of the cured product, toughness, mechanical properties, weather resistance, oil resistance, and heat resistance. On the other hand, 0.1-100 weight part is preferable.

<Metal soap>
The curable composition of 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 one or more selected from the group consisting of calcium stearate, magnesium stearate, and zinc stearate from the viewpoint of economy. 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 of the present invention, various fillers may be used as necessary in addition to the reinforcing silica as the component (E).
The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, graphite, clay, silica (crystalline silica, fused silica, dolomite, silicic anhydride, water content Reinforcing fillers such as silicic acid, carbon black, etc .; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, bengara , Aluminum fine powder, Flint powder, Zinc oxide, Active zinc white, Zinc powder, Zinc carbonate, Shirasu balloon and other fillers; Asbestos, Glass fiber, Glass filament, Carbon fiber, Kevlar fiber, Polyethylene fiber, etc. Etc.
Of these fillers, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

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

Moreover, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added.
In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength and breaking elongation of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the breaking strength and breaking elongation of the cured product.
Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved and the storage stability effect of the curable composition is further improved as compared with the case where calcium carbonate that is not surface-treated is used. I think that.

As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. Salts of these fatty acids such as sodium and potassium; alkyl esters of these fatty acids. Specific examples of surfactants include polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, and sulfate-type anionic surfactants such as sodium salts and potassium salts thereof; alkylbenzene sulfonic acids and alkylnaphthalene sulfones. Examples thereof include acids, paraffin sulfonic acids, α-olefin sulfonic acids, alkyl sulfosuccinic acids, and the like, and sulfonic acid type anionic surfactants such as sodium salts and potassium salts thereof.
The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability improvement effect may not be sufficient, and when it exceeds 20% by weight, the storage stability of the curable composition may be lowered.

Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is preferably used when the effect of improving the thixotropy of the blend, the breaking strength of the cured product, the elongation at break and the like is particularly expected.
On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, use the following as necessary. be able to.

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

Further, although not particularly limited, for example, if a combination of heavy calcium carbonate and colloidal calcium carbonate having a specific surface area value of 1.5 m ² / g or more as required, 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>
To the curable composition of the present invention, fine hollow particles can be added in combination with these reinforcing fillers for the purpose of reducing the weight and cost without causing a significant decrease in physical properties.
Such fine hollow particles (hereinafter sometimes referred to as “balloons”) are not particularly limited, but have a diameter as described in “Latest Technology for Functional Fillers” (CMC). Examples thereof include hollow bodies (inorganic balloons and organic balloons) made of inorganic or organic materials of 1 mm or less, preferably 500 μm or less, more preferably 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and it is more preferable to use a micro hollow body having a 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 made by Sumitomo 3M, Cellstar Z-28 made by Sumitomo 3M, and MICRO made by EMERSON & CUMING. BALLON, PELTSBURGE CORNING's CELAMIC GLASSMMODULES, 3M's GLASS BUBBLES, Asahi Glass's Q-CEL, Taiheiyo Cement's E-SPHERES, Fly Ash Balloon's, PERAMARKET's CEROSPHERES S. FILLITE manufactured by A, BW manufactured by Showa Denko as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA as a zirconia balloon, clecas sphere manufactured by Kureha Chemical Co., Ltd. and boss sphere manufactured by GENERAL TECHNOLOGIES as a carbon balloon are commercially available.

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

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

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

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

Among them, 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.

The amount of the plasticizer used is not limited, but is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). is there. If it is less than 5 parts by weight, the effect as a plasticizer tends to be difficult to develop, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient.

<Solvent>
A solvent can be mix | blended with the curable composition of this invention as needed.
Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone Is mentioned. These solvents may be used during production of the polymer.

<Adhesive agent>
When the curable composition of the present invention is used alone as a molding rubber, it is not particularly necessary to add an adhesion-imparting agent. However, when it is used for two-color molding with a different type of substrate, a vinyl heavy It is possible to add an adhesion-imparting agent to such an extent that the crosslinking reaction of the combined (I) is not significantly inhibited and the physical properties of the resulting cured product are not significantly affected.
Although it will not specifically limit as an adhesive provision agent which can be mix | blended, if adhesiveness is provided to a curable composition, Adhesion provision resin and a crosslinkable silyl group containing compound are preferable.

The adhesion-imparting resin is not particularly limited, but specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester. Examples thereof include resins.

Although it does not restrict | limit especially as a crosslinkable silyl group containing compound, A silane coupling agent is preferable. Specific examples thereof include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkyl such as dimethyldiisopropenoxysilane and methyltriisopropenoxysilane. Isopropenoxysilane; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; Silicone varnishes; polysiloxanes and the like.

In addition, an organic group having an atom other than a carbon atom and a hydrogen atom such as an epoxy group, an isocyanate group, an isocyanurate group, a carbamate group, an amino group, a mercapto group, a carboxyl group, a halogen group, and a (meth) acryl group in the molecule; A silane coupling agent having a crosslinkable silyl group can be used.

Specifically, alkoxysilanes having an epoxy group include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- Epoxysilanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; having an isocyanate group Alkoxysilanes include isocyanates such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane. Group-containing silanes; as alkoxysilanes having an isocyanurate group, isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; as alkoxysilanes having an amino group, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)- γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane N-phenyl-γ-amino Amino group-containing silanes such as propyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; alkoxysilanes having a mercapto group include γ-mercapto Mercapto group-containing silanes such as propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; alkoxy-silanes having a carboxyl group include β-carboxyl Carboxysilanes such as ethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; Examples of alkoxysilanes having a gen group include halogen-containing silanes such as γ-chloropropyltrimethoxysilane; examples of alkoxysilanes having a (meth) acryl group include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxy. Propyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane And (meth) acrylic group-containing silanes.

In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. .
Among these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness.
These may be used alone or in combination of two or more.

Moreover, in order to further improve adhesiveness, a crosslinkable silyl group condensation catalyst can be used in combination with the above-mentioned adhesiveness-imparting agent. Examples of the crosslinkable silyl group condensation catalyst include organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimethoxide, tin octylate; organoaluminum compounds such as aluminum acetylacetonate; tetraisopropoxytitanium, tetrabutoxytitanium And organic titanium compounds.

The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). If the amount is less than 0.01 part by weight, the effect of improving the adhesiveness is small, and if it exceeds 20 parts by weight, the physical properties of the cured product tend to be lowered. More preferably, it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.
The adhesiveness-imparting agent may be used alone or in combination of two or more.

<< Curing method >>
Although the curable composition of this invention is not specifically limited, It is preferable to harden | cure by active energy rays, such as UV and an electron beam, or a heat | fever. A cured product can be obtained by curing the curable composition in this manner.

<Active energy ray curing>
In the case of curing with active energy rays, it is preferable to contain a photopolymerization initiator as (B) polymerization initiator (II).
The active energy ray source is not particularly limited. An electron beam irradiation etc. are mentioned.

<Heat curing>
In the case of curing by heat, it is preferable to contain a thermal polymerization initiator as (B) polymerization initiator (II).
The thermosetting conditions are not particularly limited, but the temperature varies depending on the type of the thermal polymerization initiator used, the vinyl polymer (I) and the compound to be added, etc., but preferably within the range of 50 ° C to 250 ° C. A range of 70 ° C to 200 ° C is more preferable. The curing time varies depending on the thermal polymerization initiator, monomer, solvent, reaction temperature, etc. used, but is usually in the range of 1 minute to 10 hours.

<< Molding method >>
The molding method when the curable composition of the present invention is used as a molded body is not particularly limited, and various commonly used molding methods can be used. Examples thereof include cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, and thermoforming. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.

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

Furthermore, the molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings.
For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. Engine parts can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts.

In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake 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 Oil packing for combustion equipment such as heater packing, steam outlet seal, etc., O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube Speaker gaskets, speaker edges, turntables for sound equipment such as diaphragm valves and air pipes Over door, belts, pulleys, and the like.

In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like.
In the sports field, it can be used for all-weather pavement materials, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. as ball for ball games.
In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like.

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

The curable composition of the present invention contains a vinyl polymer having at least one (meth) acryloyloxy group per molecule and at the molecular end, and exhibits good mechanical properties, oil resistance, weather resistance, etc. Further, the curable composition of the present invention contains a combination of specific antioxidants, and can provide a cured product having excellent hardness retention and non-colorability in a heat aging resistance test. it can.

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.

[Number average molecular weight and 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.
[Average number of terminal (meth) acryloyloxy groups]
The average number of terminal (meth) acryloyloxy groups is the number of (meth) acryloyloxy groups introduced per polymer molecule, and was calculated based on the number average molecular weight determined by ¹ H-NMR analysis and GPC.

[Heat resistance aging test]
Three 2 cm × 2 cm square sheets were cut out from the cured sheets obtained in the following examples and comparative examples, and the samples were subjected to 150 ° C. (SHPS-212, manufactured by Tabai) or 175 ° C. oven (High-Spec HT310, Applied Engineering Laboratory). (Made by Sangyo Co., Ltd.) and allowed to stand for a predetermined time, and the hardness change and the colorability were examined.
1) Change in hardness When the sample was allowed to stand in an oven at 150 ° C., the sample after 500 hours, 1000 hours, and 2000 hours was evaluated by finger touch. When the sample was left in an oven at 175 ° C., the sample after 168 hours and after 500 hours was evaluated by finger touch. Specifically, the evaluation by finger touch was performed by leaving the square sheet taken out of the oven in a constant temperature room (23 ° C.) for 1 hour, and then pressing each sheet with a finger and pulling it by hand to obtain rubber elasticity and a sample. The hardness was evaluated by sensory evaluation. A soft sample having rubber elasticity was soft, and a sample that had lost rubber elasticity and was hard was evaluated in four stages. From the soft order, soft <slightly hard <pretty hard <hard.
2) Colorability The appearance of the sample before and after exposure to a high temperature state (standing in an oven at 150 ° C. or 175 ° C.) was visually observed to evaluate the colorability. Specifically, when the sample is allowed to stand in a 150 ° C. oven, the appearance of the sample is observed before being left in the 150 ° C. oven (initial stage) and after being left in the 150 ° C. oven for 500 hours. did. When the sample was allowed to stand in a 175 ° C. oven, the appearance of the sample was observed before being left in the 175 ° C. oven (initial stage) and after 168 hours after being left in the 175 ° C. oven. The coloration of the sample was evaluated in six levels, with the lightest sample being colorless and the sample losing rubber elasticity and having the most intense color as black. Brown <dark brown <black.

[Production Example 1] (Synthesis of acryloyloxy group-terminated poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) (25/46/29))
Cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate as initiator, n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in 25 / mole Polymerization was performed at a ratio of 46/29 to obtain a terminal bromine group poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a number average molecular weight of 21,000 and a molecular weight distribution of 1.16.
400 g of this polymer was dissolved in N, N-dimethylacetamide (400 mL), 10.7 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. A mixture of -butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [1]) was obtained. After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. Toluene in the filtrate was distilled off under reduced pressure to purify the polymer [1].
The purified acryloyloxy group both-end polymer [1] has a number average molecular weight of 21,400, a molecular weight distribution of 1.17, and an average number of terminal acryloyloxy groups of 1.8 (that is, the introduction rate of acryloyloxy groups at the ends is 90). %)Met.

[Production Example 2] (Synthesis of n-butyl polyacrylate with both ends of acryloyloxy group)
A polymer [2] was obtained in the same manner as in Production Example 1 except that n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in Production Example 1 was changed to only n-butyl acrylate. The purified polymer [2] had a number average molecular weight of 27,100, a molecular weight distribution of 1.31, and an average number of terminal acryloyloxy groups of 2.0.

[Production Example 3] (Synthesis of acryloyloxy group both terminal poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) (48/2/50))
N-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate (25/46/29 in moles) of Production Example 1 was converted to n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate (in moles). The polymer [3] was obtained in the same manner as in Production Example 1 except that the ratio was changed to 48/2/50). The purified polymer [3] had a number average molecular weight of 28,000, a molecular weight distribution of 1.20, and an average number of terminal acryloyloxy groups of 1.9.

[Production Example 4] (Synthesis of acryloyloxy group both terminal polyethyl acrylate)
A polymer [4] was obtained in the same manner as in Production Example 1 except that n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in Production Example 1 was changed to only ethyl acrylate. The purified polymer [4] had a number average molecular weight of 15,300, a molecular weight distribution of 1.28, and an average number of terminal acryloyloxy groups of 1.8.

[Production Example 5] (Synthesis of 2-methoxyethyl acrylate with both ends of acryloyloxy group)
A polymer [5] was obtained in the same manner as in Production Example 1 except that n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in Production Example 1 was changed to 2-methoxyethyl acrylate alone. . The purified polymer [5] had a number average molecular weight of 17,800, a molecular weight distribution of 1.26, and an average number of terminal acryloyloxy groups of 1.9.

Example 1
To 100 parts of the polymer [1] obtained in Production Example 1, 20 parts of Aerosil R974 (average particle diameter of 12 nm: made by Nippon Aerosil) as reinforcing silica and calcium stearate (trade name SC-100, 堺1) Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (trade name IRGANOX 1010, manufactured by Ciba Specialty Chemicals) as a phenolic antioxidant 1 part of pentaerythrityl-tetrakis (3-laurylthiopropionate) (trade name Sumitizer TP-D, manufactured by Asahi Denka Kogyo Co., Ltd.) as a sulfur-based antioxidant, and further using three paint rolls Mixed. Thereafter, 0.5 part of t-butyl peroxyisopropyl monocarbonate (trade name Perbutyl I, manufactured by NOF Corporation) was added as a thermal polymerization initiator, and further mixed uniformly to obtain a curable composition.
The curable composition thus obtained is sufficiently degassed in a vacuum oven at 50 ° C., then poured into a mold, press vulcanized at a temperature of 180 ° C. for 10 minutes, and then in a 180 ° C. oven. After vulcanization for 22 hours, a rubber-like cured sheet having a thickness of about 2 mm was obtained.
The obtained cured sheet was subjected to a heat aging resistance test at 150 ° C. The results are shown in Table 1.

(Examples 2 to 8)
A rubber-like cured product sheet is produced in the same manner as in Example 1 except that A1 to A3 shown below as phenolic antioxidants and a1 to a4 as sulfur antioxidants are used in the amounts (parts) shown in Table 1. Then, a heat aging resistance test at 150 ° C. was performed. The results are shown in Table 1.

Example 9
A rubber-like cured product sheet was produced in the same manner as in Example 1 except that 100 parts of the polymer [2] obtained in Production Example 2 was used instead of the polymer [1] as the vinyl polymer (I). A heat aging resistance test at 150 ° C. was performed. The results are shown in Table 1.

(Example 10)
A rubbery cured material sheet was produced in the same manner as in Example 1 except that 100 parts of the polymer [3] obtained in Production Example 3 was used instead of the polymer [1] as the vinyl polymer (I). A heat aging resistance test at 150 ° C. was performed. The results are shown in Table 1.

(Example 11)
A rubber-like cured product sheet was produced in the same manner as in Example 1 except that 100 parts of the polymer [4] obtained in Production Example 4 was used instead of the polymer [1] as the vinyl polymer (I). A heat aging resistance test at 150 ° C. was performed. The results are shown in Table 1.

(Example 12)
A rubber-like cured material sheet was produced in the same manner as in Example 1 except that 100 parts of the polymer [5] obtained in Production Example 5 was used instead of the polymer [1] as the vinyl polymer (I). A heat aging resistance test at 150 ° C. was performed. The results are shown in Table 1.

(Example 13)
Instead of the t-butyl peroxyisopropyl monocarbonate of Example 1 (trade name Perbutyl I, manufactured by NOF Corporation) as a thermal polymerization initiator, benzoyl peroxide (trade name: NIPER BW, manufactured by NOF Corporation) was used, and the curing temperature was 180. A rubber-like cured material sheet was produced in the same manner as in Example 1 except that the temperature was changed to 100 ° C., and a heat aging resistance test at 150 ° C. was performed. The results are shown in Table 1.

(Comparative Examples 1 to 13)
A rubber-like cured product sheet was produced in the same manner as in Example 1 except that the antioxidant was blended in the types and blending amounts shown in Table 2, and a heat aging resistance test at 150 ° C. was performed. The results are shown in Table 2.

From the comparison of Table 1 and Table 2, the following is clear. When a phenolic antioxidant is used alone as an antioxidant, in a 150 ° C. heat resistance test, the ability to retain rubber elasticity is low with a small amount, and it becomes a hard resin after 500 to 1000 hours (Comparative Examples 1 to 11). ). Further, when the blending amount (part) of the phenolic antioxidant was increased in order to maintain rubber elasticity, the time for maintaining rubber elasticity was extended, but the cured product was colored after the heat aging resistance test. The amine-based antioxidant (B1), which is a general antioxidant for acrylic rubber, maintained a rubber elasticity even after 2000 hours, but exhibited a dark brown color from the beginning (Comparative Examples 12 and 13). However, when the phenolic antioxidant and the sulfurous antioxidant were used in combination, the rubber elasticity was maintained even after 2000 hours, and even after the heat test, there was little coloration (Examples 1 to 1). 13).

(Examples 14 to 25)
A rubber-like cured product sheet was prepared in the same manner as in Example 1 except that A1 to A6 shown below as phenolic antioxidants and a1 to a2, a5, and a6 as sulfur antioxidants were used in the amounts shown in Table 3. A heat aging resistance test was performed at 175 ° C. The results are shown in Table 3.

(Comparative Examples 14-23)
A rubber-like cured product sheet was produced in the same manner as in Example 1 except that the antioxidant was blended in the types and blending amounts shown in Table 4, and a heat aging resistance test at 175 ° C. was performed. The results are shown in Table 4.

From the comparison of Table 3 and Table 4, the following is clear. When a phenolic antioxidant alone was used as an antioxidant, the ability to retain rubber elasticity was low with a small amount and the resin was hardened after 168 hours (Comparative Example 14). Moreover, even when the number of blending parts was increased in order to maintain rubber elasticity, after 500 hours it was hardened into a resin and the cured product was colored (Comparative Examples 15 to 17). When the amine antioxidant (B1), which is a general antioxidant for acrylic rubber, is used alone, the rubber elasticity is lost after 168 hours in a small amount, and the rubber elasticity is maintained by increasing the amount. However, dark brown was exhibited from the beginning (Comparative Examples 18 to 20). When the sulfur-based antioxidant was used in combination with the amine-based antioxidant, the initial coloration was improved, but a dark brown color was exhibited after the heat aging resistance test (Comparative Examples 21 and 22). Further, when the sulfur-based antioxidant was used alone, the rubber elasticity was not retained after the heat aging resistance test, and coloring could not be prevented (Comparative Example 23). However, when a phenolic antioxidant and a sulfurous antioxidant are used in combination, the rubber elasticity is maintained even after 168 hours, and a phenolic antioxidant (A1, A2, A3) having a molecular weight of 600 or more and a molecular weight of 1000 or more. When the sulfur-based antioxidant (a1) was combined, rubber elasticity was maintained even after 500 hours, and coloring could be improved (Examples 14 to 25).

(Example 26)
To 100 parts of the polymer [1] obtained in Production Example 1, tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (product) as a phenolic antioxidant 1 part of the name IRGANOX 1010, manufactured by Ciba Specialty Chemicals), 1 part of dilauryl-thiodipropionate (trade name Sumitizer TPL-R, manufactured by Sumitomo Chemical Co., Ltd.) as the sulfur-based antioxidant, and 2, 2 as the radical photopolymerization initiator -0.5 part of diethoxyacetophenone was added and mixed uniformly to obtain a curable composition.
The curable composition thus obtained was sufficiently degassed in a vacuum oven at 50 ° C. and then poured into a mold, and a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min). ) Was irradiated three times to obtain a rubber-like cured product sheet having a thickness of about 2 mm.
The obtained cured sheet was subjected to a heat aging resistance test at 150 ° C. As a result, even after 2000 hours, the hardness change due to finger touch was a soft sample having rubber elasticity, and the coloration was light brown.

(Comparative Example 24)
A rubber-like cured material sheet was obtained in the same manner as in Example 26 except that dilauryl-thiodipropionate (trade name: Sumilizer TPL-R, manufactured by Sumitomo Chemical Co., Ltd.) was not added as a sulfur-based antioxidant.
The obtained cured sheet was subjected to a heat aging resistance test at 150 ° C. As a result, the hardness change due to finger touch was hard without rubber elasticity in 1000 hours. The coloration was brown after 500 hours.

<Phenolic antioxidant>
A1: Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (trade name IRGANOX1010, manufactured by Ciba Specialty Chemicals, molecular weight 1178)
A2: 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetra Oxaspiro [5,5] undecane (trade name: Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd., molecular weight 741)
A3: Tris- [N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate (trade name ADK STAB AO-20, manufactured by Asahi Denka Kogyo, molecular weight 784)
A4: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (trade name IRGANOX 1330, manufactured by Ciba Specialty Chemicals, molecular weight 775)
A5: 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) (trade name Sumitizer MDP-S, manufactured by Sumitomo Chemical Co., Ltd., molecular weight 341)
A6: 4,4′-Butylidenebis (3-methyl-6-tert-butylphenol) (trade name Sumitizer BBM-S, manufactured by Sumitomo Chemical Co., Ltd., molecular weight 383)
A7: 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX259, manufactured by Ciba Specialty Chemicals, molecular weight 639)
A8: Triethylene glycol-bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (trade name IRGANOX245, manufactured by Ciba Specialty Chemicals, molecular weight 587)

<Sulfur-based antioxidant>
a1: Pentaerythrityl-tetrakis (3-lauryl thiopropionate) (trade name Sumitizer TP-D, manufactured by Sumitomo Chemical Co., Ltd., molecular weight 1162)
a2: Distearyl-thiodipropionate (trade name Sumitizer TPS, manufactured by Sumitomo Chemical Co., Ltd., molecular weight 683)
a3: 4,6-bis [(octylthio) methyl] o-cresol (trade name IRGANOX 1520L, manufactured by Ciba Specialty Chemicals, molecular weight 425)
a4: 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX 1035, manufactured by Ciba Specialty Chemicals, molecular weight 643)
a5: Dilauryl-thiodipropionate (trade name Sumitizer TPL-R, manufactured by Sumitomo Chemical Co., Ltd., molecular weight 515)
a6: Dimyristyl-3,3′-thiodipropionate (trade name Sumitizer TPM, manufactured by Sumitomo Chemical Co., Ltd., molecular weight 571)

<Other antioxidants: amine-based antioxidants>
B1: 4,4 ′-(α, α-dimethylbenzyl) diphenylamine (trade name NOCRACK CD, manufactured by Ouchi Shinsei Chemical Industry, molecular weight 406)

The curable composition of the present invention provides a cured product exhibiting good mechanical properties, oil resistance, weather resistance, etc., and also provides a cured product excellent in retention of hardness and non-colorability in a heat aging resistance test. is there.

Claims (18)

(A) General formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.)
A vinyl polymer (I) obtained by polymerizing a monomer having at least one group represented by the formula :
(B) 0.001 to 10 parts by weight of a radical photoinitiator with respect to 100 parts by weight of the vinyl polymer (I), or a monomer capable of adding a thermal polymerization initiator to the vinyl polymer (I) and / or 0.01 to 5 parts by weight based on 100 parts by weight of the total oligomer mixture,
(C) 0.1 to 10 parts by weight of an antioxidant having a hindered phenol structure or a hindered phenol structure in the molecule with respect to 100 parts by weight of the vinyl polymer (I), and (D) a thioether structure A curable composition comprising 0.1 to 10 parts by weight of an antioxidant not containing a thiol structure with respect to 100 parts by weight of the vinyl polymer (I) . The curable composition of claim 1 wherein the molecular weight distribution of vinyl Le polymer (I) is less than 1.8. Vinyl Le polymer (I) is (meth) acrylate curable composition according to any one of claims 1-2, characterized in that Le is a polymer. Vinyl Le polymer (I) is curable composition according to any one of claims 1 to 3, characterized in that an acrylic Le polymer. Vinyl Le polymer (I) is curable composition according to any one of claims 1-4, characterized in that the acrylic acid ester le polymer. Vinyl Le polymer main chain curable composition according to any one of claims 1 to 5, characterized in that those produced by living radical polymerization method (I). The curable composition according to claim 6 , wherein the living radical polymerization is atom transfer radical polymerization. Vinyl Le polymer (I) is, the following steps:
The vinyl Le polymer having a halogen group at the end,
General formula (2)
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.)
Reacting a compound represented by:
The curable composition according to any one of claims 1 to 7, which is a vinyl Le polymer obtained by. Vinyl Le polymer having a halogen group at the end has the general formula (3)
-CR ¹ R ² X (3)
(Wherein, R ^1, R ² is a group bonded to an ethylenically unsaturated group of vinyl makes the chromophore at the distal end Nomar .X represents chlorine atom, bromine atom, or iodine atom.)
The curable composition of Claim 8 which has group shown by these. Vinyl Le polymer (I) is, the following steps:
The vinyl Le polymer having terminal hydroxyl groups,
General formula (4)
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. X ¹ represents a chlorine atom, a bromine atom, or a hydroxyl group.)
Reacting a compound represented by:
The curable composition according to any one of claims 1 to 7 , wherein the curable composition is produced by the method. Vinyl Le polymer (I) the following steps:
(1) the vinyl Le polymer having terminal hydroxyl groups, is reacted with a diisocyanate compound,
(2) Residual isocyanate group and general formula (5)
HO-R'- OC (O) C (R ^a ) ═CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ′ represents a divalent organic group having 2 to 20 carbon atoms.)
Reacting with a compound of formula;
The curable composition according to any one of claims 1 to 7 , wherein the curable composition is produced by the method. The curable composition according to any one of claims 1 to 11, wherein the photopolymerization initiator is a photoradical initiator. The curable composition according to any one of claims 1 to 11 , wherein the photopolymerization initiator is a photoanion initiator. The thermal polymerization initiator is at least one selected from the group consisting of an azo-based initiator, a peroxide initiator, a persulfate initiator, and a redox initiator . The curable composition as described in any one . The curable composition according to any one of claims 1 to 14 , wherein the antioxidant (C ) has a molecular weight of 600 or more. Antioxidant (D ) is molecular weight 1000 or more, The curable composition as described in any one of Claims 1-15 . Furthermore, according reinforcing silica, in any one of claims 1 to 16, characterized in that it contains 0.1 parts by weight of the vinyl polymer (I) 100 parts by weight of component (E) Curable composition. Cured product obtained from the curable composition according to any one of claims 1 to 17.