JPH1180571A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition containing a vinylic polymer having crosslinkable silyl groups at the molecular terminals in a high ratio as a main component. SOLUTION: This curable composition contains a vinylic polymer having crosslinkable silyl groups represented by formula I: -[Si(R<3> )2-b (Y)b O]m Si(R<4> )3-a (Y) [R<3> and R<4> are each a l-20C alkyl group, a 6-20C aryl group, a 7-20C aralkyl group, or a triorganosiloxy group of the formula: (R')3 Si- (R' is a 1-20C hydrocarbon group); Y is a hydroxyl group or a hydrolyzable group; (a) is 0-3; (b) is 0-2; (m) is 0-19, wherein (a)+(m)(b)>=1] at the terminals. The vinylic polymer having the croslinkable groups represented by formula I at the terminals is obtained by the following processes. (1) A vinylic monomer is polymerized in the presence of an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst to produce a vinylic polymer having terminal structures of formula II: -C(R<1> )(R<2> )(X) (R<1> , R<2> are each a group bound to the ethylenic unsaturated group of the vinylic monomer; X is chlorine, bromine or iodine). (2) The halogen in the group of formula II is converted into the silyl group-containing substituent in the group of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition mainly comprising a vinyl polymer having a crosslinkable silyl group at a molecular terminal and providing a cured product having excellent weather resistance.

[0002]

2. Description of the Related Art As moisture-curable liquid polymers having a crosslinkable silyl group at a terminal, polysiloxane-based, polyoxypropylene-based, and polyisobutylene-based polymers are already known. However, curable compositions using these have many problems. Polysiloxane type has weather resistance, heat resistance,
Although it is excellent in cold resistance and flexibility, it still has problems in stainability and paintability due to bleeding of low molecular components. Polyoxypropylene-based resins are excellent in flexibility, paintability, and stain resistance, but have insufficient weather resistance, and cannot be used particularly for applications around glass. Although polyisobutylene-based materials are characterized by weather resistance and permeability resistance, they have problems that they have extremely high viscosity and are difficult to handle, and that one-packing is difficult.

[0003]

A moisture-curable composition which solves these problems and is excellent in weather resistance and heat resistance, and which can be made into one liquid and which is easy to handle, has a crosslinkable silyl group at the terminal. A curable composition containing an acrylic polymer as a main component has been proposed (for example, Japanese Patent Publication No. 3-140).
68, Japanese Patent Publication 5-72427, Japanese Patent Publication 4-55444,
JP-A-6-212922). JP-B-3-14068 and JP-B5-72427 disclose a mercaptan-based chain transfer agent having a crosslinkable silyl group, a disulfide-based chain transfer agent having a crosslinkable silyl group, and an azo-based polymerization initiator having a crosslinkable silyl group. A curable composition obtained by using an acrylic polymer having a crosslinkable silyl group at a terminal as a main component is disclosed. It is difficult to introduce a silyl group, and a cured product having satisfactory physical properties cannot be obtained. In Japanese Patent Publication No. 4-55444,
A curable composition containing, as a main component, an acrylic polymer having a crosslinkable silyl group at a terminal obtained by using a hydrosilane having a crosslinkable silyl group or a tetrahalosilane as a chain transfer agent is disclosed. However, even in this method, it is difficult to introduce a crosslinkable silyl group at a high ratio into the terminal of the polymer. Therefore, the curability of the composition prepared therefrom is not sufficient, and properties such as weather resistance inherent to the acrylic polymer are impaired. JP 6
In -212922, a terminal group obtained by converting a hydroxyl group of a (meth) acrylic polymer having a hydroxyl group at a terminal obtained by using a large excess of a hydroxyl group-containing polysulfide chain transfer agent with respect to an initiator. A curable composition containing a (meth) acrylic polymer having a crosslinkable silyl group as a main component is disclosed. In this method, a crosslinkable silyl group is introduced into the terminal at a relatively high ratio, but a large amount of an expensive chain transfer agent must be used, which is a problem in the production process.

Accordingly, it is an object of the present invention to solve these problems and to provide a curable composition containing, as a main component, a vinyl polymer having a high ratio of crosslinkable silyl groups at its terminals.

[0005]

The above object can be achieved by using a curable composition containing a vinyl polymer having a crosslinkable silyl group at a terminal represented by the general formula 1 as a main component. _{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1) ( wherein, R ³ and R ⁴ are both 1 carbon atoms An alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ Si—
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R 'groups may be the same, shows a triorganosiloxy group represented by different may be), when R ³ or R ⁴ there are two or more, they may be the same , May be different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0,
1, 2, or 3 and b represents 0, 1, or 2. m is an integer of 0-19. However, a + mb ≧ 1
Is satisfied. ) The vinyl polymer having a crosslinkable silyl group at the terminal represented by the general formula 1 can be prepared by the following steps: By polymerization, a vinyl polymer having a terminal structure represented by the general formula 2 is produced; -C (R ¹ ) (R ² ) (X) (2) (wherein R ¹ and R ² are vinyl X represents chlorine, bromine, or iodine.) (2) converting a halogen of the general formula 2 into a silyl group-containing substituent represented by the general formula 1; The resulting polymer is used.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The curable composition of the present invention contains a vinyl polymer having a crosslinkable silyl group represented by the general formula 1 at the terminal. _{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1) ( wherein, R ³ and R ⁴ are both 1 carbon atoms An alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ Si—
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R 'groups may be the same, shows a triorganosiloxy group represented by different may be), when R ³ or R ⁴ there are two or more, they may be the same , May be different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0,
1, 2, or 3 and b represents 0, 1, or 2. m is an integer of 0-19. However, a + mb ≧ 1
Is satisfied. The hydrolyzable group represented by Y is not particularly limited, and a conventionally known hydrolyzable group can be used.
Hydrogen, a halogen atom, an alkoxy group, an acyloxy group,
Ketoximate group, amino group, amide group, acid amide group,
Examples thereof include an aminooxy group, a mercapto group, and an alkenyloxy group. An alkoxy group is particularly preferable in that it has mild hydrolyzability and is easy to handle. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and a + mb, that is, the total of the hydrolyzable groups is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one, or two or more. In the case of silicon atoms linked by a siloxane bond, the number may be up to about 20.

The monomer constituting the main chain of the vinyl polymer having a crosslinkable silyl group at the terminal represented by the general formula 1 is not particularly limited, and various monomers can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate,
N-butyl (meth) acrylate, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate,
N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth)
Phenyl acrylate, toluyl (meth) acrylate,
Benzyl (meth) acrylate, (meth) acrylic acid-2
-Methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane,
Ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate,
Perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (Meth) acrylic acid-based monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrene,
Styrene-based monomers such as vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride;
Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl Maleimide monomers such as maleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; acrylamide; Vinyl monomers containing an amide group such as methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate Le, vinyl esters such as vinyl cinnamate, ethylene, alkenes such as propylene, butadiene, conjugated dienes such as isoprene, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of them may be copolymerized. Among them, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers. In such a case, it is preferable that these preferable monomers are contained in a weight ratio of 40%.

The molecular weight distribution of the vinyl polymer, that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is usually less than 1.8, preferably 1. 7 or less, more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. G in the present invention
In the PC measurement, chloroform is usually used as a mobile phase, and a polystyrene gel column is used, 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 is not particularly limited,
The range of 500 to 1,000,000 is preferable, and 100
0-100,000 is more preferable.

The vinyl polymer having a crosslinkable silyl group at the terminal of the general formula 1 can be obtained by the above-mentioned production method. In the present invention, the following steps are used: (1) an organic halide or Radical polymerization of a vinyl monomer with a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst to produce a vinyl polymer having a terminal structure represented by the general formula 2; -C (R ¹ ) (R ² ) (X) (2) (in the formula, R ^1, R ² represents a group bonded to an ethylenically unsaturated group of a vinyl monomer. in addition, X represents chlorine, bromine, or iodine.) (2 A) converting the halogen of the general formula 2 into a crosslinkable silyl group-containing substituent represented by the general formula 1;

R ¹ and R ² may be, for example, a vinyl-based monomer having a terminal structure represented by the general formula 2 used in the production of a vinyl-based polymer.
In the polymerization using a halide as a chain transfer agent (telogen), a method using carbon tetrachloride, methylene chloride, carbon tetrabromide, methylene bromide, etc. is known. In this method, halogen is surely added to both terminals. It is difficult to introduce.

In contrast to this method, the use of atom transfer radical polymerization, which has been energetically studied recently, ensures that a halogen is introduced at the terminal (for example, Matyja).
szewski et al. Am. Chem. Soc. 19
95, 117, 5614, Macromolecule
s 1995, 28, 7901, Science 19
96, 272, 866, or Sawamoto et al.
Macromolecules 1995, 28, 17
21). According to these methods, in general, the polymerization rate is very high, and the polymerization proceeds in a living manner and the molecular weight distribution is narrow (Mw / Mn =
1.1-1.5) A polymer is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position) Alternatively, a sulfonyl halide compound is used as an initiator. In order to obtain a crosslinkable vinyl polymer using this polymerization method, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. Specific examples thereof include o
_{-, m-, p-XCH 2} -C 6 H 4 -CH 2 X, o-, m
_{-, p-CH 3 C (} H) (X) -C 6 H 4 -C (H)
_{(X) CH 3, o-,} m-, p- (CH 3) 2 C (X) -
C ₆ H ₄ —C (X) (CH ₃ ) ₂ (wherein,
₆ H ₄ is a phenylene group, X is chlorine, bromine, or iodine) RO ₂ CC (H) (X)-(CH ₂ ) _n -C (H)
_{(X) -CO 2 R, RO} 2 C-C (CH 3) (X) - (C
_{H 2) n -C (CH 3} ) (X) -CO 2 R, RC (O) -C
(H) (X) - ( CH 2) n -C (H) (X) -C (O)
R, RC (O) -C ( CH 3) (X) - (CH 2) n -C
(CH ₃ ) (X) —C (O) R, wherein R is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, n is an integer of 0 to 20, X is chlorine, bromine, Iodine) XCH ₂ —C (O) —CH ₂ X, H ₃ C—C (H) (X)
—C (O) —C (H) (X) —CH ₃ , (H ₃ C) ₂ C
(X) -C (O) -C (X) (CH 3) 2, C 6 H 5 C
(H) (X) - ( CH 2) n -C (H) (X) C 6 H 5,
(Where X is chlorine, bromine or iodine, and n is 0 to 20)
XCH ₂ CO ₂ — (CH ₂ ) _n —OCOCH ₂ X, CH ₃ C
_{(H) (X) CO 2} - (CH 2) n -OCOC (H)
_{(X) CH 3, (CH} 3) 2 C (X) CO 2 - (CH 2) n -
OCOC (X) (CH ₃ ) ₂ , wherein n is 1 to 20
XCH ₂ C (O) C (O) CH ₂ X, CH ₃ C (H)
(X) C (O) C (O) C (H) (X) CH ₃ , (C
H ₃ ) ₂ C (X) C (O) C (O) C (X) (CH ₃ ) ₂ ,
_{o-, m-, p-XCH 2} CO 2 -C 6 H 4 -OCOCH 2
X, o-, m-, p- CH 3 C (H) (X) CO 2 -C 6
_{H 4 -OCOC (H) (X} ) CH 3, o-, m-, p-
_{(CH 3) 2 C (X} ) CO 2 -C 6 H 4 -OCOC (X)
_{(CH 3) 2, o-,} m-, p-XSO 2 -C 6 H 4 -SO 2
X, wherein X is chlorine, bromine or iodine, and the like.

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably 7
It is a metal complex complex having a Group 7, 8, 9, 10 or 11 element as a central metal. More preferably,
Examples thereof include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine and the like for enhancing the catalytic activity A ligand such as a polyamine is added. Tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ )
Are also suitable as catalysts. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Furthermore, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and bistriphenylphosphine complex of divalent nickel (NiCl
₂ (PPh ₃ ) ₂ ) and bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ ) are also suitable as the catalyst.

The vinyl monomer used in the polymerization is not particularly limited, and any of those already exemplified can be suitably used. The polymerization reaction can be performed without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene;
Ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ethylene carbonate And carbonate-based solvents such as propylene carbonate. These can be used alone or in combination of two or more. The polymerization can also be carried out in an emulsion system or a system using a supercritical fluid CO ₂ as a medium.

[0015] The polymerization can be carried out in the range of 0 to 200 ° C, preferably in the range of room temperature to 150 ° C. The vinyl polymer having a crosslinkable silyl group of the formula 1 at the terminal can be obtained by converting the halogen of the vinyl polymer having a halogen at the terminal obtained by the above polymerization into a crosslinkable silyl group.

As such a conversion method, a vinyl polymer having a terminal structure represented by the general formula 2 is obtained by radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. A method in which a compound having both a polymerizable alkenyl group and a crosslinkable silyl group is reacted as a second monomer. The second monomer is
After the first polymerization is completed and the polymer is isolated, it may be added together with a catalyst and newly reacted, or may be added during the polymerization (in-situ) and reacted. In the latter case, the higher the monomer conversion in the first polymerization, the better, preferably 80% or more. If it is at most 80%, the crosslinkable silyl groups will be distributed not in the molecular terminals but in the side chains, and the mechanical properties of the cured product will be impaired. In a compound having such a polymerizable alkenyl group and a crosslinkable silyl group, a crosslinkable silyl group is introduced into all terminals in principle by adding an equal amount to the number of all terminals. In order to surely introduce a functional group, it is preferable to use an excess amount, specifically, 1 to 5 times the number of terminals. If it is used five times or more, a crosslinkable group is introduced into the terminal of the polymer at a high density, which is not preferable in terms of physical properties of a cured product.

Such a compound having both a polymerizable alkenyl group and a crosslinkable silyl group is not particularly limited, but specific examples include the following general formula 3: H ₂ C ＝ C (R ⁵ ) ^{-R 6 -R 7 - [Si (} R 3) 2-b (Y) b O] m -Si (R 4) 3-a (Y) a (3) ( wherein, R ^3, R ^4, Y , a, b, m are as defined above, R ⁵
Is hydrogen or a methyl group, R ⁶ is —C (O) O—, or o-, m-, p-phenylene group, R ⁷ is a direct bond,
Alternatively, a divalent organic group having 1 to 20 carbon atoms may contain one or more ether bonds. )). When R ⁶ is —C (O) O— (ester group), it is a (meth) acrylate compound, and when R ⁶ is a phenylene group, it is a styrene compound. R ⁷
As is methylene, ethylene, alkylene groups such as propylene, o-, m-, p-phenylene group, aralkyl groups such as benzyl _{group, -CH 2 CH 2 -O-CH} 2 - or -O-
Examples thereof include an alkylene group containing an ether bond such as CH ₂ —.

The hydrolyzable group represented by Y is not particularly limited, and any of those already exemplified can be suitably used. Among them, an alkoxy group is particularly preferable because of its mild hydrolyzability and easy handling. The hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and the sum of a + mb, that is, the sum of the hydrolyzable groups is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one, or two or more. In the case of silicon atoms connected by a siloxane bond, the number may be up to about 20.

Among them, H ₂ C ＝ C (H) CO _2- (CH ₂ ) _n -S is preferred in that the reactivity of the hydrolyzable silyl group is mild and easy to handle and easy to obtain.
_{i (OCH 3) 3, H} 2 C = C (H) CO 2 - (CH 2) n -
_{Si (CH 3) (OCH 3} ) 2, H 2 C = C (H) CO 2 -
_{(CH 2) n -Si (OC} 2 H 5) 3, H 2 C = C (H) CO
_{2 - (CH 2) n -Si} (CH 3) (OC 2 H 5) 2, H 2 C =
_{C (H) CO 2 - (} CH 2) n -Si (OC 3 H 7) 3, H 2
_{C = C (H) CO 2} - (CH 2) n -Si (CH 3) (OC
_{3 H 7) 2, H 2} C = C (CH 3) CO 2 - (CH 2) n -Si
_{(OCH 3) 3, H 2} C = C (CH 3) CO 2 - (CH 2) n
—Si (CH ₃ ) (OCH ₃ ) ₂ , H ₂ C = C (CH ₃ ) C
O _2- (CH ₂ ) _n -Si (OC ₂ H ₅ ) ₃ , H ₂ C = C (C
_{H 3) CO 2 - (CH} 2) n -Si (CH 3) (OC
_{2 H 5) 2, H 2} C = C (CH 3) CO 2 - (CH 2) n -Si
_{(OC 3 H 7) 3,} H 2 C = C (CH 3) CO 2 - (CH 2) n
—Si (CH ₃ ) (OC ₃ H ₇ ) ₂ (wherein n is 2
20 _{integer) H 2 C = C (H} ) CO 2 - (CH 2) n -O- (CH 2) m -
_{Si (OCH 3) 3, H} 2 C = C (H) CO 2 - (CH 2) n
_{-O- (CH 2) m -Si (} CH 3) (OCH 3) 2, H 2 C
_{= C (H) CO 2 -} (CH 2) n -O- (CH 2) m -Si
_{(OC 2 H 5) 3,} H 2 C = C (H) CO 2 - (CH 2) n -
_{O- (CH 2) m -Si (} CH 3) (OC 2 H 5) 2, H 2 C
_{= C (H) CO 2 -} (CH 2) n -O- (CH 2) m -Si
_{(OC 3 H 7) 3,} H 2 C = C (H) CO 2 - (CH 2) n -
_{O- (CH 2) m -Si (} CH 3) (OC 3 H 7) 2, H 2 C
_{= C (CH 3) CO 2} - (CH 2) n -O- (CH 2) m -S
_{i (OCH 3) 3, H} 2 C = C (CH 3) CO 2 - (CH 2)
_{n -O- (CH 2) m -Si} (CH 3) (OCH 3) 2, H 2
_{C = C (CH 3) CO} 2 - (CH 2) n -O- (CH 2) m -
_{Si (OC 2 H 5) 3} , H 2 C = C (CH 3) CO 2 - (CH
_{2) n -O- (CH 2)} m -Si (CH 3) (OC 2 H 5) 2,
_{H 2 C = C (CH 3} ) CO 2 - (CH 2) n -O- (CH 2)
_{m -Si (OC 3 H 7)} 3, H 2 C = C (CH 3) CO 2 -
_{(CH 2) n -O- (CH} 2) m -Si (CH 3) (OC 3 H
₇ ) ₂ (In the above formulas, n is an integer of 1 to 20, and m is 2-2.
0 integer) o-, m-, p-H 2 C = CH-C 6 H 4 - (CH 2) n -
_{Si (OCH 3) 3, o-} , m-, p-H 2 C = CH-C 6
_{H 4 - (CH 2) n} -Si (CH 3) (OCH 3) 2, o-,
_{m-, p-H 2 C =} CH-C 6 H 4 -O- (CH 2) n -S
_{i (OCH 3) 3, o-} , m-, p-H 2 C = CH-C 6 H
₄ —O— (CH ₂ ) _n —Si (CH ₃ ) (OCH ₃ ) ₂ (where C ₆ H ₄ is a phenylene group, and n is 2 to 2
Integer of 0. Is preferred.

Another method for converting the terminal halogen represented by the general formula 2 into a crosslinkable silyl group includes a reaction with a stabilized carbanion represented by the general formula 4. ^{M + C - (R 8)} (R 9) -R 10 -C (R 11) -CH 2 - [Si (R 3) 2-b (Y) b O] m -Si (R 4) 3-a (Y) _a (4) (wherein, R ³ , R ⁴ , Y, a, b, and m are the same as those described above;
⁸ and R ⁹ together carbanion C ^- or an electron withdrawing group stabilizing, or one of the electron-withdrawing group at the other is hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group,, R ¹⁰ is a direct bond A divalent organic group having 1 to 10 carbon atoms, which may contain one or more ether bonds, R ¹¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
An aryl group of 10 or an aralkyl group of 7 to 10 carbon atoms, M ⁺ is an alkali metal ion or a quaternary ammonium ion) R ⁸ and R ⁹ are at least one of electron withdrawing groups for stabilizing a carbanion. For example, -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. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms.
And preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ⁸ and R ⁹ , —CO ₂ R, —C (O) R, and —CN are particularly preferable.

M ⁺ is a carbanion counter cation;
Examples thereof include alkali metal ions such as lithium ion, sodium ion, and potassium ion, and quaternary ammonium ions such as tetramethylammonium ion, tetraethylammonium ion, and trimethylbenzylammonium ion. The carbanion of the general formula 4 can be obtained by allowing a basic compound to act on the precursor and extracting an active proton.

The precursor of the carbanion represented by the general formula 4 is as follows: (CH ₃ O) ₃ Si
_{(CH 2) n -CH (CO} 2 C 2 H 5) 2, (CH 3 O) 3 Si
(CH ₂ ) _n CH (CO ₂ CH ₃ ) ₂ , o-, m-, p-
(CH ₃ O) ₃ SiCH ₂ CH ₂ —C ₆ H ₄ —CH (CO ₂ C
_{H 3) 2, o-, m-} , p- (CH 3 O) 3 SiCH 2 CH 2
_{-C 6 H 4 -CH (CO 2} C 2 H 5) 2, o-, m-, p-
(CH ₃ O) ₃ SiCH ₂ CH ₂ —C ₆ H ₄ —CH ₂ CH (C
O ₂ CH ₃ ) ₂ , o-, m-, p- (CH ₃ O) ₃ SiCH ₂
CH ₂ —C ₆ H ₄ —CH ₂ CH (CO ₂ C ₂ H ₅ ) ₂ , (CH _{3
O) 3 Si (CH 2)} n -CH (C (O) CH 3) (CO 2
_{CH 3), (CH 3 O} ) 3 Si (CH 2) n -CH (C
(O) CH ₃ ) (CO ₂ C ₂ H ₅ ), o-, m-, p- (C
_{H 3 O) 3 SiCH 2 CH} 2 -C 6 H 4 -CH (C (O) CH
₃ ) (CO ₂ C ₂ H ₅ ), o-, m-, p- (CH ₃ O) ₃ S
iCH ₂ CH ₂ —C ₆ H ₄ —CH ₂ CH (C (O) CH ₃ )
(CO ₂ C ₂ H ₅ ), (CH ₃ O) ₃ Si (CH ₂ ) _n CH
_{(C (O) CH 3)} 2, o-, m-, p- (CH 3 O) 3 S
iCH ₂ CH ₂ —C ₆ H ₄ —CH (C (O) CH ₃ ) ₂ , o
_{-, m-, p- (CH 3} O) 3 SiCH 2 CH 2 -C 6 H 4 -
CH ₂ CH (C (O) CH ₃ ) ₂ , (CH ₃ O) ₃ Si (C
H ₂ ) _n CH (CN) (CO ₂ C ₂ H ₅ ), o-, m-, p
_{- (CH 3 O) 3 SiCH} 2 CH 2 -C 6 H 4 -CH (CN)
(CO ₂ C ₂ H ₅ ), o-, m-, p- (CH ₃ O) ₃ Si
CH ₂ CH ₂ —C ₆ H ₄ —CH ₂ CH (CN) (CO ₂ C
_{2 H 5), (CH 3} O) 3 Si (CH 2) n CH (CN) 2,
_{o-, m-, p- (CH 3} O) 3 SiCH 2 CH 2 -C 6 H 4
_{-CH (CN) 2, o-,} m-, p- (CH 3 O) 3 Si
_{CH 2 CH 2 -C 6 H 4} -CH 2 CH (CN) 2, (CH
₃ O) ₃ Si (CH ₂ ) _n CH ₂ NO ₂ , o-, m-, p-
(CH ₃ O) ₃ SiCH ₂ CH ₂ —C ₆ H ₄ —CH ₂ NO ₂ , o
_{-, m-, p- (CH 3} O) 3 SiCH 2 CH 2 -C 6 H 4 -
_{CH 2 CH 2 NO 2, (} CH 3 O) 3 Si (CH 2) n -CH
(C ₆ H ₅ ) (CO ₂ C ₂ H ₅ ), o-, m-, p- (CH ₃
O) ₃ SiCH ₂ CH ₂ —C ₆ H ₄ —CH (C ₆ H ₅ ) (CO ₂
C ₂ H ₅ ), o-, m-, p- (CH ₃ O) ₃ SiCH ₂ C
_{H 2 -C 6 H 4 -CH 2} CH (C 6 H 5) (CO 2 C 2 H 5),
_{(CH 3 O) 2 (CH} 3) Si (CH 2) n -CH (CO 2 C
_{2 H 5) 2, (CH} 3 O) 2 (CH 3) Si (CH 2) n CH
(CO ₂ CH ₃ ) ₂ , o-, m-, p- (CH ₃ O) ₂ (C
_{H 3) SiCH 2 CH 2 -C} 6 H 4 -CH (CO 2 CH 3) 2,
_{o-, m-, p- (CH 3} O) 2 (CH 3) SiCH 2 CH
_{2 -C 6 H 4 -CH (CO} 2 C 2 H 5) 2, o-, m-, p-
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 -C 6 H 4 -CH 2
CH (CO ₂ CH ₃ ) ₂ , o-, m-, p- (CH ₃ O) ₂
(CH ₃ ) SiCH ₂ CH ₂ —C ₆ H ₄ —CH ₂ CH (CO _{2
C 2 H 5) 2, (} CH 3 O) 2 (CH 3) Si (CH 2) n -C
H (C (O) CH ₃ ) (CO ₂ CH ₃ ), (CH ₃ O)
_{2 (CH 3) Si (CH} 2) n -CH (C (O) CH 3)
(CO ₂ C ₂ H ₅ ), o-, m-, p- (CH ₃ O) ₂ (C
_{H 3) SiCH 2 CH 2 -C} 6 H 4 -CH (C (O) CH 3)
(CO ₂ C ₂ H ₅ ), o-, m-, p- (CH ₃ O) ₂ (C
_{H 3) SiCH 2 CH 2 -C} 6 H 4 -CH 2 CH (C (O) C
H ₃ ) (CO ₂ C ₂ H ₅ ), (CH ₃ O) ₂ (CH ₃ ) Si
(CH ₂ ) _n CH (C (O) CH ₃ ) ₂ , o-, m-, p-
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 -C 6 H 4 -CH
_{(C (O) CH 3)} 2, o-, m-, p- (CH 3 O)
_{2 (CH 3) SiCH 2 CH} 2 -C 6 H 4 -CH 2 CH (C
(O) CH ₃ ) ₂ , (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ )
_n CH (CN) (CO ₂ C ₂ H ₅ ), o-, m-, p- (C
_{H 3 O) 2 (CH 3} ) SiCH 2 CH 2 -C 6 H 4 -CH (C
_{N) (CO 2 C 2 H} 5), o-, m-, p- (CH 3 O) 2
_{(CH 3) SiCH 2 CH 2} -C 6 H 4 -CH 2 CH (CN)
(CO ₂ C ₂ H ₅ ), (CH ₃ O) ₂ (CH ₃ ) Si (C
H ₂ ) _n CH (CN) ₂ , o-, m-, p- (CH ₃ O) _{2
(CH 3) SiCH 2 CH 2} -C 6 H 4 -CH (CN) 2, o
_{-, m-, p- (CH 3} O) 2 (CH 3) SiCH 2 CH 2
—C ₆ H ₄ —CH ₂ CH (CN) ₂ , (CH ₃ O) ₂ (C
H ₃ ) Si (CH ₂ ) _n CH ₂ NO ₂ , o-, m-, p-
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 -C 6 H 4 -CH 2
_{NO 2, o-, m-, p-} (CH 3 O) 2 (CH 3) SiC
_{H 2 CH 2 -C 6 H 4} -CH 2 CH 2 NO 2, (CH 3 O)
_{2 (CH 3) Si (CH} 2) n -CH (C 6 H 5) (CO 2 C 2
_{H 5), o-, m-,} p- (CH 3 O) 2 (CH 3) SiC
_{H 2 CH 2 -C 6 H 4} -CH (C 6 H 5) (CO 2 C 2 H 5),
_{o-, m-, p- (CH 3} O) 2 (CH 3) SiCH 2 CH
(In the formula, n represents an integer of 1 to _{10) 2 -C 6 H 4 -CH 2} CH (C 6 H 5) (CO 2 C 2 H 5) , and the like.

The proton is extracted from the above compound,
Various basic compounds are used in order to obtain a carbanion. These basic compounds include: potassium,
Alkali metals such as sodium and lithium; sodium methoxide, potassium methoxide, lithium methoxide,
Metal alkoxides such as sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium tert-butoxide, potassium tert-butoxide; carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate; sodium hydroxide, water Hydroxides such as potassium oxide; hydrides such as sodium hydride, potassium hydride, methyllithium, ethyllithium; n
Organic metals such as -butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide; ammonia; alkylamines such as trimethylamine, triethylamine and tributylamine; polyamines such as tetramethylethylenediamine and pentamethyldiethylenetriamine; Examples thereof include pyridine compounds such as picoline. The amount of the base used may be an equivalent amount or a small excess amount with respect to the precursor, and is preferably 1 to 1.2 equivalents.

A carbanion represented by the general formula 1 is prepared by reacting a basic compound on the above precursor, and reacted with a halogen-terminated vinyl polymer represented by the general formula 2 to obtain the desired compound represented by the general formula 4 And a vinyl polymer having a crosslinkable silyl group at the terminal. An organic halide, or a sulfonyl halide compound as an initiator, a method for producing a vinyl polymer, which comprises radically polymerizing a vinyl monomer using a transition metal complex as a catalyst, wherein an organic halide having a crosslinkable silyl group is used. When used as an initiator, a vinyl polymer having a crosslinkable silyl group at one terminal and the other terminal having the structure of Formula 2 can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into a crosslinkable silyl group-containing substituent, a vinyl polymer having a crosslinkable silyl group at both terminals can be obtained. As the conversion method, the method already described can be used.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, an organic halide having a structure represented by the general formula 5 is exemplified. ^{R 12 R 13 C (X)} -R 14 -R 7 -C (H) (R 5) CH 2 - [Si (R 3) 2- b (Y) b O] m -Si (R 4) 3- _a (Y) _a (5) (wherein, R ³ , R ⁴ , R ⁵ , R ⁷ , a, b, m, X and Y are the same as above, and R ¹² and R ¹³ are hydrogen or carbon number. 1-20
An alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, or those mutually linked at the other end, wherein R ¹⁴ is -C (O) O-, -C (O)
-Or o-, m-, p-phenylene group) In these compounds, the carbon to which the halogen is bonded is bonded to the carbonyl group or the phenyl group, and the carbon-halogen bond is activated to cause polymerization. Start.

Specific examples of the substituents R ¹² and R ¹³ include hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl and hexyl. R ¹² and R ¹³ may be linked at the other end to form a cyclic skeleton. In such a case, —R ¹² —R ¹³ — is, for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH _2- , -CH _{2
CH 2 CH 2 CH 2 -,} - CH 2 CH 2 CH 2 CH 2 CH 2 -,
Etc. are exemplified.

To specifically illustrate the compound of formula 5,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ , CH ₃
C (H) (X) C (O) O (CH ₂ ) _n Si (OC
H 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 (C
H 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 each of the above formulas, X is chlorine, bromine, iodine, n
Is an integer of 0 to 20.) XCH ₂ C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OC
H 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 , C
H 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, m is an integer of 0 to 20) o, m , P-XCH ₂ —C ₆ H ₄ — (CH ₂ ) ₂ Si (OC
_{H 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 (OC
_{H 3) 3, o, m} , p-XCH 2 -C 6 H 4 - (CH 2) 3 S
_{i (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-C
_{H 3 CH 2 C (H)} (X) -C 6 H 4 - (CH 2) 3 Si (O
_{CH 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 (O
_{CH 3) 3, o, m} , p-XCH 2 -C 6 H 4 -O- (C
_{H 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 (O
_{CH 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).

Further examples of the organic halide having a crosslinkable silyl group include those having a structure represented by the following general formula 6. ^{_{(R 4) 3-a (}} Y) a Si- [OSi (R 3) 2-b (Y) b] m -CH 2 - C (H) (R 5) -R 7 -C (R 12) ( ^{X) -R 14 -R 13 (6} ) ( ^{wherein, R 3, R 4, R} 5, R 7, R 12, R 13, R 14, a,
b, m, X, and Y are the same as above. If such a compound is specifically exemplified, (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) -C
O 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 S
_{i (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 (C
H ₃₎ Si (CH ₂₎ at _{4 C (H) (X)} -C 6 H 5 ( above equations, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group Aralkyl group).

When an organic halide having a crosslinkable silyl group is used as an initiator, a polymer having a crosslinkable silyl group at one end and a halogen end represented by the formula (2) is obtained. Can be substituted for a halogen of formula 1
A vinyl polymer having a crosslinkable silyl group at a terminal can also be obtained by coupling halogen terminals with a compound having a total of two or more same or different functional groups.

There are no particular restrictions on the group having two or more identical or different functional groups capable of substituting a terminal halogen, but polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides, etc. Is preferred. Specific examples of these compounds include: ethylene glycol, 1,2-propanediol, 1,3
-Propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, , 3-butanediol, pinacol, 1,5-pentanediol, 1,4-
Pentanediol, 2,4-pentanediol, 1,6
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, 1,12-dodecanediol,
1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,
3-cyclohexanediol, 1,4-cyclohexanediol, glycerol, 1,2,4-butanetriol, catechol, resorcinol, hydroquinone, 1,
2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-
Dihydroxynaphthalene, 2,2′-biphenol,
4,4′-biphenol, bis (4-hydroxyphenyl) methane, 4,4′-isopropylidenephenol,
3,3 ′-(ethylenedioxy) diphenol, α,
α′-dihydroxy-p-xylene, 1,1,1-tris (4-hydroxyphenyl) ethane, pyrogallol,
1,2,4-benzenetriol, and an alkali metal salt of the above polyol compound, ethylenediamine,
3-diaminopropane, 1,2-diaminopropane,
1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine, 1,7-heptane Diamine, 1,8-octanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4′-methylenebis (cyclohexylamine), 1,2-diaminocyclohexane, 1,3 -Diaminocyclohexane,
1,4-diaminocyclohexane, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, α, α′-diamino-p-xylene,
And alkali metal salts of the above polyamine compounds, oxalic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid,
1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4
-Cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid,
2,4,5-benzenetetracarboxylic acid and alkali metal salts of the above polycarboxylic acids, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, , 5-pentanedithiol, 1,6-hexanedithiol, 1,7-
Heptanedithiol, 1,8-octanedithiol,
1,9-nonanedithiol, 2-mercaptoethyl ether, p-xylene-α, α′-dithiol, 1,2-
Benzenedithiol, 1,3-benzenedithiol,
1,4-benzenedithiol, and alkali metal salts of the above-mentioned polythiol compounds, lithium sulfide, sodium sulfide, potassium sulfide, and the like.

When the above polyols, polyamines, polycarboxylic acids, and polythiols are used, a basic compound is used in combination to promote the substitution reaction. As a specific example, when a carbanion of the general formula 4 is prepared, Examples of the base used include lithium, sodium, potassium, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, and potassium hydride.

As another method for producing a vinyl polymer having a crosslinkable silyl group at a terminal, the halogen terminal of the formula (2) is once converted into an alkenyl group-containing substituent, and a crosslinkable group is further added to the alkenyl group. A method of adding a hydrosilane compound having the same. Various methods can be used for converting the halogen terminal of Formula 2 into an alkenyl group-containing substituent.

For example, a vinyl polymer having a terminal structure represented by the general formula 2 is produced by radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. And a method in which a compound having both a polymerizable alkenyl group and at least one other alkenyl group is reacted as the second monomer. No particular limitation is imposed on the compound having both a polymerizable alkenyl group other at least one alkenyl group, for example, the general formula _{7 H 2 C = C (R} 5) -R 6 -R 7 -C (R 5 ) = CH ₂ (7) wherein R ⁵ is hydrogen or a methyl group, which may be the same or different, and R ⁶ and R ⁷ are the same as above. When R ⁶ is an ester group, it is a (meth) acrylate compound, and when R ⁶ is a phenylene group, it is a styrene compound. The R ⁷ in the formula 7, methylene, ethylene, alkylene groups such as propylene, o-, m-, p-phenylene group, aralkyl groups such as benzyl _{group, -CH 2 CH 2 -O-CH} 2 - and - OC
Examples thereof include an alkylene group containing an ether bond such as H ₂ —.

Among them, H ₂ C ＝ C (H) C (O) O (CH ₂ ) _n -CH
ＣＨCH ₂ , H ₂ C ＝ C (CH ₃ ) C (O) O (CH ₂ ) _n −
(In the formulas above, n represents an integer of _{0~20) CH = CH 2 H 2} C = C (H) C (O) O (CH 2) n -O- (CH 2)
_m CH = CH ₂ , H ₂ C = C (CH ₃ ) C (O) O (C
In _{H 2) n -O- (CH 2} ) m CH = CH 2 ( above equations, n represents an integer of 1 to 20, m an integer of 0~20) o-, m-, p- divinylbenzene, o-, m-, p-
_{H 2 C = CH-C 6} H 4 -CH 2 CH = CH 2, o-, m
_{-, p-H 2 C =} CH-C 6 H 4 -CH 2 -C (CH 3) =
_{CH 2, o-, m-, p} -H 2 C = CH-C 6 H 4 -CH 2
_{CH 2 CH = CH 2, o-} , m-, p-H 2 C = CH-C 6
_{H 4 -OCH 2 CH = CH 2} , o-, m-, p-H 2 C = C
_{H-C 6 H 4 -OCH 2} -C (CH 3) = CH 2, o-, m
_{-, p-H 2 C =} CH-C 6 H 4 -OCH 2 CH 2 CH = C
_{H 2, o-, m-, p} -H 2 C = C (CH 3) -C 6 H 4 -
_{C (CH 3) = CH 2} , o-, m-, p-H 2 C = C (C
_{H 3) -C 6 H 4 -CH} 2 CH = CH 2, o-, m-, p-
_{H 2 C = C (CH 3} ) -C 6 H 4 -CH 2 C (CH 3) = CH
_{2, o-, m-, p-} H 2 C = C (CH 3) -C 6 H 4 -C
_{H 2 CH 2 CH = CH 2} , o-, m-, p-H 2 C = C (C
_{H 3) -C 6 H 4 -OCH} 2 CH = CH 2, o-, m-, p
_{-H 2 C = C (CH 3} ) -C 6 H 4 -OCH 2 -C (CH 3)
_{= CH 2, o-, m-,} p-H 2 C = C (CH 3) -C 6 H
_{4 -OCH 2 CH 2 CH = CH} 2 ( provided that in the above chemical formula,
C ₆ H ₄ represents a phenylene group. Is preferred.

Further, a compound having at least two alkenyl groups having low polymerizability may be reacted as the second monomer. Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (8). ^{_{H 2 C = C (R 11}} ) -R-C (R 11) = CH 2 (8) ( wherein, R ¹¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, Or 7 to 1 carbon atoms
0 may be the same or different from each other in the aralkyl group, and R may be a divalent organic group having 1 to 20 carbon atoms and may include one or more ether bonds. Although not particularly limited, 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene are preferable because they are easily available.

As another method for introducing an alkenyl group at the terminal, a halogen-substituted polymer represented by the formula 2 is substituted with various organometallic compounds having an alkenyl group. A method can also be used. Such organometallic compounds include organic lithium, organic sodium, organic potassium, organic magnesium, organic tin, organic zinc, organic copper, and the like. In particular, organotin and organocopper compounds are preferred because they selectively react with the halogen of the formula 2 and have low reactivity with a carbonyl group. The organotin compound having an alkenyl group is not particularly limited, but a compound represented by the general formula 9 is preferable. H ₂ C ＝ C (R ¹⁵ ) C (R ¹⁶ ) (R ¹⁷ ) Sn (R ¹⁸ ) ₃ (9) (wherein, R ¹⁵ , R ¹⁶ and R ¹⁷ are hydrogen or have 1 to 1 carbon atoms)
The alkyl group having 0, the aryl group having 6 to 10 carbon atoms, or the aralkyl group having 7 to 10 carbon atoms may be the same or different. R ¹⁸ is an alkyl group having 1 to 10 carbon atoms,
An aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms) Specific examples of the organotin compound of the formula 9 include allyltributyltin, allyltrimethyltin, allyltri (n-octyl) tin, and allyltritin. (Cyclohexyl) tin and the like are exemplified.

Examples of the organic copper compound having an alkenyl group include lithium divinyl copper, lithium diallyl copper, lithium lithium diisopropenyl, and the like. By reacting a stabilized carbanion having an alkenyl group of the general formula 8 on a polymer having a halogen at the terminal of the formula 2,
A vinyl polymer having an alkenyl group at a terminal can be obtained. ^{M + C - (R 8)} (R 9) -R 10 -C (R 11) = CH 2 (10) ( ^{wherein, R 8, R 9, R} 10, R 11, M + is the same) As already exemplified, at least one of R ⁸ and R ⁹ is an electron withdrawing group for stabilizing the carbanion, and —CO ₂ R,
-C (O) R and -CN are particularly preferred. Also, M ⁺
Is a counter cation of a carbanion, and is exemplified by an alkali metal ion or a quaternary ammonium ion.

The carbanion of the general formula 10 can be obtained by allowing a basic compound to act on its precursor and extracting an active proton. Examples of the precursor compound of the carbanion represented by the general formula 10 include the following compounds: H ₂ C ＝ CH—CH (CO ₂ CH ₃ ) ₂ , H ₂ C ＝ C
_{H-CH (CO 2 C 2} H 5) 2, H 2 C = CH- (CH 2) n
_{CH (CO 2 CH 3) 2} , H 2 C = CH- (CH 2) n CH
_{(CO 2 C 2 H 5)} 2, o-, m-, p-H 2 C = CH-C 6
_{H 4 -CH (CO 2 CH 3} ) 2, o-, m-, p-H 2 C =
_{CH-C 6 H 4 -CH (} CO 2 C 2 H 5) 2, o-, m-, p
_{-H 2 C = CH-C 6} H 4 -CH 2 CH (CO 2 CH 3) 2,
_{o-, m-, p-H 2} C = CH-C 6 H 4 -CH 2 CH (C
_{O 2 C 2 H 5) 2} , H 2 C = CH-CH (C (O) CH 3)
_{(CO 2 C 2 H 5)} , H 2 C = CH- (CH 2) n CH (C
(O) CH ₃ ) (CO ₂ C ₂ H ₅ ), o-, m-, p-H _{2
C = CH-C 6 H 4} -CH (C (O) CH 3) (CO 2 C 2
_{H 5), o-, m-,} p-H 2 C = CH-C 6 H 4 -CH 2
_{CH (C (O) CH 3} ) (CO 2 C 2 H 5), H 2 C = CH
_{-CH (C (O) CH 3} ) 2, H 2 C = CH- (CH 2) n
_{CH (C (O) CH 3} ) 2, o-, m-, p-H 2 C = C
_{H-C 6 H 4 -CH (} C (O) CH 3) 2, o-, m-, p
_{-H 2 C = CH-C 6} H 4 -CH 2 CH (C (O) C
_{H 3) 2, H 2 C} = CH-CH (CN) (CO 2 C 2 H 5),
_{H 2 C = CH- (CH 2} ) n CH (CN) (CO 2 C
_{2 H 5), o-, m-} , p-H 2 C = CH-C 6 H 4 -CH
_{(CN) (CO 2 C 2} H 5), o-, m-, p-H 2 C = C
_{H-C 6 H 4 -CH 2} CH (CN) (CO 2 C 2 H 5), H 2
C = CH-CH (CN) 2, H 2 C = CH- (CH 2) n C
_{H (CN) 2, o-,} m-, p-H 2 C = CH-C 6 H 4 -
_{CH (CN) 2, o-,} m-, p-H 2 C = CH-C 6 H 4
_{-CH 2 CH (CN) 2,} H 2 C = CH- (CH 2) n N
_{O 2, o-, m-, p} -H 2 C = CH-C 6 H 4 -CH 2 N
_{O 2, o-, m-, p} -H 2 C = CH-C 6 H 4 -CH 2 C
_{H 2 NO 2, H 2 C} = CH-CH (C 6 H 5) (CO 2 C
_{2 H 5), H 2 C} = CH- (CH 2) n CH (C 6 H 5) (C
_{O 2 C 2 H 5),} o-, m-, p-H 2 C = CH-C 6 H 4 -
CH (C ₆ H ₅ ) (CO ₂ C ₂ H ₅ ), o-, m-, p-H _{2
C = CH-C 6 H 4} -CH 2 CH (C 6 H 5) (CO 2 C
During ₂ H ₅₎ (above formula, n an integer of 1 to 10) are exemplified.

The proton is extracted from the above compound,
In order to obtain a carbanion of 0, a basic compound used in preparing the carbanion represented by the general formula 4;
All solvents can be suitably used. As a method for introducing an alkenyl group, an oxyanion having an alkenyl group represented by the formula 11 may be reacted. M ⁺ O ^-- R ⁴ -C (R ¹¹ ) = CH ₂ (11) (wherein R ⁴ , R ¹¹ and M ⁺ are the same as above) The precursor compound of the oxyanion of the general formula (11) is as follows. compounds such _{as: H 2 C = CH-CH} 2 -OH, H 2
_{C = CH-CH (CH 3} ) -OH, H 2 C = C (CH 3)
_{-CH 2 -OH, H 2 C =} CH- (CH 2) n -OH (n
Represents an integer of 2 to 20. _{), H 2 C = CH-} CH 2 -
_{O- (CH 2) 2 -OH,} H 2 C = CH-C (O) O-
_{(CH 2) 2 -OH, H} 2 C = C (CH 3) -C (O) O-
_{(CH 2) 2 -OH, o-} , m-, p-H 2 C = CH-C 6
_{H 4 -CH 2 -OH, o-,} m-, p-H 2 C = CH-C
_{H 2 -C 6 H 4 -CH 2} -OH, o-, m-, p-H 2 C =
_{CH-CH 2 -O-C 6} H 4 alcoholic hydroxyl group-containing compounds such as _{-CH 2 -OH; o-, m-,} p-H 2 C = CH-
_{C 6 H 4 -OH, o-,} m-, p-H 2 C = CH-CH 2 -
_{C 6 H 4 -OH, o-,} m-, p-H 2 C = CH-CH 2 -
A phenolic hydroxyl group-containing compound such as OC ₆ H ₄ —OH;
_{H 2 C = CH-C (} O) -OH, H 2 C = C (CH 3) -
_{C (O) -OH, H 2} C = CH-CH 2 -C (O) -O
_{H, H 2 C = CH- (} CH 2) n -C (O) -OH (n
Represents an integer of 2 to 20. _{), H 2 C = CH- (} C
_{H 2) n -OC (O)} - (CH 2) m -C (O) -OH (m
And n are the same or different and represent an integer of 0 to 19. ), O-, m-, p- H 2 C = CH-C 6 H 4 -C
(O) -OH, o-, m- , p-H 2 C = CH-CH 2 -
_{C 6 H 4 -C (O)} -OH, o-, m-, p-H 2 C = C
_{H-CH 2 -O-C 6} H 4 -C (O) -OH, o-, m
_{-, p-H 2 C =} CH- (CH 2) n -OC (O) -C 6 H
_4- C (O) -OH (n represents an integer of 0 to 13)
And other carboxyl group-containing compounds.

The proton is abstracted from the above compound.
Various bases are used to obtain one anion, and specific examples thereof include all the basic compounds and solvents used when preparing the carbanion of the formula (4). As another method of introducing an alkenyl group, a vinyl-based polymer having a terminal at a halogen is reacted with a simple metal or an organometallic compound to form an enolate anion, and then reacted with an electrophilic compound having an alkenyl group. It is also possible to use the method. Zinc is particularly preferable as the metal simple substance in that the generated enolate anion is unlikely to cause a side reaction such as attacking or transferring another ester group. Various kinds of electrophilic compounds having an alkenyl group can be used.
Examples thereof include an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group. Of these, when an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group is used, a hetero atom is not introduced into the main chain, and the weather resistance, which is an original feature of the vinyl polymer, is not lost. It is preferred.

In a process for producing a vinyl polymer, which comprises polymerizing a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, an organic halide having an alkenyl group is used. When used as an initiator, a vinyl polymer having an alkenyl group at one terminal and the other terminal having the structure of Formula 2 can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into an alkenyl group-containing substituent, a vinyl polymer having alkenyl groups at both ends can be obtained. As the conversion method, the method already described can be used.

The organic halide having an alkenyl group is not particularly limited, and examples thereof include those having a structure represented by the following general formula 9. R ¹² R ¹³ C (X) -R ¹⁴ -R ⁷ -C (R ⁵ ) = CH ₂ (12) (wherein, R ⁵ , R ⁷ , R ¹² , R ¹³ , R ¹⁴ , and X are the same as described above. As specific examples of the organic halide having an alkenyl group represented by the general formula 12, XCH ₂ C (O) O (C
H 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 ,

[0043]

Embedded image

(In the above formulas, X represents chlorine, bromine,
Or iodine, n represents an integer of _{0~20) XCH 2 C (O)} O (CH 2) n O (CH 2) m CH = C
H ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (C
H 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 ,

[0045]

Embedded image

(In the above formulas, X represents chlorine, bromine,
Or iodine, n represents an integer of 1 to 20, m is an integer of 0~20) o, m, p- XCH 2 -C 6 H 4 - (CH 2) n -CH = C
_{H 2, o, m, p} -CH 3 C (H) (X) -C 6 H 4 - (C
_{H 2) n -CH = CH 2} , o, m, p-CH 3 CH 2 C
_{(H) (X) -C 6} H 4 - in _{(CH 2) n -CH = CH} 2 ( above equations, X is chlorine, bromine or iodine,, n
0-20 integer) o, m, p-XCH 2 -C 6 H 4 - (CH 2) n -O- (C
_{H 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₎ in _{n -O- (CH 2) m CH} = CH 2 ( above equations, X is chlorine, bromine or iodine,, n is 1 to
20 integer, m is 0 to 20 integer) 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 = C
H ₂ (in each of 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 -C
_{H = CH 2, o, m} , p-CH 3 CH 2 C (H) (X) -
_{C 6 H 4 -O- (CH 2} ) n -O- (CH 2) m -CH = CH
₂ (In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, m is an integer of 0 to 20) Further, as an organic halide having an alkenyl group, a compound represented by the general formula 15 Is mentioned. ^{_{H 2 C = C (R 5}} ) -R 7 -C (R 12) (X) -R 15 -R 13 (15) ( ^{wherein, R 5, R 7, R} 12, R 13, X in the above Same, R ¹⁵
Is a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenylene group) R ⁷ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (one or more ether bonds However, in the case of a direct bond, a vinyl group is bonded to the carbon to which the halogen is bonded, and the compound is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, C (O) O is used as R ^17.
It is not always necessary to have a group or a phenylene group, and a direct bond may be used. When R ⁷ is not a direct bond, R ¹⁵ may be C to activate a carbon-halogen bond.
(O) O group, C (O) group and phenylene group are preferred.

If the compound of formula 13 is specifically exemplified, CH ₂ ＝ CHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH
₂ X, CH ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (C
H ₃ ) C (H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (C
H ₃ ) ₂ , CH ₂ （CHC (H) (X) C ₂ H ₅ , CH ₂ ＣC
HC (H) (X) CH (CH 3) 2, CH 2 = CHC
(H) (X) C ₆ H ₅ , CH ₂ ＣＨCHC (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 = CH
_{CH 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
(In each formula mentioned above, X is chlorine, bromine or iodine,, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group) (H) (X) -C 6 H 5 and the like can be given .

Specific examples of the sulfonyl halide compound having an alkenyl group include o-, m-, p-C
_{H 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 each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

An organic halide having an alkenyl group,
Alternatively, when a halogenated sulfonyl compound is used as an initiator, a polymer having one terminal of an alkenyl group and the other terminal of a halogen terminal represented by the formula 2 is obtained. A vinyl polymer having an alkenyl group at the terminal can also be obtained by coupling halogen terminals with a compound having a total of two or more same or different functional groups. As the compounds used for coupling, all of the compounds described above can be suitably used.

When a hydrosilane compound having a crosslinkable silyl group is added to the vinyl polymer having an alkenyl terminal at the terminal obtained by the above method in the presence of a hydrosilylation catalyst, the crosslinkable silyl at the terminal is obtained. A vinyl polymer having a group can be obtained. The hydrosilane compound having a crosslinkable silyl group is not particularly limited, but a typical example is a compound represented by the general formula 14. _{^{H- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (14) ( ^{wherein, R 3, R 4, a} , b, m, Y is the same as described above.) Specific examples of the hydrolyzable group, R ³ , and R ⁴ represented by Y include the same as those already exemplified in the description of the general formula 1.

Among these hydrogen silicon compounds, particularly, they are represented by the general formula 15 H-Si (R ⁴ ) _3-a (Y) _a (15) (wherein R ⁴ , Y and a are the same as above). Compounds having a crosslinkable group are preferred in that they are easily available. Specific examples of the hydrosilane compound having a crosslinkable group represented by the general formula 14 or 15 include HSiCl ₃ , HSi (C
_{H 3) Cl 2, HSi (} CH 3) 2 Cl, HSi (OC
_{H 3) 3, HSi (CH} 3) (OCH 3) 2, HSi (C
_{H 3) 2 OCH 3, HSi} (OC 2 H 5) 3, HSi (C
H ₃ ) (OC ₂ H ₅ ) ₂ , HSi (CH ₃ ) ₂ OC ₂ H ₅ , HS
i (OC ₃ H ₇ ) ₃ , HSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , H
_{Si (C 2 H 5) 2} OCH 3, HSi (C 6 H 5) (OC
_{H 3) 2, HSi (C} 6 H 5) 2 (OCH 3), HSi (CH
_{3) (OC (O) CH} 3) 2, HSi (CH 3) 2 O- [S
i (CH ₃ ) ₂ O] ₂ -Si (CH ₃ ) (OCH ₃ ) ₂ , HS
i (CH ₃ ) [ON = C (CH ₃ ) ₂ ] ₂ (where C ₆ H ₅ represents a phenyl group in the above chemical formula) and the like.

When the above-mentioned hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. As the transition metal catalyst, for example, platinum alone, alumina, silica, a dispersion of platinum solids on a carrier such as carbon black, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc.
Platinum-olefin complexes and platinum (0) -divinyltetramethyldisiloxane complexes are exemplified. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ and RhC
l ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ ,
PdCl ₂ .H ₂ O, NiCl ₂ , TiCl _{4 and the} like.

As another method for producing a vinyl polymer having a crosslinkable silyl group at a terminal, a method in which the halogen terminal of the formula (2) is once converted into a hydroxyl group-containing substituent and the reactivity of the hydroxyl group is utilized. Can be Various reactions can be used for converting the terminal into a hydroxyl group-containing substituent. For example, the general formula 2
A method of producing a vinyl polymer having a terminal represented by, and further reacting a compound having both a polymerizable alkenyl group and a hydroxyl group as a second monomer, for a vinyl polymer having a halogen terminal represented by the general formula 2, A method of metallizing a halogen by reacting a simple metal or an organometallic compound and reacting with a carbonyl compound such as an aldehyde or ketone, a method of directly substituting a halogen with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide,
For example, a method of substituting a halogen with a polyalcohol.

Other methods for introducing a hydroxyl group into the terminal include a halide having a hydroxyl group as an initiator,
By polymerization using a transition metal complex as a catalyst, a vinyl polymer having a hydroxyl group at one end and a halogen represented by the formula 2 at the other end is produced, and then the hydroxyl group-containing substituent is added to the halogen end by the method described above. How to convert to
There is a method in which halogen terminals are coupled with each other using a compound having two or more identical or different functional groups capable of substituting the halogen.

As a method of converting the hydroxyl group at the terminal of the vinyl polymer thus obtained into a crosslinkable silyl group, a method of reacting an isocyanate compound having a crosslinkable silyl group can be mentioned. In addition, it is also possible to use a method in which a terminal hydroxyl group is converted into an alkenyl group-containing substituent, and thereafter, a hydrosilane compound having a crosslinkable silyl group is added.

Examples of a method for converting a terminal hydroxyl group into an alkenyl group-containing group include a method of reacting an alkenyl group-containing halide such as allyl chloride with a base such as sodium methoxide, or a method of converting an alkenyl group-containing group such as allyl isocyanate. A method of reacting an isocyanate compound, a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine, and a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst. A reaction method and the like can be mentioned.

As the crosslinkable silyl group-containing hydrosilane compound to be added to the terminal alkenyl group of the vinyl polymer thus obtained, all the compounds of formulas 11 and 12 described above can be used. A curable composition containing a vinyl polymer having a terminal having a crosslinkable silyl group represented by the general formula 1 and obtained by various methods as described above as a main component can be obtained.

In curing the composition of the present invention, a condensation catalyst may or may not be used. Titanate such as tetrabutyl titanate and tetrapropyl titanate; organic tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; lead octylate;
Butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine , 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N
-Methylmorpholine, 1,3-diazabicyclo (5,
4,6) amine compounds such as undecene-7 or carboxylate thereof; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; silane having amino group A coupling agent, for example, one or more known silanol catalysts such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. The amount used is based on the vinyl polymer having a crosslinkable silyl group at the terminal.
It is preferably used at 0 to 10% by weight. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst because the curing speed is slow only with this polymer.

The curable composition of the present invention may contain various fillers depending on the use. Reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite Fillers such as organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon; fibrous fillers such as asbestos, glass fibers and filaments can be used. In order to obtain a high-strength cured product with these fillers, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc are mainly used. Use of a filler selected from flowers and the like in a range of 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl-based polymer provides a preferable result. 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 is used. When used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the united product, preferable results can be obtained. These fillers may be used alone or in combination of two or more.

In the present invention, when a plasticizer is used in combination with a filler, the elongation of the cured product can be increased, and a large amount of the filler can be mixed, which is more effective. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; and dioctyl adipate and dioctyl sebacate. Non-aromatic dibasic acid esters; Polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Paraffin chloride; Alkyl diphenyl, partial water Hydrocarbon oils such as terphenyl and the like can be used alone or as a mixture of two or more, but are not necessarily required. In addition, these plasticizers can be blended at the time of polymer production.

When the amount of the plasticizer is in the range of 0 to 100 parts by weight based on 100 parts by weight of the vinyl polymer having a crosslinkable silyl group at a terminal, a preferable result is obtained. Fillers, plasticizers, and condensation catalysts are mainly used in the blended composition of the present invention, but adhesion-imparting agents such as phenolic resins, sulfur, silane coupling agents, etc .; Modifiers such as siloxanes; additives such as tack and weatherability improvers such as UV curable resins, pigments, antioxidants, UV absorbers and the like may optionally be used.

As the anti-dripping material, hydrogenated castor oil derivatives;
Calcium stearate, aluminum stearate,
Metal soaps such as barium stearate may be mentioned, but may not be necessary depending on the purpose of use or the blending of fillers, reinforcing materials and the like. As the coloring agent, ordinary inorganic pigments, organic pigments, dyes and the like can be used as necessary.

Various silane coupling agents such as alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyl Alkylisopropenoxysilanes such as triisopropenoxysilane and γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane , Vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N
-Alkoxysilanes having a functional group such as-(β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; silicone varnishes; Is added.
By using the physical property modifier, the hardness of the composition of the present invention when it is cured can be increased, or the hardness can be decreased, and elongation can be obtained.

As the adhesion promoter, the polymer itself according to the present invention has adhesiveness to glass, ceramics other than glass, metal and the like, and can be adhered to a wide range of materials by using various primers. Although not necessary, it is possible to adhere to more types of adherends by using one or more of epoxy resin, phenol resin, various silane coupling agents, alkyl titanates, aromatic polyisocyanates, etc. Performance can be improved.

The curable composition of the present invention may be prepared as a one-component type in which all the components are premixed, sealed and stored, and cured by the moisture in the air after application. Ingredients such as a filler, a plasticizer, and water may be blended in advance, and the blended material and the polymer composition may be mixed as a two-component type before use. Specific applications of the cured product obtained from the above composition include sealing materials, adhesives, pressure-sensitive adhesives, elastic adhesives, paints, powder coatings, foams, potting materials for electric and electronic devices, films, and moldings. Materials, artificial marble, etc.

[0066]

EXAMPLES Specific examples of the present invention will be shown below, but the present invention is not limited to the following examples. (Production Example 1) Production Example of Initiator Having Hydroxy Group Ethylene glycol (10.9 mL, 1
95 mmol) and pyridine (3 g, 39 mmol)
2-bromopropionic acid chloride (2 mL, 3.35 g, 19.5 mmol) was added to an HF solution (10 mL) at 0 ° C.
And slowly dripped. The solution was stirred for 2 hours at the same temperature. Dilute hydrochloric acid (20 mL) and ethyl acetate (30 mL)
Was added and the two layers were separated. The organic layer was washed with diluted hydrochloric acid and brine, dried over Na ₂ SO ₄ , and the volatiles were distilled off under reduced pressure to obtain a crude product (3.07 g). The crude product was distilled under reduced pressure (70-73 ° C., 0.5 m
mHg) to give hydroxyethyl-2-bromopropionate represented by the following formula (2.14 g, 56%).

CH ₃ C (H) (Br) C (O) O (CH ₂ ) ₂ —OH (Production Example 2) Production of carboxylate having alkenyl group 1 1 / 2N ethanol solution of potassium hydroxide (200m
L) to undecylenic acid (18.8 g, 0.102 mo)
1) was slowly added dropwise at 0 ° C. while stirring. The volatile product was distilled off under reduced pressure to obtain a crude product. The crude product was washed with acetone and then heated under reduced pressure to obtain a white solid of potassium undecylenic acid represented by the following formula (8.
88 g, 88% yield). _{CH 2 = CH- (CH 2)} 8 -CO 2 - K + ( Production Example 3) Preparation 2 potassium methoxide carboxylates having an alkenyl group (16.83g, 0.240mo
l) was dissolved in methanol (200 mL), and 4-pentenoic acid (24.56 g, 0.245 mol) was slowly added dropwise at 0 ° C while stirring. The volatile product was distilled off under reduced pressure to obtain a crude product. The crude product was washed with ethyl acetate and then heated under reduced pressure to obtain a white solid of potassium salt of 4-pentenoic acid represented by the following formula (29.2 g, yield 8).
8%). _{CH 2 = CH- (CH 2)} 2 -CO 2 - K + pressure glass reaction vessel (Production Example 4) 30 mL, butyl acrylate (5mL, 4.47g, 34.9mmo
l), α, α'-dibromo-p-xylene (185 m
g, 0.70 mmol), cuprous bromide (100 mg,
0.70 mmol), 2,2'-bipyridyl (217 m
g, 1.40 mmol), ethyl acetate (4 mL), and acetonitrile (1 mL), nitrogen bubbling was performed for 10 minutes to remove dissolved oxygen, and the tube was sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. After cooling the mixture, methyldimethoxysilylpropyl methacrylate (650 mg, 2.8 mmol) was added and 10
The reaction was performed at 0 ° C. for 2 hours. After cooling, the mixture was diluted with ethyl acetate (20 mL), and the resulting insoluble solid was filtered. The filtrate was washed twice with an aqueous ammonium chloride solution and once with brine. The organic layer was dried over Na ₂ SO ₄ and the volatiles were distilled off under reduced pressure to obtain 4.78 g of poly (butyl acrylate) having a methyldimethoxysilyl group at the end (90
%). The number average molecular weight of the polymer was 7,100 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.74. ¹ H NMR analysis revealed that 3.2 silyl groups were introduced per molecule. (Production Example 5) Acrylic acid-n-
Butyl (112 mL, 100 g, 0.78 mol), the hydroxyl-containing initiator synthesized in Production Example 1 (3.07 g, 1
5.6 mmol), cuprous bromide (2.24 g, 15.6)
mmol), 2,2′-bipyridyl (4.87 g, 3
1.2 mmol), ethyl acetate (89.6 mL), and acetonitrile (22.4 mL).
After blowing in for 2 minutes to remove dissolved oxygen, the tube was sealed. The mixture was heated to 130 ° C. and reacted for 1 hour. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 100 ° C. for 1 hour. The mixture was diluted with ethyl acetate, the insoluble matter was filtered off, and the filtrate was diluted with 10% hydrochloric acid.
Twice, once with brine. After the organic layer was dried over Na ₂ SO ₄ , the solvent was distilled off under reduced pressure to obtain 82 g of poly (n-butyl acrylate) having a terminal hydroxyl group. The number average molecular weight of the polymer was 5,900 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.35.

Next, the poly (n-butyl acrylate) having a hydroxyl group at the terminal obtained as described above (68)
g) and pyridine (14 mL) in toluene (10
0 mL) was slowly added dropwise with undecenoic acid chloride (7.1 mL, 33.0 mmol) at 75 ° C under a nitrogen atmosphere, and reacted at 60 ° C. The resulting white solid was filtered and the organic layer was washed with dilute hydrochloric acid and brine. By drying the organic layer over Na ₂ SO ₄ and concentrating under reduced pressure,
Poly (n-butyl acrylate) having an alkenyl group at the terminal (64 g) was obtained. Aluminum silicate (Kyowa Chemical: Kyowade 700 PEL) was added to a toluene solution of the polymer, and the mixture was stirred at the reflux temperature to remove trace impurities in the polymer. The number of alkenyl groups introduced per oligomer-1 molecule was 2.8 by ¹ H NMR analysis.

Next, the above polymer (25.3 g), dimethoxymethylhydrosilane (4.8 mL, 38.7 mmol), dimethyl orthoformate (1.4 mL, 12.9 mmol) were placed in a 100 mL pressure-resistant glass reaction vessel. as well as,
A platinum catalyst was charged. However, the amount of the platinum catalyst used was 10 ^-4 equivalent in a molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 C for 3 hours. The volatile components of the mixture were distilled off under reduced pressure to obtain poly (n-butyl acrylate) having a silyl group at the terminal. The silyl group introduced per molecule of the oligomer was analyzed by ¹ H NMR.
From analysis, it was 2.2. (Production Example 6) Cuprous bromide (0.625 g, 15.6 mmol) was placed in a 100 mL three-necked round bottom flask equipped with a reflux tube.
l), acetonitrile (5.0 mL) and pentamethyldiethylenetriamine (0.91 mL) were charged,
The atmosphere was replaced with nitrogen gas. N-butyl acrylate (50m
L, 44.7 g, 0.39 mol) and diethyl-
2,5-dibromoadipate (1.57 g, 4.36 m
mol), and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. The volatiles were distilled off under reduced pressure to obtain 35.0 g of poly (n-butyl acrylate) having a halogen at the terminal (polymerization yield: 8).
7%). The number average molecular weight of the polymer was 10,700 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.15.

Next, a poly (n-butyl acrylate) having terminal halogens (35.0 n-butyl acrylate) (35.0) obtained as described above was placed in a 200 mL three-necked round bottom flask equipped with a reflux tube.
g), potassium salt of 4-pentenoic acid synthesized in Production Example 2 (2.23 g, 16.1 mmol), and dimethylacetamide (35 mL) were charged, and the mixture was charged under nitrogen atmosphere.
The reaction was performed at 0 ° C. for 4 hours. The mixture was diluted with ethyl acetate and washed with 2% hydrochloric acid, brine. Na ₂ S
The polymer was isolated by drying over O ₄ and distilling off volatiles under reduced pressure. An aluminum silicate (Kyowa Chemical Co., Ltd .: 700 PEL) in an amount equivalent to the polymer was added and stirred at 100 ° C. for 4 hours to obtain poly (butyl acrylate) having an alkenyl group at a terminal. Oligomer -1 alkenyl groups introduced per molecule, from ¹ H NMR analysis, 1.8
There were two.

Next, the above polymer (15.0 g), dimethoxymethylhydrosilane (1.8 mL, 14.5 mmol), dimethyl orthoformate (0.26 mL, 2.42 mmol) were placed in a 200 mL pressure-resistant glass reaction vessel. And, a platinum catalyst was charged. However, the amount of the platinum catalyst used was 2 × 10 5 in molar ratio with respect to the alkenyl group of the polymer.
^-4 equivalents. The reaction mixture was heated at 100 C for 4 hours. The volatile components of the mixture were distilled off under reduced pressure to obtain poly (n-butyl acrylate) having a silyl group at the terminal. The silyl group introduced per oligomer-1 molecule is
^{From 1} H NMR analysis, it was 1.46. (Production Example 7) In a 100 mL glass reaction vessel, butyl acrylate (50.0 mL, 44.7 g, 0.349 mol) was added.
l), cuprous bromide (1.25 g, 8.72 mmol),
Pentamethyldiethylenetriamine (1.82 mL,
1.51 g, 8.72 mmol) and acetonitrile (5 mL) were charged, cooled, degassed under reduced pressure, and then replaced with nitrogen gas. After stirring well, diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) was added, and the mixture was heated and stirred at 70 ° C. After 60 minutes, 1,7-octadiene (6.44 mL, 4.80 g, 43.6 mmol)
1) was added, and heating and stirring at 70 ° C. was continued for 2 hours. After treating the mixture with activated alumina, volatiles were distilled off by heating under reduced pressure. The product was dissolved in ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer was dried over Na ₂ SO ₄ , and the volatiles were distilled off by heating under reduced pressure to obtain a polymer having a terminal alkenyl group. The number average molecular weight of the obtained polymer was 13,100 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.22. The olefin functional group introduction rate based on the number average molecular weight was 2.01. The obtained polymer (30.5 g), aluminum silicate of the same weight as the polymer (Kyowa Chemical Co., Ltd .: Kyoword 700 PEL)
Was mixed with toluene and stirred at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the volatile matter of the filtrate was distilled off by heating under reduced pressure to purify the polymer.

Next, the above polymer (23.3 g), dimethoxymethylhydrosilane (2.55 mL, 20.7 mmol), dimethyl orthoformate (0.38 mL, 3.45 mmol) were placed in a 200 mL pressure-resistant glass reaction vessel. And a platinum catalyst. However, the amount of the platinum catalyst used was 2 × 10 5 in molar ratio with respect to the alkenyl group of the polymer.
^-4 equivalents. The reaction mixture was heated at 100 C for 3 hours. The volatile components of the mixture were distilled off under reduced pressure to obtain poly (n-butyl acrylate) having a silyl group at the terminal. The silyl group introduced per oligomer-1 molecule is
^{According to 1} HNMR analysis, the number was 1.41. (Example 1) Poly (butyl acrylate) having a crosslinkable silyl group at the end synthesized in Production Example 4 (2.5 g) and a curing catalyst (Nitto Kasei, U-220, 75 mg) were thoroughly mixed, The mixture was poured into a mold and defoamed at room temperature using a vacuum dryer. By leaving it at room temperature for 7 days, a uniform rubber-like cured product was obtained. The gel fraction was 54%. (Example 2) Dibutyltin dimethoxide and water were added to poly (butyl acrylate) having a silyl group at a terminal synthesized in Production Example 5 and mixed well. The amounts of the tin catalyst and water used were each 1 part by weight with respect to the polymer.

The composition thus obtained was poured into a mold, degassed under reduced pressure, and heat-cured at 50 ° C. for 20 hours to obtain a cured rubber-like sheet. The cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the weight change before and after, and was found to be 88%. A No. 2 (1/3) dumbbell test piece was punched from the sheet-shaped cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The breaking strength is 0.
32 MPa and elongation at break were 34%. (Example 3) Dibutyltin dimethoxide and water were added to poly (butyl acrylate) having a silyl group at a terminal synthesized in Production Example 6 and mixed well. The amounts of the tin catalyst and water used were each 1 part by weight with respect to the polymer.

The composition thus obtained was poured into a mold, degassed under reduced pressure, and heated and cured at 50 ° C. for 10 days to obtain a cured rubber-like sheet. The cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the weight change before and after, and was 98%. A No. 2 (1/3) dumbbell test piece was punched from the sheet-shaped cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The breaking strength is 0.
35 MPa and elongation at break were 77%. Example 4 Poly (butyl acrylate) having a silyl group at a terminal synthesized in Production Example 7, dibutyltin dimethoxide, and water were mixed well. The amounts of the tin catalyst and water used were each 1 part by weight with respect to the polymer.

The composition thus obtained was poured into a mold, degassed under reduced pressure, and heat-cured at 50 ° C. for 20 hours to obtain a cured rubber-like sheet. The cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the change in weight before and after, and was found to be 85%. A No. 2 (1/3) dumbbell test piece was punched from the sheet-shaped cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). Breaking strength is 0.3
4 MPa, elongation at break was 86%.

[0076]

According to the present invention, a curable composition having excellent curability can be obtained since a vinyl polymer having a crosslinkable silyl group at a high terminal ratio is used as a main component.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masayuki Fujita 1-80 Yoshida-cho, Hyogo-ku, Kobe Kobe Research Institute

Claims (8)

[Claims] 1. A curable composition containing a vinyl polymer having a crosslinkable silyl group at the terminal represented by the general formula 1. _{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1) ( wherein, R ³ and R ⁴ are both 1 carbon atoms An alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ Si—
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R 'groups may be the same, shows a triorganosiloxy group represented by different may be), when R ³ or R ⁴ there are two or more, they may be the same , May be different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0,
1, 2, or 3 and b represents 0, 1, or 2. m is an integer of 0-19. However, a + mb ≧ 1
Is satisfied. ) 2. A vinyl polymer having a crosslinkable silyl group at the terminal represented by the general formula 1 is prepared by the following steps: (1) an organic halide or a sulfonyl halide compound as an initiator and a catalyst of a transition metal complex. a vinyl monomer by radical polymerization, to produce a vinyl polymer having a terminal structure represented by general formula 2 ^{as; -C (R 1) (R} 2) (X) (2) ( in the formula, R ¹ , R ² represents a group bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine, or iodine.) (2) A halogen represented by the general formula 2 represents a silyl group represented by the general formula 1. The curable composition according to claim 1, wherein the curable composition is a polymer obtained by converting into a contained substituent. 3. The curable composition according to claim 1, wherein the main chain of the vinyl polymer is obtained by polymerizing a (meth) acrylic acid monomer. 4. The curable composition according to claim 3, wherein the (meth) acrylic acid-based monomer is a (meth) acrylic acid ester monomer. 5. The curable composition according to claim 4, wherein the (meth) acrylate monomer is an acrylate monomer. 6. The curable composition according to claim 1, wherein the main chain of the vinyl polymer is obtained by polymerizing a styrene monomer. 7. The vinyl polymer as the component (A) has a ratio (Mw / Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography.
7. The curable composition according to claim 1, wherein the value of n) is less than 1.8. 8. The vinyl polymer as the component (A) has a number average molecular weight in the range of 1,000 to 100,000. 3. The curable composition according to item 1.