JP2003113324A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which has excellent heat resistance and weather resistance, and further to provide a curable composition having excellent curability. SOLUTION: This curable composition comprises (I) a vinylic polymer having at least one cross-linkable functional group and (II) an antioxidant. The curable composition having improved curability, wherein a vinylic polymer having cross- linkable functional silyl groups represented by general formula (1): SiYa R3-a (1) [R is a 1 to 20C alkyl or the like; Y is OH or a hydrolysable group; (a) is 1, 2 or 3, especially 3] is used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, the following two components: a curable composition containing a vinyl polymer (I) having at least one crosslinkable functional group and an antioxidant (II),
Further, among the crosslinkable silyl groups represented by the general formula (1), the crosslinkable functional group contains a vinyl polymer having a crosslinkable silyl group in which a is 3, and the curability is improved. It relates to a composition. -SiY _a R _3-a (1) (wherein Y, R, and a are the same as above)

[0002]

2. Description of the Related Art On the other hand, vinyl polymers obtained by radical polymerization, which have functional groups, particularly those having terminal functional groups, have not been put into practical use, while polymers obtained by ionic polymerization or polycondensation. . Among the vinyl polymers, the (meth) acrylic polymers have properties such as high weather resistance and transparency that cannot be obtained by the above polyether polymers, hydrocarbon polymers, or polyester polymers. Therefore, those having an alkenyl group or a crosslinkable silyl group in the side chain are used in highly weather-resistant paints and the like. On the other hand, it is not easy to control the polymerization of the acrylic polymer due to its side reaction, and it is very difficult to introduce a functional group into the terminal.

If a vinyl polymer having an alkenyl group at the terminal of the molecular chain can be obtained by a simple method, a cured product having excellent physical properties as compared with a polymer having a crosslinkable group in its side chain can be obtained. it can. Therefore, although many researchers have studied the manufacturing method, it is not easy to manufacture them industrially. For example, Japanese Patent Laid-Open No. 1-
JP-A-247403 and JP-A-5-255415 disclose a method for synthesizing a (meth) acrylic polymer having an alkenyl group at the end, which uses an alkenyl group-containing disulfide as a chain transfer agent.

In Japanese Unexamined Patent Publication (Kokai) No. 5-262808, a vinyl polymer having hydroxyl groups at both ends is synthesized by using a disulfide having a hydroxyl group, and the reactivity of the hydroxyl group is utilized to make the terminal end. A method for synthesizing a (meth) acrylic polymer having an alkenyl group is disclosed.

In Japanese Unexamined Patent Publication (Kokai) No. 5-111922, a vinyl-based polymer having hydroxyl groups at both ends is synthesized by using a polysulfide having a hydroxyl group, and the reactivity of the hydroxyl group is utilized to further terminate the polymerization. A method for synthesizing a (meth) acrylic polymer having a silyl group is disclosed.

[0006] With these methods, it is difficult to surely introduce functional groups at both ends, and a cured product having satisfactory properties cannot be obtained. In order to surely introduce a functional group into both ends, a large amount of chain transfer agent must be used, which is a problem in the manufacturing process. In addition, since these methods use ordinary radical polymerization, it is difficult to control the molecular weight and molecular weight distribution (ratio of weight average molecular weight and number average molecular weight) of the obtained polymer.

[0007] In contrast to such conventional techniques, the present inventors have made various inventions on vinyl polymers having various crosslinkable functional groups at their ends, their production methods, curable compositions, and applications. (JP-A-11-08024)
9, JP-A-11-080250, JP-A-11-0058
15, JP-A-11-116617, JP-A-11-116
606, JP-A-11-080571, and JP-A-11-08
0570, JP-A-11-130931, JP-A-11-1
00433, JP-A-11-116763, JP-A-9-2
72714, JP-A-9-272715 and the like).

For example, a vinyl-based polymer having a silicon-bonded hydroxyl group or a hydrolyzable group and a silicon-containing group (hereinafter, also referred to as "crosslinkable silyl group") which can be crosslinked by forming a siloxane bond. The combined product, or a cured product obtained from the composition, is excellent in heat resistance or weather resistance, and is not particularly limited, but it is a sealing material in an elastic sealing material sealant for construction or a sealing material for double glazing, etc. Materials such as electric / electronic component materials, electric insulation materials such as electric wire / cable insulation coating materials,
Adhesives, adhesives, elastic adhesives, paints, powder paints, coating materials, foams, sealing materials for can lids, electric and electronic potting agents, films, gaskets, casting materials, various molding materials, artificial marble, Also, it is used for various applications such as rustproof / waterproof sealant for mesh glass and laminated glass edge (cut part), liquid sealant used in automobile parts, electrical parts, various machine parts, etc. It is available.

[0009]

However, even if such a vinyl polymer which is generally excellent in weather resistance and heat resistance is used, it may not be able to withstand under more severe conditions. For example, when it is used for a long time around seals around the engine of a car or near a heat source, or when it is used for a long time in low latitude regions or highlands, especially in places with strong UV rays such as on ice and ice. Etc.

As the vinyl polymer having such a crosslinkable silyl group, a polymer having a hydrolyzable silicon group in which two hydrolyzable groups are bonded per silicon atom is used. There were many.

When the adhesive is used, or when it is used at a low temperature,
In particular, when a very fast curing rate is required, the curing rate is not sufficient, and in order to obtain flexibility after curing, it is necessary to reduce the crosslinking density, and therefore the crosslinking density is not sufficient. There was a problem of stickiness (surface tack). Therefore, the present invention is heat resistance and weather resistance,
An object is to provide a curable composition having excellent curability.

[0012]

DISCLOSURE OF THE INVENTION In the present invention, as a result of intensive studies in view of the above-mentioned situation, at least one crosslinkable functional group is provided.
Vinyl polymer (I) and an antioxidant (I
It was found that the above problems can be improved by using a curable composition containing I), and a vinyl having a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1). The inventors have found that the curability can be further improved by using a curable composition containing a polymer, and have reached the present invention. -SiY _a R _3-a (1) (In the formula, Y, R, and a are the same as above.) The main chain of the vinyl polymer is not particularly limited, but a (meth) acrylic monomer, It is preferably produced mainly by polymerizing a monomer selected from the group consisting of acrylonitrile-based monomers, aromatic vinyl-based monomers, fluorine-containing vinyl-based monomers and silicon-containing vinyl-based monomers, and more preferably (meth) acrylic-based monomers, It is preferable to polymerize using an acrylic monomer, more preferably an acrylic ester monomer, and most preferably a butyl acrylate monomer.

The vinyl polymer is not particularly limited, but the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography.
The value of / Mn) is preferably less than 1.8.

The main chain of the vinyl polymer is not particularly limited, but it is preferably produced by a living radical polymerization method, more preferably an atom transfer radical polymerization method. At this time, the catalyst for the atom transfer radical polymerization method is not particularly limited, but is preferably a metal complex selected from the group consisting of copper, nickel, ruthenium and iron, and more preferably a copper complex.

The position of the crosslinkable silyl group of the vinyl polymer is not limited, but is preferably at the terminal. In addition, the same silyl group may be contained in the main chain, but it is preferable to have a silyl group only at the terminal when rubber elasticity is required for the crosslinked cured product.

The number of crosslinkable silyl groups in the vinyl polymer is
Although not particularly limited, in order to obtain a cured product having higher crosslinkability, one or more on average, preferably 1.2 or more,
More preferably, it is 1.5 or more.

The vinyl polymer is preferably, but not limited to, produced by living radical polymerization,
Atom transfer radical polymerization is more preferred. Further, the atom transfer radical polymerization is not limited, but a complex selected from transition metal complexes having an element of Group 7, 8, 9, 10 or 11 of the periodic table as a central metal is used as a catalyst. Is preferred, more preferably a complex selected from the group consisting of copper, nickel, ruthenium, or iron complex,
Of these, a copper complex is particularly preferable.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to curable compositions. More specifically, the following two components: a curable composition containing a vinyl polymer (I) having at least one crosslinkable functional group and an antioxidant (II), and a crosslinkable functional group. Is a crosslinkable silyl group represented by the general formula (1), and relates to a curable composition containing a vinyl polymer having a crosslinkable silyl group in which a is 3. -SiY _a R _3-a (1) (wherein Y, R, and a in the formula are the same as above.) The curable composition of the invention is described in detail below. << About vinyl-based polymer >><Mainchain> The inventors have heretofore described a vinyl-based polymer having various crosslinkable functional groups at the polymer end, a method for producing the same, a curable composition, and applications. A number of inventions have been made (JP-A-11-080249 and JP-A-11-08025).
0, JP-A-11-005815, JP-A-11-1166
17, JP-A-11-116606, JP-A-11-080
571, JP-A-11-080570, JP-A-11-13
0931, JP-A-11-100433, JP-A-11-1
16763, JP-A-9-272714, JP-A-9-2
72715, etc.). The vinyl polymer (I) of the present invention is not particularly limited, but all the polymers disclosed in the invention exemplified above can be preferably used.

The vinyl monomer constituting the main chain of the vinyl polymer of the present invention is not particularly limited, and various kinds can be used. To illustrate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (n) -propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid-n
-Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) acrylic acid-n
-Pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-
n-heptyl, (meth) acrylic acid-n-octyl,
2-Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth)
Dodecyl acrylate, phenyl (meth) acrylate,
Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Acrylic acid-2
-Hydroxypropyl, 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, 2-perfluoroethyl-2-perfluorobutyl (meth) acrylate Ethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate , (Meth) acrylic acid 2-perfluoro Shiruechiru, (meth) acrylate, 2-perfluoro decyl ethyl, (meth) acrylic acid 2
(Meth) acrylic monomers such as perfluorohexadecylethyl; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, Fluorine-containing vinyl monomers such as vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, fumaric acid Mono- and di-alkyl esters of maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide Maleimide-based monomers such as amide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile-based monomers such as acrylonitrile and methacrylonitrile; vinyl-based monomers containing amide groups such as acrylamide and methacrylamido; vinyl acetate, vinyl propionate, vinyl pivalate, and benzoic acid. Examples thereof include vinyl esters such as vinyl 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 them may be copolymerized.

The main chain of the vinyl polymer 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 it is produced mainly by polymerizing. Here, “mainly” means that 50 mol% or more, preferably 70% or more of the monomer units constituting the vinyl polymer are the above-mentioned monomers.

Of these, styrene-based monomers and (meth) acrylic acid-based monomers are preferable in view of the physical properties of the product. More preferably, acrylic acid ester monomers and methacrylic acid ester monomers, particularly preferably acrylic acid ester monomers, and further preferably,
Butyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, and further may be block copolymerized, and in this case, it is preferable that 40% by weight of these preferred monomers be contained. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Molecular weight distribution of the vinyl polymer of the present invention, that is, weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography.
The ratio (Mw / Mn) with is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, and still more preferably 1.5. Or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. GP in the present invention
In the C measurement, usually, chloroform is used as a 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 in the present invention is not particularly limited, but it is 500 to 1,000,0 when measured by gel permeation chromatography.
The range of 00 is preferable, 1,000 to 100,000 is more preferable, and 5,000 to 50,000 is further preferable. <Synthesis Method of Main Chain> In the present invention, the synthesis method of the vinyl polymer is not limited, but controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. These will be described below. Controlled radical polymerization radical polymerization method is a "general radical polymerization method" in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized by using an azo compound, a peroxide or the like as a polymerization initiator. , A controlled radical polymerization method capable of introducing a specific functional group at a controlled position such as a terminal.

Although the "general radical polymerization method" is a simple method, since a monomer having a specific functional group is stochastically introduced into the polymer by this method, a polymer having a high functionalization rate is used. In order to obtain it, it is necessary to use a considerably large amount of this monomer, and conversely, if used in a small amount, the proportion of the polymer in which this specific functional group is not introduced becomes large. Further, since it is a free radical polymerization, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The "controlled radical polymerization method" is a "chain transfer agent method" in which a vinyl-based polymer having a terminal functional group is obtained by conducting polymerization using a chain transfer agent having a specific functional group. The polymer can be classified as a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing a polymer-grown terminal without causing a termination reaction.

The "chain transfer agent method" is capable of obtaining a polymer having a high functionalization ratio, but requires a considerably large amount of the chain transfer agent having a specific functional group with respect to the initiator, and the treatment There is an economic problem including Further, like the above-mentioned "general radical polymerization method", there is also a problem that since it is a free radical polymerization, a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

In contrast to these polymerization methods, the "living radical polymerization method" is a radical polymerization which is difficult to control because the polymerization rate is high and the termination reaction is likely to occur due to coupling of radicals with each other. The reaction is difficult to occur and the molecular weight distribution is narrow (Mw / Mn is 1.
(About 1 to 1.5) A polymer can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Therefore, in the "living radical polymerization method", a polymer having a narrow molecular weight distribution and a low viscosity can be obtained, and at the same time, a monomer having a specific functional group can be introduced at almost any position of the polymer. Therefore, it is more preferable as a method for producing the vinyl polymer having the specific functional group.

In the narrow sense of living polymerization,
It is a polymerization in which the terminal always keeps the activity and the molecular chain grows. Living polymerization is also included. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 19
1994, 116, 7943, using cobalt porphyrin complexes, Macromolecules, 1994, 2
Vol. 7, p. 7228, which uses a radical scavenger such as a nitroxide compound, "atom transfer radical polymerization" using an organic halide as an initiator and a transition metal complex as a catalyst (Atom Transfer Radii).
Cal Polymerization (ATRP) and the like.

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 features of the radical polymerization method, it has a halogen, etc., which is relatively advantageous for functional group conversion reactions at the terminal, and has a high degree of freedom in the design of initiators and catalysts. It is more preferable as a method for producing a coalescence. As this atom transfer radical polymerization method, for example, Mat
yjaszewski et al., Journal of American Chemical Society (J. Am. Chem. So
c. ) 1995, 117, 5614, Macromolecules 1995.
28, 7901, Science (Science)
e) 1996, 272, 866 pages, WO96 / 30
421 publication, WO97 / 18247 publication, WO98
/ 01480, WO98 / 40415, or Sawamoto et al., Macromolecules (M
acromolecules) 1995, 28, 1
Page 721, JP-A-9-208616, JP-A-8-
No. 41117 is cited.

In the present invention, which of these living radical polymerization methods is used is not particularly limited, but the atom transfer radical polymerization method is preferred.

The living radical polymerization will be described in detail below. Before that, one of the controlled radical polymerizations which can be used for the production of vinyl polymers described later, that is, a chain transfer agent was used. The polymerization will be described.
The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.

A method of obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent as disclosed in JP-A-4-132706, and JP-A-61-2.
No. 71306, Japanese Patent No. 2594402 and Japanese Patent Laid-Open No. 54-47782, a hydroxyl group-terminated polymer is obtained by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent.

The living radical polymerization will be described below.

First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, generally stable nitroxy free radical (= N
-O.) Is used as a radical capping agent. Such compounds include, but are not limited to, 2,2
6,6-Substituted-1-piperidinyloxy radical or 2,
Nitroxy free radicals from cyclic hydroxyamines such as 2,5,5-substituted-1-pyrrolidinyloxy radicals are preferred. As a substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific examples of the nitroxy free radical compound 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, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical,
Examples thereof include N, N-di-t-butylamineoxy radical. A stable free radical such as a galvinoxyl free radical may be used instead of the nitroxy free radical.

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

Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under the polymerization temperature condition is preferable. 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 Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Benzoyl peroxide is particularly preferable. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of peroxide.

Macromolecules 199
5,28,2993, instead of using a radical capping agent and a radical generator together,
An alkoxyamine compound as shown below may be used as an initiator.

[0040]

[Chemical 1] When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a terminal functional group is obtained. When this is used in the method of the present invention, a polymer having a terminal functional group is obtained.

The polymerization conditions such as the monomer, solvent and polymerization temperature used in the polymerization using the radical scavenger such as the nitroxide compound are not limited, but may be the same as those used for the atom transfer radical polymerization described below. .. Atom Transfer Radical Polymerization Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position), Alternatively, a sulfonyl halide compound or the like is used as an initiator. If Specific _{examples, 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 ( where in the above formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine or ^{iodine,) R 1 -C (H)} (X) -CO 2 ^{R 2, R 1 -C (CH} 3)
^{_{(X) -CO 2 R 2,}} R 1 -C (H) (X) -C (O)
R ² , R ¹ -C (CH ₃ ) (X) -C (O) R ² , (in the formula, R ¹ and R ² 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 ¹ -C ₆ H ₄ -SO ₂ X (in each of the above formulas, R ¹ is a hydrogen atom or a carbon number 1).
To an alkyl group, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine).

As the initiator for atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating the polymerization can also be used. In such a case, a vinyl polymer having a functional group at one main chain terminal and a growth terminal structure of atom transfer radical polymerization at the other main chain terminal is produced. Examples of such a functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group and an amide group.

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula (2). ^{R 4 R 5 C (X)} -R 6 -R 7 -C (R 3) = CH 2 (2) ( wherein, R ³ is hydrogen or a methyl group, R ^4, R ⁵ is hydrogen or a carbon A monovalent alkyl group, an aryl group, or an aralkyl of the number 1 to 20, or those linked to each other at the other end, R ⁶ is —C (O) O— (ester group), —C (O) — ( Keto group), or o-, m-, p
-Phenylene group, R ⁷ is a direct bond or has 1 to 2 carbon atoms.
0 is a divalent organic group and may contain one or more ether bonds, and X is chlorine, bromine, or iodine.) Specific examples of the substituents R ⁴ and R ⁵ are hydrogen, methyl group, and ethyl group. , N-propyl group, isopropyl group, butyl group,
Examples thereof include a pentyl group and a hexyl group. R ⁴ and R ⁵ may be connected at the other end to form a cyclic skeleton.

Specific examples of the organic halide having an alkenyl group represented by the general formula (1) 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 ,

[0046]

[Chemical 2] (In each formula mentioned above, X is 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 ,

[0047]

[Chemical 3] (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH₂-C₆H_Four-(CH₂)_n-CH = C
H₂, O, m, p-CH₃C (H) (X) -C₆H_Four-(C
H₂)_n-CH = CH₂, O, m, p-CH₃CH₂C
(H) (X) -C₆H_Four-(CH₂)_n-CH = CH₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer from 0 to 20) o, m, p-XCH₂-C₆H_Four-(CH₂)_n-O- (C
H₂)_m-CH = CH₂, O, m, p-CH₃C (H)
(X) -C₆H_Four-(CH₂)_n-O- (CH₂)_m-CH =
CH₂, O, m, p-CH₃CH₂C (H) (X) -C₆H
_Four-(CH₂)_n-O- (CH₂)_mCH = CH₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-CH
= CH₂, O, m, p-CH₃C (H) (X) -C₆H_Four−
O- (CH₂)_n-CH = CH₂, O, m, p-CH ₃CH
₂C (H) (X) -C₆H_Four-O- (CH₂)_n-CH = C
H₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer from 0 to 20) o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-O-
(CH₂)_m-CH = CH₂, O, m, p-CH₃C (H)
(X) -C₆H_Four-O- (CH₂)_n-O- (CH₂) _m-C
H = CH₂, O, m, p-CH₃CH₂C (H) (X)-
C₆H_Four-O- (CH ₂)_n-O- (CH₂)_m-CH = CH
₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, 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
Examples thereof include compounds represented by the general formula (3). H₂C = C (R³) -R⁷-C (R^Four) (X) -R⁸-R^Five  (3) (In the formula, R³, R^Four, R^Five, R⁷, X is the same as above, R
⁸Is a direct bond, -C (O) O- (ester group), -C
(O)-(keto group), or o-, m-, p-phenyl
Represents a len group) R⁶Is a direct bond or a divalent organic group having 1 to 20 carbon atoms
(May contain one or more ether bonds)
Is a direct bond, the halogen-bonded carbon
Vinyl group is bonded to the element,
is there. In this case, carbon-halogenation is caused by adjacent vinyl groups.
R is because the bond is activated.⁸As C (O) O
It is not always necessary to have a group or phenylene group, etc.
It may be a bond. R⁷Is not a direct bond, charcoal
In order to activate the elementary-halogen bond, R⁸As C
(O) O group, C (O) group and phenylene group are preferred.

To specifically exemplify the compound of the general formula (2), CH ₂ ═CHCH ₂ X, CH ₂ ═C (CH ₃ ) CH ₂ X, C
H 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, C
_{H 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 = C
_{H (CH 2) 8 C (} H) (X) -CO 2 R, CH 2 = CHC
_{H 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 formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group,) and the like, etc. it can.

[0049] Specific examples of a halogenated sulfonyl compound having an alkenyl group, 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 each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20) and the like.

Organic halogen having the above-mentioned crosslinkable silyl group
The compound is not particularly limited and is represented by, for example, the general formula (4).
An example is one having a structure. R^FourR^FiveC (X) -R⁶-R⁷-C (H) (R³) CH₂-[Si (R⁹)_2-b(Y)_b O]_m-Si (R^Ten)_3-a(Y)_a  (4) (In the formula, R³, R^Four, R^Five, R⁶, R⁷, X is the same as above,
R⁹, R^TenAre all alkyl groups having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ')₃SiO-
(R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different.
And a triorganosiloxy group represented by⁹Well
Or R^TenWhen two or more exist, they are the same
May be different. Y is a hydroxyl group or water
A decomposable group is shown, and when two or more Y are present, they are the same.
It may be one or different. a is 0, 1,
2, or 3, and b represents 0, 1, or 2.
m is an integer of 0-19. However, if a + mb ≧ 1
Be satisfied) To specifically exemplify the compound of the general formula (3), XCH₂C (O) O (CH₂)_nSi (OCH₃)₃, CH₃
C (H) (X) C (O) O (CH₂)_nSi (OC
H₃)₃, (CH₃)₂C (X) C (O) O (CH₂)_nSi
(OCH₃)₃, XCH₂C (O) O (CH₂)_nSi (C
H₃) (OCH₃)₂, CH ₃C (H) (X) C (O) O
(CH₂)_nSi (CH₃) (OCH₃)₂, (CH₃)₂C
(X) C (O) O (CH₂)_nSi (CH₃) (OCH₃)
₂, (In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 0 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_mSi (OC
H₃)₃, H₃CC (H) (X) C (O) O (CH₂)_nO
(CH₂)_mSi (OCH₃)₃, (H₃C)₂C (X) C
(O) O (CH₂)_nO (CH₂)_mSi (OCH₃)₃, C
H₃CH₂C (H) (X) C (O) O (CH₂)_nO (CH
₂)_mSi (OCH₃)₃, XCH₂C (O) O (CH₂)_n
O (CH₂)_mSi (CH₃) (OCH₃)₂, H₃CC
(H) (X) C (O) O (CH₂)_nO (CH₂)_m-Si
(CH₃) (OCH₃)₂, (H₃C)₂C (X) C (O)
O (CH₂)_nO (CH₂)_m-Si (CH₃) (OCH₃)
₂, CH₃CH ₂C (H) (X) C (O) O (CH₂)_nO
(CH₂)_m-Si (CH₃) (OCH₃)₂, (In each of the above formulas, X is chlorine, bromine, iodine, and n is
1 to 20 integer, m is 0 to 20 integer) o, m, p-XCH₂-C₆H_Four-(CH₂)₂Si (OC
H₃)₃, O, m, p-CH₃C (H) (X) -C₆H_Four−
(CH₂)₂Si (OCH₃)₃, O, m, p-CH₃CH₂
C (H) (X) -C₆H_Four-(CH₂)₂Si (OC
H₃)₃, O, m, p-XCH₂-C₆H_Four-(CH₂)₃S
i (OCH₃)₃, O, m, p-CH₃C (H) (X)-
C₆H_Four-(CH₂)₃Si (OCH₃)₃, O, m, p-C
H₃CH₂C (H) (X) -C₆H_Four-(CH₂)₃Si (O
CH₃)₃, O, m, p-XCH₂-C₆H_Four-(CH₂)₂
-O- (CH₂)₃Si (OCH₃)₃, O, m, p-CH
₃C (H) (X) -C₆H_Four-(CH₂)₂-O- (CH₂)
₃Si (OCH₃)₃, O, m, p-CH₃CH₂C (H)
(X) -C₆H_Four-(CH₂)₂-O- (CH₂)₃Si (O
CH₃)₃, O, m, p-XCH₂-C₆H_Four-O- (C
H₂)₃Si (OCH₃)₃, O, m, p-CH₃C (H)
(X) -C₆H_Four-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃CH₂C (H) (X) -C₆H_Four-O-
(CH₂)₃-Si (OCH₃)₃, O, m, p-XCH₂
-C₆H_Four-O- (CH₂)₂-O- (CH₂)₃-Si (O
CH₃)₃, O, m, p-CH₃C (H) (X) -C₆H_Four
-O- (CH₂)₂-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃CH₂C (H) (X) -C₆H_Four-O-
(CH₂)₂-O- (CH₂)₃Si (OCH₃)₃, (In each of the above formulas, X is chlorine, bromine, or iodine.
And the like.

Further examples of the organic halide having a crosslinkable silyl group include those having a structure represented by the general formula (5). ^{_{(R 10) 3-a (}} Y) a Si- [OSi (R 9) 2-b (Y) b] m -CH 2 -C (H) (R 3) -R 7 -C (R 4) ( ^{X) -R 8 -R 5 (5} ) ( ^{wherein, R 3, R 4, R} 5, R 7, R 8, R 9, R 10, a,
b, m, X, and Y are the same as above). To specifically exemplify such a compound, (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 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)} 4 C (H) (X) -C 6 H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, aryl Group, aralkyl group) and the like.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. HO- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl having 1 to 20 carbon atoms, Base,
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the above amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. H ₂ N- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or 1 to 20 carbon atoms, An alkyl group of
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the above epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0053]

[Chemical 4] (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,
(Aryl group, aralkyl group, n is an integer of 1 to 20) In order to obtain a polymer having two or more growth terminal structures in one molecule, an organic halide having two or more starting points, or a sulfonyl halide Preference is given to using the compounds as initiators. To give a concrete example,

[0054]

[Chemical 5]

[0055]

[Chemical 6] Etc.

There are no particular restrictions on the vinyl-based monomer used in this polymerization, and all of the above-exemplified ones can be preferably used.

With a transition metal complex used as a polymerization catalyst
It is not particularly limited, but it is preferable that
Group 8, Group 8, Group 10, Group 10 or Group 11 elements as the central metal
It is a metal complex complex. More preferably,
0-valent copper, 1-valent copper, 2-valent ruthenium, 2-valent iron or
An example is a divalent nickel complex. Among them, the complex of copper
The body is preferred. To specifically exemplify a monovalent copper compound
For example, cuprous chloride, cuprous bromide, cuprous iodide, cyanide
Cuprous, cuprous oxide, cuprous perchlorate and the like. Copper compound
In order to increase the catalytic activity of the product, 2,2'-bi
Pyridyl and its derivatives, 1,10-phenanthroline
And its derivatives, tetramethylethylenediamine, pen
Tamethyldiethylenetriamine, hexamethyltris
Ligands such as polyamines such as (2-aminoethyl) amine
Is added. Preferred ligands are nitrogen-containing compounds
More preferred ligands are chelate-type nitrogen-containing compounds.
And more preferred ligands are N, N, N ', N ",
N ″ -pentamethyldiethylenetriamine.
And divalent ruthenium chloride tristriphenylphosphine
In complex (RuCl₂(PPh₃)₃) Is also suitable as a catalyst
Is. When using a ruthenium compound as a catalyst,
Aluminum alkoxides are added as activators
It Further, divalent iron bistriphenylphosphine complex
(FeCl₂(PPh₃)₂) Bivalent nickel bistro
Liphenylphosphine complex (NiCl₂(PP
h ₃)₂), And bivalent nickel bistributylphosphine
Fin complex (NiBr₂(PBu₃)₂) Also as a catalyst
It is suitable.

The polymerization can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile and benzonitrile, ester solvents such as ethyl acetate and butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, which may be used alone or in admixture of two or more.

Although not limited, the polymerization may be performed at 0 ° C to 2 ° C.
It can be carried out in the range of 00 ° C, preferably 50 to 15
It is 0 ° C.

The atom transfer radical polymerization of the present invention also 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 a radical, for example, Cu (II ′) when Cu (I) is used as a catalyst.
On the other hand, a general radical initiator such as a peroxide is allowed to act, and as a result, an equilibrium state similar to atom transfer radical polymerization is produced (Macromolecule
es 1999, 32, 2872). <Functional group> Number of crosslinkable functional groups The number of crosslinkable functional groups of the vinyl polymer is not particularly limited, but from the viewpoint of curability of the composition and physical properties of the cured product,
The average number is preferably 1 or more, more preferably 1.1 or more and 4.0 or less, still more preferably 1.2 or more and 3.5 or less. Position of crosslinkable functional group When the rubbery property is particularly required for the cured product obtained by curing the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased, At least one of the crosslinkable functional groups is preferably at the end of the molecular chain. More preferably, it has all the crosslinkable functional groups at the end of the molecular chain.

A method for producing a vinyl polymer having at least one crosslinkable functional group at the terminal of the molecule, especially a (meth) acrylic polymer, is disclosed in JP-B-3-14068 and JP-B-4-55444. JP-A-6-2119
No. 22, for example. However, since these methods are free radical polymerization methods using the above-mentioned "chain transfer agent method", the resulting polymer has a relatively high proportion of crosslinkable functional groups at the ends of the molecular chain, while Mw / Mn
The value of the molecular weight distribution represented by is generally as large as 2 or more, and there is a problem that the viscosity becomes high. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at a molecular chain terminal at a high ratio, the above-mentioned "living radical polymerization method" is used. It is preferable.

These functional groups will be described below. The crosslinking silyl group of the crosslinkable silyl group present invention, the general formula (6); - [Si ( R 9) 2-b (Y) b O] m -Si (R 10) 3-a (Y) a (6) {In the formula, R ⁹ and R ¹⁰ are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
Or an aralkyl group of (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms and has 3 R ′
May be the same or different) and R ⁹ or R ¹⁰ is 2
When there are one or more, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y 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 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. } The group represented by these is mentioned.

Examples of the hydrolyzable group include commonly used groups such as hydrogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amido group, aminooxy group, mercapto group and alkenyloxy group. To be Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of 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 (a + Σ
The range of b) is preferably 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is 1 or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula ^{(7) -Si (R 10)} 3-a (Y) a (7) ( wherein, R ^10, Y, a is the same. As above) is crosslinkable silyl group represented by Get Is preferable because it is easy.

Although not particularly limited, in consideration of curability, a is preferably 2 or more. In addition, those having 3 a (eg, trimethoxy functional group) have faster curability than those having 2 (eg, dimethoxy functional group), but two have more storage stability and mechanical properties (elongation, etc.). May be better. In order to balance curability and physical properties, two (for example, dimethoxy functional group) and three (for example, trimethoxy functional group) may be used in combination. Alkenyl Group The alkenyl group in the present invention is not limited, but is preferably one represented by the general formula (7). ^{_{H 2 C = C (R 11}} ) - (7) ( wherein, R ¹¹ is a hydrocarbon group of a hydrogen atom or 1 to 20 carbon atoms) in the general formula (7), R ¹¹ is a hydrogen atom or a carbon atoms It is a hydrocarbon group of 1 to 20, and the following groups are specifically exemplified. _{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -
_{CH 3, -CH (CH 2 CH} 3) - (CH 2) n -CH 3, -
_{CH (CH 2 CH 3) 2} , -C (CH 3) 2 - (CH 2) n -
_{CH 3, -C (CH 3)} (CH 2 CH 3) - (CH 2) n -C
_{H 3, -C 6 H 5,} -C 6 H 4 (CH 3), - C 6 H 3 (C
_{H 3) 2, - (CH} 2) n -C 6 H 5, - (CH 2) n -C 6 H 4
_{(CH 3), - (CH} 2) n -C 6 H 3 (CH 3) 2 (n is an integer of 0 or more, and the total number of carbon atoms in each group is 20 or less) Among these, a hydrogen atom is preferable.

Further, but not limited to, the polymer (I)
It is preferable that the alkenyl group is not activated by a carbonyl group, an alkenyl group, or an aromatic ring which is conjugated with the carbon-carbon double bond.

The bond form between the alkenyl group and the polymer main chain is not particularly limited, but it may be bonded via a carbon-carbon bond, an ester bond, an ether bond, a carbonate bond, an amide bond, a urethane bond, or the like. preferable. Amino Group The amino group in the present invention is not limited, but may be —NR ¹² ₂ (R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² may be the same or different. even if well, also connected to each other at the other end, but may form a cyclic structure) and the _{^{like, -. (NR 12 3)}} + X - (R 12 is the same .X as above ^- Is an anion.) There is no problem even if it is an ammonium salt shown in.

In the above formula, R ¹² is hydrogen or has 1 to 2 carbon atoms.
A monovalent organic group of 0, for example, hydrogen, carbon number 1 to 2
Examples thereof include an alkyl group having 0, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Two R ^12's may be the same or different from each other. Further, the other ends may be connected to each other to form a ring structure. Polymerizable carbon-carbon double bond The group having a polymerizable carbon-carbon double bond preferably has the general formula (8): —OC (O) C (R ¹³ ) ═CH ₂ (8) (formula R ¹³ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms), and more preferably R ¹³ is hydrogen or a methyl group. is there.

In the general formula (8), the specific example of R ¹³ is not particularly limited and includes, for example, —H, —CH ₃ , —CH _{2
CH 3, - (CH 2)} n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, but -CN, and the like, preferably -H, -CH ₃ Is. <Functional Group Introducing Method> The functional group introducing method to the vinyl polymer of the present invention will be described below, but the present invention is not limited thereto.

First, a method of introducing a crosslinkable silyl group, an alkenyl group and a hydroxyl group by converting a terminal functional group will be described. Since these functional groups can be precursors to each other, they will be described in order from the crosslinkable silyl group.

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a vinylsilane polymer having at least one alkenyl group, a hydrosilane compound having a crosslinkable silyl group,
Method of addition in the presence of hydrosilylation catalyst (B) Method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule (C) Method of reacting compound having both polymerizable alkenyl group and crosslinkable silyl group in one molecule when synthesizing vinyl polymer by radical polymerization (D) Synthesis of vinyl polymer by radical polymerization At this time, a method using a chain transfer agent having a crosslinkable silyl group (E) at least one carbon-halogen bond having high reactivity is used.
A method of reacting a vinyl-based polymer having one unit with a compound having a crosslinkable silyl group and a stable carbanion in one molecule;
And so on.

The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. The synthesis method is illustrated below, but the synthesis method is not limited thereto.

(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a polymerizable alkenyl group and a low-polymerizable alkenyl group in one molecule as represented by the following general formula (9) are used. A method of reacting a compound having both as a second monomer. ^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (9) ( wherein, R ¹⁴ represents a hydrogen or a methyl group, R ¹⁵ is -C
(O) O-, or o-, m-, p-phenylene group, R ¹⁶ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, and contains at least one ether bond. You may stay. R ¹⁷ is hydrogen, or an alkyl group having 1 to 20 carbon atoms,
It represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms) It should be noted that there is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. In particular, in the case of expecting rubber-like properties in living radical polymerization, it is preferable to react as the second monomer at the end of the polymerization reaction or after the reaction of a predetermined monomer.

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

(Ac) Various organic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin in a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of reacting a metal compound to replace halogen.

(A-d) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group as represented by the general formula (10) to give halogen. How to replace. ^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10) ( wherein, R ¹⁷ is as defined above, R ^18, R ¹⁹ together carbanion C ^- stable Is an electron-withdrawing group, or one is the electron-withdrawing group and the other is hydrogen or a carbon number of 1 to 10
Represents an alkyl group or a phenyl group. R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and may contain one or more ether bonds. M ⁺ represents an alkali metal ion or a quaternary ammonium ion) The electron withdrawing group of R ¹⁸ and R ¹⁹ is —CO ₂ R or —C.
Those having a structure of (O) R and —CN are particularly preferable.

(Ae) The enolate anion is prepared by reacting a vinyl-based polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. An electrophilic compound having an alkenyl group, such as 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. How to react.

(Af) A vinyl polymer having at least one carbon-halogen bond having high reactivity is added to an oxyanion or carboxy having an alkenyl group as represented by the general formula (11) or (12). A method of substituting halogen by reacting a rate anion. ^{_{H 2 C = C (R 17}} ) -R 21 -O - M + (11) ( wherein, R ^17, M ⁺ is the same .R ²¹ above are 1 to 2 carbon atoms
0 bivalent may contain one or more ether bonds with organic _{groups) H 2 C = C (R} 17) -R 22 -C (O) O - M + (12) ( wherein, R ¹⁷ and M ⁺ are the same as above, and R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds).

The above-mentioned method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is carried out by using the above-mentioned organic halide or the like as an initiator and an atom transfer radical catalyzed by a transition metal complex. Examples of the polymerization method include, but are not limited to, the following.

The vinyl polymer having at least one alkenyl group can also be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto. is not.
A method of reacting a hydroxyl group of a vinyl polymer having at least one hydroxyl group with a base such as (A-g) sodium methoxide and reacting it with an alkenyl group-containing halide such as allyl chloride.

(A-h) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.

(Ai) A method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine.

(Aj) A method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst; and the like.

In the present invention, when the halogen does not directly participate in the method of introducing an alkenyl group such as (Aa) and (Ab), a vinyl polymer should be synthesized by the living radical polymerization method. Is preferred. The method (Ab) is more preferable because it is easier to control.

When the alkenyl group is introduced by converting the halogen of the vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halogen having at least one highly reactive carbon-halogen bond. Compound, or a sulfonyl halide compound as an initiator,
Obtained by radical polymerization of a vinyl monomer using a transition metal complex as a catalyst (atom transfer radical polymerization method),
At least one highly reactive carbon-halogen bond at the end
It is preferable to use a vinyl polymer having a number of individual units. The method (Af) is more preferable because it is easier to control.

The hydrosilane compound having a crosslinkable silyl group is not particularly limited, but a typical example thereof is a compound represented by the general formula (13). _{^{H- [Si (R 9) 2}} -b (Y) b O] m -Si (R 10) 3-a (Y) a (13) { wherein, R ^9, R ¹⁰ are both carbons 1 ~ 20 alkyl groups, C6-20 aryl groups, C7-20
Or an aralkyl group of (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms and has 3 R ′
May be the same or different) and R ⁹ or R ¹⁰ is 2
When there are one or more, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y 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 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. } Of these hydrosilane compounds, particularly the general formula (1
4) A compound having a crosslinkable group represented by H-Si (R ¹⁰ ) _3-a (Y) _a (14) (wherein R ¹⁰ , Y and a are the same as above) is preferable from the viewpoint of easy availability. .

When the above-mentioned hydrosilane compound having a crosslinkable silyl group is added to the alkenyl group, a transition metal catalyst is usually used. As the transition metal catalyst, for example, platinum simple substance, alumina, silica, a dispersion of platinum solid in a carrier such as carbon black, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone,
Examples thereof include a platinum-olefin complex and a platinum (0) -divinyltetramethyldisiloxane complex. 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 can be mentioned.

The following methods are exemplified as the method for producing the vinyl polymer having at least one hydroxyl group used in the methods (B) and (A-g) to (A-j). These methods are exemplified. It is not limited to.

(Ba) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (15) is used. Method of reacting as a monomer of 2. ^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -OH (15) ( ^{wherein, R 14, R 15, R} 16 are as defined above) The polymerization of the alkenyl group and a hydroxyl group per molecule There is no limitation on the timing of reacting the compound having both of the two, but particularly in living radical polymerization, when rubber properties are expected, the reaction is performed as the second monomer at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. Is preferred.

(Bb) When synthesizing a vinyl polymer by living radical polymerization, alkenyl such as 10-undecenol, 5-hexenol or allyl alcohol is added at the end of the polymerization reaction or after the reaction of a predetermined monomer. A method of reacting alcohol.

(B-c) For example, JP-A-5-262808
A method of radically polymerizing a vinyl-based monomer by using a large amount of a chain transfer agent containing a hydroxyl group such as a polysulfide containing a hydroxyl group as shown in.

(Bd) For example, JP-A-6-23991
2. A method of radically polymerizing a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as shown in JP-A-8-283310.

(Be) For example, Japanese Patent Laid-Open No. 6-116312
A method of radically polymerizing a vinyl-based monomer by using an alcohol in excess as shown in 1).

(Bf) For example, Japanese Patent Laid-Open No. 4-132706
And the like, a method of introducing a hydroxyl group at the terminal by hydrolyzing or reacting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond with a hydroxyl group-containing compound.

(B-g) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as represented by the general formula (16) to substitute halogen. how to. ^{M + C - (R 18)} (R 19) -R 20 -OH (16) as an electron withdrawing group ^{(wherein, R 18, R 19, R} 20, are the same) R ^18, R ¹⁹ are, -CO ₂ R, -C
Those having a structure of (O) R and —CN are particularly preferable.

(Bh) A vinyl polymer having at least one carbon-halogen bond having high reactivity is reacted with a metal element such as zinc or an organometallic compound to prepare an enolate anion. A method of reacting aldehydes or ketones later.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is added to an oxyanion or carboxylate having a hydroxyl group as represented by the general formula (17) or (18). A method of substituting halogen by reacting an anion. ^{HO-R 21 -O - M +} (17) ( wherein, R ²¹ and M ⁺ are the ^{same) HO-R 22 -C (O} ) O - M + (18) ( wherein, R ²² and M ⁽⁺ Is the same as above) (B-j) When synthesizing a vinyl-based polymer by living radical polymerization, at the end of the polymerization reaction or after the reaction of a predetermined monomer, as a second monomer, polymerizable in one molecule. A method of reacting a compound having a low alkenyl group and a hydroxyl group.

Such compounds are not particularly limited, but include compounds represented by the general formula (19). ^{_{H 2 C = C (R 14}} ) -R 21 -OH (19) ( wherein, R ¹⁴ and R ²¹ are the same as those described above.) In particular limitation is imposed on the compound represented by the above general formula (19) However, it is easy to obtain, so 10-
Alkenyl alcohols such as undecenol, 5-hexenol, allyl alcohol are preferred. Etc.

In the present invention, when the halogen does not directly participate in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a living radical polymerization method is used for vinyl-based polymerization. It is preferable to synthesize a polymer. The method (Bb) is more preferable because it is easier to control.

When a hydroxyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide,
Alternatively, a vinyl-based compound having at least one highly reactive carbon-halogen bond at a terminal, which is obtained by radically polymerizing a vinyl-based monomer (atom transfer radical polymerization method) using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. Preference is given to using polymers. The method (Bi) is more preferable because it is easier to control.

The compound having a group capable of reacting with a crosslinkable silyl group and a hydroxyl group such as an isocyanate group in one molecule is, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane and the like can be mentioned, and if necessary, a generally known catalyst for urethanization reaction can be used.

Examples of the compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include, for example, trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. Examples include those represented by the following general formula (20). ^{_{H 2 C = C (R 14}} ) -R 15 -R 23 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) 3-a (Y) a (20) ( Formula In the formula, R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ , Y, a, b, and m are the same as above, and R ²³ is a direct bond or a divalent organic group having 1 to 20 carbon atoms. It may contain an ether bond.) There is no particular limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule, but it is expected to have rubber-like properties particularly in living radical polymerization. In that case, it is preferable to react as the second monomer at the end of the polymerization reaction or after the reaction of the predetermined monomer.

Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method (D) include, for example, Japanese Patent Publication No.
-14068 and Japanese Patent Publication No. 4-55444, mercaptans having a crosslinkable silyl group, hydrosilanes having a crosslinkable silyl group and the like can be mentioned.

The above-mentioned method for synthesizing the vinyl polymer having at least one highly reactive carbon-halogen bond used in the method (E) uses the above-mentioned organic halide as an initiator and transition. An atom transfer radical polymerization method using a metal complex as a catalyst can be mentioned, but the method is not limited thereto. Examples of the compound having a crosslinkable silyl group and a stabilizing carbanion in one molecule include compounds represented by the general formula (21). ^{M + C - (R 18)} (R 19) -R 24 -C (H) (R 25) -CH 2 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) _3-a (Y) _a (21) (In the formula, R ⁹ , R ¹⁰ , R ¹⁸ , R ¹⁹ , Y, a, b and m are the same as above. R ²⁴ is a direct bond or has 1 to 1 carbon atoms. R ²⁵ is hydrogen, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms, which is a divalent organic group having 10 or more and may contain one or more ether bonds.
The aralkyl group of is shown. ) Examples of the electron withdrawing group for R ¹⁸ and R ¹⁹ include —CO ₂ R and —C.
Those having a structure of (O) R and —CN are particularly preferable. Vinyl polymer having a terminal reactive functional group in the epoxy group present invention include, but are not limited to, the following steps: (1) producing a vinyl polymer by polymerizing a vinyl monomer to living radical polymerization (2) Subsequently, a compound having both a reactive functional group and an ethylenically unsaturated group is reacted;

In addition, in the atom transfer radical polymerization, a method in which allyl alcohol is reacted at the final stage of the polymerization and then epoxy cyclization is carried out with a hydroxyl group and a halogen group can be mentioned. Amino Group As a method for producing a vinyl polymer having at least one amino group at the terminal of the main chain, the following steps can be mentioned. (1) A vinyl polymer having at least one halogen group at the terminal of the main chain is produced, and (2) terminal halogen is converted into a substituent having an amino group by using an amino group-containing compound.

The substituent having an amino group is not particularly limited, but the group represented by the general formula (22) is exemplified. —O—R ²⁶ —NR ¹² ₂ (22) (In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms, which may have one or more ether bonds or ester bonds. ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² may be the same or different from each other, and they are connected to each other at the other end to form a cyclic structure. In the above general formula (22), R ²⁶ has 1 to more carbon atoms which may have one or more ether bonds or ester bonds.
It is a divalent organic group having 20 carbon atoms, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and 7 carbon atoms.
Although like aralkylene group ^{_{~20, -C 6 H 4 -R 27}} - ( wherein, C ₆ H ₄ is a phenylene group, R ²⁷ is includes a direct bond or one or more ether or ester bonds even Idei represents an divalent organic group having 1 to 14 carbon atoms) ^{or, -C (O) -R 28 -} . ( wherein, R ²⁸ is a direct bond or one or more ether or ester bonds 1 to 19 carbon atoms which may contain
Represents a divalent organic group. ) Is preferred.

By converting the terminal halogen of the vinyl polymer, an amino group can be introduced at the polymer terminal. The substitution method is not particularly limited, but a nucleophilic substitution reaction using an amino group-containing compound as a nucleophile is preferable because the reaction can be easily controlled. Examples of such a nucleophile include compounds having both a hydroxyl group and an amino group represented by the general formula (23). ¹² ₂ (23) (wherein HO-R ²⁶ -NR, R ²⁶ is, .R ¹² representing one or more ether bond or a divalent organic group having carbon atoms which may contain 1 to 20 ester bond Is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ^{12 s} may be the same or different from each other, and they are connected to each other at the other end to form a cyclic structure. In the general formula (23), R ²⁶ has from 1 to more carbon atoms which may contain one or more ether bonds or ester bonds.
It is a divalent organic group having 20 carbon atoms, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and 7 carbon atoms.
-20 aralkylene groups etc. are mentioned. Among these compounds having both a hydroxyl group and an amino group, R ²⁶ is —C ₆ H ₄ —R ²⁷ — (wherein C ₆ H ₄ is a phenylene group, R ²⁷ is a direct bond or one or more ethers. aminophenols represented by bonds or contain an ester bond represents a divalent organic group having carbon atoms which may 1~14); -C (O) -R 28 - ( wherein, R ²⁸ is a direct 1 to 19 carbon atoms which may contain a bond or one or more ether bond or ester bond
Which represents a divalent organic group of);

Specific compounds include, for example, ethanolamine; o, m, p-aminophenol; o, m, p-
_{NH 2 -C 6 H 4 -CO 2} H; glycine, alanine, etc. aminobutanoic acid.

A compound having both an amino group and an oxyanion can also be used as a nucleophile. The compound is not particularly limited, but for example, the compound represented by the general formula (2
The compounds shown in 4) are mentioned. M ⁺ O ⁻ —R ²⁶ —NR ¹² ₂ (24) (In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms, which may have one or more ether bonds or ester bonds. R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and the two R ¹² may be the same or different from each other, and they are connected to each other at the other end to form a cyclic structure. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) In the general formula (24), M ⁺ is a counter cation of an oxyanion, and is an alkali metal ion or a quaternary ammonium ion. Represent Examples of the alkali metal ion include lithium ion, sodium ion, potassium ion and the like, and sodium ion or potassium ion is preferable. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion and dimethylpiperidinium ion.

Of the above-mentioned compounds having both an amino group and an oxyanion, the aminophenol salt represented by the general formula (25), or the general formula ( The salts of amino acids shown in 26) are preferable. ^{_{M + O - -C 6 H 4}} -R 27 -NR 12 2 (25) M + O - -C (O) -R 28 -NR 12 2 (26) ( wherein, C ₆ H ₄ is a phenylene group, R ²⁷ is a direct bond or a divalent organic group having 1 to 14 carbon atoms which may contain one or more ether bonds or ester bonds, and R ²⁸ is a direct bond or one or more ether bonds or ester bonds. represents a divalent organic group comprise also good to 19 carbon atoms and .R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ¹² are different may be the same with each other even if well, also connected to each other at the other end, the compounds may also form a cyclic structure .M ⁺ is having an oxy anion represented the same.) in formula (24) to (26) and the Is easily obtained by reacting the compound represented by the general formula (23) with a basic compound. That.

Various compounds can be used as the basic compound. For example, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium-tert-butoxide, potassium-tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, hydrogen carbonate. Sodium, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyl lithium, ethyl lithium, n-butyl lithium, ter
t-butyllithium, lithium diisopropylamide,
Examples thereof include lithium hexamethyldisilazide. The amount of the base used is not particularly limited, but is 0.5 to 5 equivalents, preferably 0.8 to 1.2 equivalents, relative to the precursor.

Examples of the solvent used in reacting the above precursor with the above base include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated methylene chloride and chloroform. Hydrocarbon-based solvent; ketone-based solvent such as acetone, methyl ethyl ketone, 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 Carbonate solvents such as propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide. These may be used alone or in combination of two or more.

The compound having an oxyanion in which M ⁺ is a quaternary ammonium ion can be obtained by preparing a compound in which M ⁺ is an alkali metal ion and reacting this with a quaternary ammonium halide. Examples of the quaternary ammonium halide include tetramethylammonium halide, tetraethylammonium halide, trimethylbenzylammonium halide, trimethyldodecylammonium halide, tetrabutylammonium halide and the like.

As the solvent used for the substitution reaction of the polymer terminal halogen, various solvents may be used. For example, hydrocarbon solvents such as benzene and toluene; diethyl ether,
Ether-based solvent such as tetrahydrofuran; halogenated hydrocarbon-based solvent such as methylene chloride and chloroform; ketone-based solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, ter
Alcohol solvents such as t-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; dimethylformamide and dimethyl. Examples thereof include amide solvents such as acetamide; sulfoxide solvents such as dimethyl sulfoxide. They are,
They can be used alone or in combination of two or more.

The reaction temperature may be 0 to 150 ° C. The amount of the amino group-containing compound used is not particularly limited, but is 1 to 5 equivalents, and preferably 1 to 1.2 equivalents, relative to the polymer terminal halogen.

A basic compound may be added to the reaction mixture in order to accelerate the nucleophilic substitution reaction. Examples of such a basic compound include, in addition to those already exemplified, alkylamines such as trimethylamine, triethylamine and tributylamine; polyamines such as tetramethylethylenediamine and pentamethyldiethylenetriamine; pyridine compounds such as pyridine and picoline.

When the amino group of the amino group-containing compound used in the nucleophilic substitution reaction affects the nucleophilic substitution reaction, it is preferably protected by a suitable substituent. As such a substituent, a benzyloxycarbonyl group,
Examples thereof include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

Further, a method of substituting the halogen terminal of the vinyl polymer with an azide anion and then reducing with LAH or the like can be mentioned. Polymerizable carbon-carbon double bond The method of introducing a polymerizable carbon-carbon double bond into the polymer (I) of the present invention is not limited, but the following methods may be mentioned. A method for producing a vinyl polymer by substituting a halogen group of the vinyl polymer with a radically polymerizable compound having a carbon-carbon double bond. As a specific example, a method of reacting a vinyl polymer having a structure represented by the general formula (27) with a compound represented by the general formula (28). —CR ²⁹ R ³⁰ X (27) (In the formula, R ²⁹ and R ³⁰ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine, or iodine.) M ^{+ - OC (O) C (R} 13) = CH 2 (28) ( wherein, R ¹³ is hydrogen, or, .M ⁺ is an alkali metal represents an organic group having 1 to 20 carbon atoms, or a quaternary ammonium ion A method of reacting a vinyl polymer having a hydroxyl group with a compound represented by the general formula (29). XC (O) C (R ¹³ ) ═CH ₂ (29) (In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.) A vinyl polymer having a diisocyanate compound is reacted with the residual isocyanate group and the general formula (3
A method by reaction with a compound represented by 0). ^{HO-R 31 -OC (O)} C (R 13) = CH 2 (30) ( wherein, R ¹³ is hydrogen or,, .R ³¹ 2 to 20 carbon atoms represents an organic group having 1 to 20 carbon atoms Represents a divalent organic group.) Hereinafter, each of these methods will be described in detail.

The above method will be described. A method comprising reacting a vinyl polymer having a terminal structure represented by the general formula (27) with a compound represented by the general formula (28). —CR ²⁹ R ³⁰ X (27) (In the formula, R ²⁹ and R ³⁰ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine, or iodine.) M ^{+ - OC (O) C (R} 13) = CH 2 (28) ( wherein, R ¹³ is hydrogen, or, .M ⁺ is an alkali metal represents an organic group having 1 to 20 carbon atoms, or a quaternary ammonium ion The vinyl polymer having a terminal structure represented by the general formula (27) is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl compound as an initiator and a transition metal complex as a catalyst. Alternatively, it is produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, and the former is preferable.

The compound represented by the general formula (28) is not particularly limited, but specific examples of R ¹³ include, for example,
_{-H, -CH 3, -CH 2 CH} 3, - (CH 2) n CH 3 (n
Represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH,
—CN and the like are mentioned, and —H and —CH ₃ are preferable. M ⁺ is a counter cation of the oxyanion, and examples of M ⁺ include alkali metal ions, specifically, lithium ion, sodium ion, potassium ion, and quaternary ammonium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion and dimethylpiperidinium ion, and sodium ion and potassium ion are preferable. The amount of the oxyanion of the general formula (28) used is preferably 1 to 5 equivalents, more preferably 1.0 to 5 equivalents, relative to the halogen group of the general formula (27).
1.2 equivalents. The solvent for carrying out this reaction is not particularly limited, but a polar solvent is preferable because it is a nucleophilic substitution reaction, and examples thereof include tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and hexamethylphosphoric. Triamide, acetonitrile,
Etc. are used. The temperature at which the reaction is carried out is not limited,
Generally, it is carried out at 0 to 150 ° C, preferably at room temperature to 100 ° C in order to retain the polymerizable end group.

The above method will be described. A method comprising reacting a vinyl polymer having a hydroxyl group with a compound represented by the general formula (29). XC (O) C (R ¹³ ) ═CH ₂ (29) (In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.) General The compound represented by formula (29) is not particularly limited, but specific examples of R ¹³ include, for example, —H, —CH.
_{3, -CH 2 CH 3, -} (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like are exemplified, preferably - H, is a -CH _3.

The vinyl polymer having a hydroxyl group, preferably 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 hydroxyl group. It is produced by a method of polymerizing a vinyl-based monomer using a compound having a chain transfer agent as a chain transfer agent, and the former is preferable. The method for producing a vinyl polymer having a hydroxyl group by these methods is not limited, but the following methods are exemplified.

(A) When synthesizing a vinyl polymer by living radical polymerization, the second monomer is a compound represented by the following general formula (31) or the like and having a polymerizable alkenyl group and a hydroxyl group in one molecule. As a reaction. ^{_{H 2 C = C (R 32}} ) -R 33 -R 34 -OH (31) ( wherein, R ³² is preferably a hydrogen or a methyl group with an organic group having 1 to 20 carbon atoms, being the same or different R ³³ represents —C (O) O— (ester group), or o-, m- or p-phenylene group, and R ³⁴ has a direct bond or has one or more ether bonds. Which represents a divalent organic group having 1 to 20 carbon atoms, wherein R ³³ is an ester group and is a (meth) acrylate compound, and R ³³ is a phenylene group is a styrene compound. Although there is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, especially in the case of expecting rubber-like properties, at the end of the polymerization reaction or after the reaction of a predetermined monomer, It is preferable to react as a monomer of 2. There.

(B) When synthesizing a vinyl polymer by living radical polymerization, at the end of the polymerization reaction or after the reaction of a predetermined monomer, as a second monomer, an alkenyl group having low polymerizability in one molecule and A method of reacting a compound having a hydroxyl group.

Such compounds are not particularly limited, but include compounds represented by the general formula (32). ^{_{H 2 C = C (R 32}} ) -R 35 -OH (32) ( wherein, R ³² are the same as those described above .R ³⁵ number of 1 or more which may contain an ether bond carbons 1 ~ 20
Represents a divalent organic group. ) The compound represented by the general formula (32) is not particularly limited, but 10- because it is easily available.
Alkenyl alcohols such as undecenol, 5-hexenol, allyl alcohol are preferred.

(C) At least one carbon-halogen bond represented by the general formula (27), which is obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706, is obtained. A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of the vinyl polymer having with a compound having a hydroxyl group.

(D) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (27) obtained by atom transfer radical polymerization is added to the general formula (3).
A method of substituting halogen by reacting a stabilized carbanion having a hydroxyl group as described in 3). M ⁺ C ⁻ (R ³⁶ ) (R ³⁷ ) —R ³⁵ —OH (33) (In the formula, R ³⁵ is the same as described above. Both R ³⁶ and R ³⁷ are electrons for stabilizing carbanion C ^−. An attracting group, or one of them is an electron withdrawing group and the other is hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group.
^Examples of the electron withdrawing group for R ³⁶ and R ³⁷ include —CO ₂ R (ester group), —C (O) R (keto group), and —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.
Is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ³⁶ and R ³⁷ , —CO ₂ R, —C (O) R and —CN are particularly preferable. (E) General formula (2) obtained by atom transfer radical polymerization
7) A vinyl-based polymer having at least one carbon-halogen bond is reacted with a metal element such as zinc or an organometallic compound to prepare an enolate anion, and then an aldehyde or a ketone is prepared. Method of reacting a class.

(F) A vinyl polymer having at least one halogen at the terminal of the polymer, preferably at least one halogen represented by the general formula (27) is added to a hydroxyl group-containing oxyanion represented by the following general formula (34). Alternatively, a method of reacting a hydroxyl group-containing carboxylate anion represented by the following general formula (35) or the like to substitute the halogen with a hydroxyl group-containing substituent. ^{HO-R 35 -O - M +} (34) ( wherein, R ³⁵ and M ⁺ are the same as those described ^{above.) HO-R 35 -C (} O) O - M + (35) ( in the formula , R ³⁵ and M ⁺ are the same as those described above.) In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), it is easier to control. The method (b) is more preferable.

Further, in the case of introducing a hydroxyl group by converting the halogen of the vinyl polymer having at least one carbon-halogen bond as in (c) to (f), it is easier to control ( The method of f) is more preferable.

The above method will be described. A vinyl-based polymer having a hydroxyl group is reacted with a diisocyanate compound, and the residual isocyanate group and the general formula (3
A method by reaction with a compound represented by 6). ^{HO-R 31 -OC (O)} C (R 13) = CH 2 (36) ( wherein, R ¹³ is hydrogen or,, .R ³¹ 2 to 20 carbon atoms represents an organic group having 1 to 20 carbon atoms The divalent organic group of is represented by the formula.) The compound represented by formula (36) is not particularly limited, but specific examples of R ¹³ include, for example, —H, —CH.
_{3, -CH 2 CH 3, -} (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like are exemplified, preferably - H, is a -CH _3. Specific examples of the compound include 2-hydroxypropyl methacrylate.

The vinyl polymer having a hydroxyl group at the terminal is
As above.

The diisocyanate compound is not particularly limited, but any conventionally known diisocyanate compound can be used. For example, toluylene diisocyanate, 4,4′-
Diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and other isocyanate compounds; and the like. be able to. These may be used alone or in combination of two or more. Blocked isocyanate may also be used.

In order to take advantage of the better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate. << About Antioxidants (III) and Light Stabilizers (IV) >> Various kinds of antioxidants (III) or light stabilizers (IV) are known in the present invention. For example, published by Taiseisha. "Handbook of Antioxidants", "Degradation and Stabilization of Polymer Materials" published by CMC (235-235)
242) and the like, but are not limited to these.

The antioxidant (III) is not particularly limited, but MARK PEP-36 and MARK AO.
A thioether system such as -23 (all of which are manufactured by ADEKA A-GAS CHEMICAL), Irgafos38, Irgafos16
8, and phosphorus-based antioxidants such as IrgafosP-EPQ (all of which are manufactured by Nippon Ciba Geigy) and the like. Among them, the hindered phenol compounds shown below are preferable.

As the hindered phenol compound,
Specifically, the following can be exemplified. 2,6-ge-te
rt-butyl-4-methylphenol, 2,6-di-t
ert-Butyl-4-ethylphenol, mono (or di or tri) (α-methylbenzyl) phenol, 2,2 ′
-Methylenebis (4ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-t)
ert-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, triethyleneglycol-bis- [3- ( 3-t-
Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4
-Hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-
4-Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4) -Hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl)
Benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, Tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyl] hydrazine, tris (2,4-di-t-
Butylphenyl) phosphite, 2- (5-methyl-)
2-hydroxyphenyl) benzotriazole, 2-
[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
Condensation with t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight about 300). Substance, hydroxyphenylbenzotriazole derivative, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-
Hydroxy benzoate etc. are mentioned.

Speaking of product names, Nocrac 200, Nocrac M-17, Nocrac SP, Nocrac SP-
N, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Nocrac 300, Nocrac NS-
7, Nocrac DAH (all manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), MARK AO-30, MARK AO-40,
MARK AO-50, MARK AO-60, MAR
K AO-616, MARK AO-635, MARK
AO-658, MARK AO-80, MARK A
O-15, MARK AO-18, MARK 328,
MARK AO-37 (all manufactured by Adeka Argus Chemical Co., Ltd.), IRGANOX-245, IRGANOX-2
59, IRGANOX-565, IRGANOX-10
10, IRGANOX-1024, IRGANOX-1
035, IRGANOX-1076, IRGANOX-
1081, IRGANOX-1098, IRGANOX
-1222, IRGANOX-1330, IRGANO
X-1425WL (all from Japan Ciba Geigy), Sumilizer GM, Sumilizer G
Examples thereof include A-80 (all of which are manufactured by Sumitomo Chemical Co., Ltd.), but are not limited thereto.

As the light stabilizer (IV), tinuvin P, tinuvin 234, tinuvin 320, tinuvin 32 are used.
6, tinuvin 327, tinuvin 329, tinuvin 213
Benzotriazole compounds such as (all manufactured by Ciba Geigy), triazines such as Tinuvin 1577, benzophenone such as CHIMASSORB 81, Tinuvin 120 (manufactured by Ciba Geigy)
Examples thereof include UV absorbers such as benzoate compounds.

Of these, hindered amine compounds are more preferable. Specific examples of the hindered amine compound include the following. Dimethyl succinate-1
-(2-hydroxyethyl) -4-hydroxy-2,
2,6,6-Tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl}
{(2,2,6,6-tetramethyl-4-piperidyl)
Imino}], N, N'-bis (3aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,
2,2,6,6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl)
Examples thereof include sebacate and succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) ester.

Speaking by product name, tinuvin 622LD, tinuvin 144, CHIMASSORB944LD, CH
IMASSORB119FL, (all of which are manufactured by Ciba-Geigy), MARK LA-52, MARK LA
-57, MARK LA-62, MARK LA-6
7, MARK LA-63, MARK LA-68, M
ARK LA-82, MARK LA-87 (all of which are manufactured by ADEKA A-GAS CHEMICAL CO., LTD.), SANOL LS-770,
Examples thereof include Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, and Sanol LS-440 (all of which are manufactured by Sankyo), but are not limited thereto.

Antioxidant (III) is light stabilizer (IV)
It may be used in combination with, and it is particularly preferable because the effect may be further exhibited and the heat resistance may be improved by using in combination. It is also possible to use TINUVIN C353, TINUVIN B75 (both of which are manufactured by Nippon Ciba Geigy) and the like in which the antioxidant (III) and the light stabilizer (IV) are mixed in advance.

The antioxidant (III) or the light stabilizer (IV) is not particularly limited, but by using a high molecular weight compound, the heat resistance improving effect of the present invention can be exhibited for a longer period of time. More preferable.

Antioxidant (III) or light stabilizer (I
The amount of V) used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl polymer. If it is less than 0.1 part by weight, the effect of improving heat resistance is small, and if it exceeds 5 parts by weight, there is no great difference in effect and it is economically disadvantageous. << Regarding Light Stabilizer (IV ') and Antioxidant (III') >> Various kinds of light stabilizer (IV ') and antioxidant (III') in the present invention are known, For example, "Handbook of Antioxidants" issued by Taisei Co.,
"Degradation and stabilization of polymer materials" published by CMC
Examples thereof include, but are not limited to, those described in (235-242).

The light stabilizer (IV ') is not particularly limited, but an ultraviolet absorber is preferable, and specifically, tinuvin P, tinuvin 234, tinuvin 320, tinuvin 326, tinuvin 327, tinuvin 329, tinuvin 2 are preferable.
Benzotriazole-based compounds such as 13 (all manufactured by Ciba-Geigy), triazine-based compounds such as Tinuvin 1577, benzophenone-based compounds such as CHIMASSORB81, benzoate-based compounds such as Tinuvin 120 (manufactured by Ciba-Geigy) Can be illustrated.

Further, hindered amine compounds are also preferable, and such compounds are described below. Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate,
Poly [{6- (1,1,3,3-tetramethylbutyl)
Amino-1,3,5-triazine-2,4-diyl}
{(2,2,6,6-tetramethyl-4-piperidyl)
Imino}], N, N'-bis (3aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,
2,2,6,6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl)
Examples thereof include sebacate and succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) ester.

Speaking by product name, tinuvin 622LD, tinuvin 144, CHIMASSORB944LD, CH
IMASSORB119FL, Irgafos168,
(All above are made by Ciba-Geigy Japan), MARK LA
-52, MARK LA-57, MARK LA-6
2, MARK LA-67, MARK LA-63, M
ARK LA-68, MARK LA-82, MARK
LA-87, (all of which are manufactured by ADEKA AG-Chemicals), SANOL LS-770, SANOL LS-765,
Examples thereof include Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, and Sanol LS-440 (all of which are manufactured by Sankyo), but are not limited thereto.

Further, the combination of the ultraviolet absorber and the hindered amine type compound may exert more effects, and therefore is not particularly limited, but may be used in combination, and it is preferable to use in combination.

The antioxidant (III ') is not particularly limited, but MARK PEP-36, MARK A
Thioether type such as O-23 (all of them are ADEKA-
Gas chemical), Irgafos38, Irgafos1
68, phosphorus-based antioxidants such as IrgafosP-EPQ (all of which are manufactured by Ciba-Geigy) and the like. Among them, the hindered phenol compounds shown below are preferable.

As the hindered phenol compound,
Specifically, the following can be exemplified. 2,6-ge-te
rt-butyl-4-methylphenol, 2,6-di-t
ert-Butyl-4-ethylphenol, mono (or di or tri) (α-methylbenzyl) phenol, 2,2 ′
-Methylenebis (4ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-t)
ert-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, triethyleneglycol-bis- [3- ( 3-t-
Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4
-Hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-
4-Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4) -Hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl)
Benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, Tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyl] hydrazine, tris (2,4-di-t-
Butylphenyl) phosphite, 2- (5-methyl-)
2-hydroxyphenyl) benzotriazole, 2-
[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
Condensation with t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight about 300). Substance, hydroxyphenylbenzotriazole derivative, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-
Hydroxy benzoate etc. are mentioned.

Speaking of product names, Nocrac 200, Nocrac M-17, Nocrac SP, Nocrac SP-
N, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Nocrac 300, Nocrac NS-
7, Nocrac DAH (all manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), MARK AO-30, MARK AO-40,
MARK AO-50, MARK AO-60, MAR
K AO-616, MARK AO-635, MARK
AO-658, MARK AO-80, MARK A
O-15, MARK AO-18, MARK 328,
MARK AO-37 (all manufactured by Adeka Argus Chemical Co., Ltd.), IRGANOX-245, IRGANOX-2
59, IRGANOX-565, IRGANOX-10
10, IRGANOX-1024, IRGANOX-1
035, IRGANOX-1076, IRGANOX-
1081, IRGANOX-1098, IRGANOX
-1222, IRGANOX-1330, IRGANO
X-1425WL (all from Japan Ciba Geigy), Sumilizer GM, Sumilizer G
Examples thereof include A-80 (all of which are manufactured by Sumitomo Chemical Co., Ltd.), but are not limited thereto.

The light stabilizer (IV ') is an antioxidant (II
I ′) may be used in combination, and the combination thereof is particularly preferable because the effect may be further exhibited and the weather resistance may be improved. The light stabilizer (IV ') and the antioxidant (II
I ') mixed with tinuvin C353, tinuvin B7
5 (all of which are manufactured by Nippon Ciba Geigy) or the like may be used.

The light stabilizer (IV ') or the antioxidant (III') is not particularly limited, but by using a high molecular weight one, the effect of improving the weather resistance of the present invention is exhibited for a longer period of time. Is more preferable because

The light stabilizer (IV ′) and / or antioxidant (III ′) are used in the respective amounts of the vinyl polymer 1
It is preferably in the range of 0.1 to 10 parts by weight with respect to 00 parts by weight. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 5 parts by weight, there is no great difference in the effect and it is economically disadvantageous. << Curable Composition >> In the curable composition of the present invention, a curing catalyst or a curing agent may be required depending on each crosslinkable functional group. Further, various compounding agents may be added depending on the desired physical properties. <Curing Catalyst / Curing Agent> In the Case of Crosslinkable Silyl Group A polymer having a crosslinkable silyl group is crosslinked and cured by forming a siloxane bond in the presence or absence of various conventionally known condensation catalysts. With regard to the properties of the cured product, it can be widely prepared from rubber-like to resin-like depending on the molecular weight of the polymer and the main chain skeleton.

Examples of such condensation catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethyl hexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, Dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctyl Tetravalent tin compounds such as malate; Divalent tin compounds such as tin octylate, tin naphthenate and tin stearate; Monobutyl such as monobutyltin trisoctoate and monobutyltin triisopropoxide Monoalkyl tins such as tin compounds and monooctyl tin compounds; titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organics such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate Aluminum compounds; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate;
Lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, Guanidine, diphenylguanidine,
2,4,6-Tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-
Amine-based compounds such as 4-methylimidazole and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), or salts of these amine-based compounds with carboxylic acids; laurylamine and tin octylate Reactants and mixtures of amine compounds and organotin compounds such as reactants or mixtures; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds; γ -Aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, and other silane coupling agents having amino groups; silanol condensation catalysts such as, and other known acidic catalysts, basic catalysts, etc. Examples of silanol condensation catalysts include

These catalysts may be used alone,
You may use 2 or more types together. The amount of the condensation catalyst blended is preferably about 0.1 to 20 parts, more preferably 1 to 10 parts, relative to 100 parts (parts by weight, the same hereinafter) of the vinyl polymer. If the compounding amount of the silanol condensation catalyst is less than this range, the curing rate may be slow and the curing reaction may not be able to proceed sufficiently. On the other hand, if the content of the silanol condensation catalyst exceeds this range, local heat generation or foaming occurs during curing, and it becomes difficult to obtain a good cured product, and the pot life becomes too short, and it is also preferable from the viewpoint of workability. Absent. In addition, although not particularly limited, it is preferable to use a tin-based curing catalyst in order to control the curability.

In the curable composition of the present invention, in order to further enhance the activity of the condensation catalyst, the general formula (37) R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (37) (in the formula, R ⁴⁹ and R ⁵⁰ is independently carbon number 1
To 20 substituted or unsubstituted hydrocarbon groups. Further, a is 0, 1, 2, or 3. ), A silicon compound having no silanol group may be added.

The above-mentioned silicon compound is not limited, but in the general formula (37) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like. R ^{49 of} is an aryl group having 6 to 20 carbon atoms,
It is preferable because it has a large effect of accelerating the curing reaction of the composition. Particularly, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because they are low in cost and easily available.

The amount of the silicon compound compounded is preferably about 0.01 to 20 parts, and more preferably 0.1 to 10 parts, per 100 parts of the vinyl polymer. If the blending amount of the silicon compound is less than this range, the effect of accelerating the curing reaction may be reduced. On the other hand, if the content of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease. In the case of alkenyl group When the alkenyl group is used for crosslinking, it is not limited, but it is preferable to use a hydrosilyl group-containing compound as a curing agent and perform crosslinking by a hydrosilylation reaction using a hydrosilylation catalyst.

As the hydrosilyl group-containing compound,
Hydropolymers that can be cured by cross-linking with polymers containing kenyl groups
There is no particular limitation as long as it is a silyl group-containing compound, and various compounds
Can be used. For example, the general formula (38)
Is a chain polysiloxane represented by (39); R⁵¹ ₃SiO- [Si (R⁵¹)₂O]_a-[Si (H) (R⁵²) O]_b-[Si (R ⁵² ) (R⁵³) O]_c-SiR⁵¹ ₃    (38) HR⁵¹ ₂SiO- [Si (R⁵¹)₂O]_a-[Si (H) (R⁵²) O]_b-[Si ( R⁵²) (R⁵³) O]_c-SiR⁵¹ ₂H (39) (In the formula, R⁵¹And R⁵²Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁵³Is alkyl having 1 to 10 carbons
Represents a group or an aralkyl group. a is 0 ≦ a ≦ 100, b
Is an integer satisfying 2 ≦ b ≦ 100 and c is an integer satisfying 0 ≦ c ≦ 100.
Show. ) A cyclic siloxane represented by the general formula (40);

[0159]

[Chemical 7] (In the formula, R⁵⁴And R⁵⁵Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁵⁶Is alkyl having 1 to 10 carbons
Represents a group or an aralkyl group. d is 0 ≦ d ≦ 8, e is 2
≤e≤10, f represents an integer of 0≤f≤8, and 3≤d
+ E + f ≦ 10 is satisfied. ) Etc.
it can.

These may be used alone or in admixture of two or more. Among these siloxanes, from the viewpoint of compatibility with the (meth) acrylic polymer, chain siloxanes represented by the following general formulas (41) and (42) having a phenyl group, and general formulas (43) and (43) Cyclic siloxanes represented by 44) are preferred. _{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -S i (CH 3) 3 (41) (CH 3) 3 SiO- _{[Si (H) (CH 3} ) O] g - [Si (CH 3) {CH 2 C (H) (R 57) C 6 H 5} O] h -Si (CH 3) 3 (42) ( formula Wherein R ⁵⁷ represents hydrogen or a methyl group, and g is 2 ≦ g
≦ 100 and h are integers of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group. )

[0161]

[Chemical 8] (In the formula, R ⁵⁷ represents hydrogen or a methyl group. I is 2 ≦
i ≦ 10 and j are integers satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. As the hydrosilyl group-containing compound, a hydrosilyl group-containing compound represented by any one of formulas (38) to (44) may be partially reacted even after the reaction with respect to a low molecular weight compound having two or more alkenyl groups in the molecule. It is also possible to use the compound obtained by the addition reaction with the hydrosilyl group remaining. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4-pentadiene, 1,5-hexadiene,
1,6-heptadiene, 1,7-octadiene, 1,8
-Hydrocarbon compounds such as nonadiene and 1,9-decadiene, O, O'-diallylbisphenol A, 3,3'-
Examples thereof include ether compounds such as diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, and carbonate compounds such as diethylene glycol diallyl carbonate.

The above-mentioned alkenyl group-containing compound was slowly added dropwise to the excess amount of the hydrosilyl group-containing compound represented by the above general formulas (38) to (44) in the presence of a hydrosilylation catalyst to give the compound. Obtainable. Among these compounds, considering the availability of raw materials, the ease of removing excess siloxane, and the compatibility of the vinyl polymer (I) component with the polymer,
The following are preferred.

[0163]

[Chemical 9] The polymer and the curing agent can be mixed in any ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is preferably in the range of 5 to 0.2, and further, 2.5 It is particularly preferable that it is ˜0.4. If the molar ratio is 5 or more, curing will be insufficient and only a cured product with low tackiness and low strength will be obtained, and if it is less than 0.2, a large amount of active hydrosilyl groups will remain in the cured product after curing. However, cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The curing reaction between the polymer and the curing agent proceeds by mixing the two components and heating, but a hydrosilylation catalyst can be added to accelerate the reaction more rapidly. Such a hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.

The radical initiator is not particularly limited,
For example, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Such as 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) isopropylbenzene Dialkyl peroxides such as dialkyl peroxides, benzoyl peroxides, p-chlorobenzoyl peroxides, m-chlorobenzoyl peroxides, 2,4-dichlorobenzoyl peroxides, lauroyl peroxides, peracid esters such as perbenzoic acid-t-butyl, perdialkyl peroxides. Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl perdicarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke like cyclohexane It can be mentioned Lumpur and the like.

The transition metal catalyst is also not particularly limited and includes, for example, platinum simple substance, platinum solid dispersed in a carrier such as alumina, silica, carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples thereof include complexes with ketones, platinum-olefin complexes, and platinum (0) -divinyltetramethyldisiloxane complexes. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , R
hCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl
₃ , PdCl ₂ · H ₂ O, NiCl ₂ , TiCl _{4 and the} like. These catalysts may be used alone or in combination of two or more kinds. The catalyst amount is not particularly limited, but 1 mol of the alkenyl group of the vinyl polymer (I) is used.
On the other hand, it is preferably used in the range of 10 ^-1 to 10 ^-8 mol, and more preferably 10 ^-3 to 10 ^-6 mol. If it is less than 10 ^-8 mol, curing will not proceed sufficiently. Also, since hydrosilylation catalysts are expensive, 10 ^-1
It is preferable not to use more than mol.

The curing temperature is not particularly limited, but it is generally 0 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., more preferably 80 ° C. to 150 ° C. In case of hydroxyl group The polymer having a hydroxyl group of the present invention is uniformly cured by using a compound having two or more functional groups capable of reacting with the hydroxyl group as a curing agent. Specific examples of the curing agent include, for example, a polyvalent isocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as a methylolated melamine and its alkyl ether compound or a low condensation product, a polyfunctional carboxylic acid, and the like. The halide etc. are mentioned. When a cured product is prepared using these curing agents, an appropriate curing catalyst can be used. In the case of amino group The polymer having an amino group of the present invention is uniformly cured by using a compound having two or more functional groups capable of reacting with an amino group as a curing agent. Specific examples of the curing agent include, for example, a polyvalent isocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as a methylolated melamine and its alkyl ether compound or a low condensation product, a polyfunctional carboxylic acid, and the like. The halide etc. are mentioned. When a cured product is prepared using these curing agents, an appropriate curing catalyst can be used. In the case of an epoxy group, the curing agent for the polymer having an epoxy group of the present invention is not particularly limited, and examples thereof include aliphatic amines, alicyclic amines, aromatic amines; acid anhydrides; polyamides; imidazoles; Amine imide; urea; melamine and its derivatives; polyamine salt; phenol resin; polymercaptan, polysulfide; aromatic diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium salt, etc. . In the case of a polymerizable carbon-carbon double bond A polymer having a polymerizable carbon-carbon double bond can be crosslinked by the polymerization reaction of the polymerizable carbon-carbon double bond.

Examples of the crosslinking method include a method of curing with active energy rays and a method of curing with heat. In the active energy ray-curable composition, the photopolymerization initiator is preferably a photoradical initiator or a photoanion initiator. In the thermosetting composition,
Thermal polymerization initiator, azo initiator, peroxide, persulfate,
And a redox initiator.

These crosslinking reactions will be described in detail below.

In the case of crosslinking a polymer having a polymerizable carbon-carbon double bond, a polymerizable monomer and / or oligomer and various additives may be used in combination depending on the purpose. The polymerizable monomer and / or oligomer is preferably a monomer and / or oligomer having a radical polymerizable group, or a monomer and / or oligomer having an anionic polymerizable group. Examples of radically polymerizable groups include acrylic functional groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, vinyl chloride groups, etc. Is mentioned. Among them, those having a (meth) acrylic group similar to the polymer of the present invention are preferable. Examples of the anionic polymerizable group include (meth) acrylic group, styrene group, acrylonitrile group, N-vinylpyrrolidone group, acrylamide group,
Examples thereof include conjugated diene groups and vinyl ketone groups. Among them, those having an acrylic functional group are preferable.

Specific examples of the above-mentioned monomers include (meth) acrylate-based monomers, cyclic acrylates, N-
Examples thereof include vinylpyrrolidone, styrene-based monomers, acrylonitrile, N-vinylpyrrolidone, acrylamide-based monomers, conjugated diene-based monomers, vinylketone-based monomers and the like. Examples of the (meth) acrylate-based monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and compounds of the following formulae. it can.

[0172]

[Chemical 10]

[0173]

[Chemical 11]

[0174]

[Chemical 12]

[0175]

[Chemical 13]

[0176]

[Chemical 14] Styrene-based monomers include styrene and α-methylstyrene, acrylamide-based monomers such as acrylamide and N, N-dimethylacrylamide, and conjugated diene-based monomers such as butadiene and isoprene.
Examples of the vinyl ketone-based monomer include methyl vinyl ketone.

Examples of the polyfunctional monomer include neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate and bisphenol A.
Polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, 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, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and the like. As the oligomer, an epoxy acrylate resin such as a bisphenol A type epoxy acrylate resin, a phenol novolac type epoxy acrylate resin, a cresol novolac type epoxy acrylate resin, a COOH group modified epoxy acrylate resin,
Polyol (polytetramethylene glycol, polyester diol of ethylene glycol and adipic acid, ε-
Caprolactone-modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc. and organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylyl) Urethane resin obtained from (diisocyanate, etc.) hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Urethane acrylate resin obtained by reacting acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc., resin obtained by introducing (meth) acrylic group into the above polyol through an ester bond, polyester acrylate resin, etc. Is mentioned.

These monomers and oligomers are selected according to the initiator used and the curing conditions.

The number average molecular weight of the monomer and / or oligomer having an acrylic functional group is preferably 2000 or less, more preferably 1000 or less for the reason of good compatibility.

As a method of crosslinking the polymer having a polymerizable carbon-carbon double bond, it is preferable to use active energy rays such as UV and electron rays.

In the case of crosslinking with active energy rays, it is preferable to contain a photopolymerization initiator.

The photopolymerization initiator used in the present invention is not particularly limited, but photoradical initiators and photoanion initiators are preferable, and photoradical initiators are particularly preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorenone, benzaldehyde,
Anthraquinone, triphenylamine, carbazole,
3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 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-
Examples thereof include chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, and 2-chlorothioxanthone. These initiators may be used alone or in combination with other compounds. Specific examples include combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue. To be

A near infrared ray absorbing cationic dye may be used as the near infrared ray polymerization initiator. The near-infrared light absorbing cationic dye is excited by light energy in the region of 650 to 1500 nm, for example, JP-A-3-11.
It is preferable to use a near infrared absorptive cationic dye-borate anion complex disclosed in JP-A No. 1402 and JP-A-5-194619, and it is more preferable to use a boron sensitizer together.

The amount of the photopolymerization initiator to be added is not particularly limited, since the system may be slightly photofunctionalized. preferable.

The method for curing the active energy ray-curable composition of the present invention is not particularly limited, but depending on the nature of the photopolymerization initiator initiator, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, a halogen lamp, Irradiation with light and an electron beam by a light emitting diode, a semiconductor laser or the like can be mentioned.

The method of crosslinking the polymer having a polymerizable carbon-carbon double bond is preferably by heat.

In the case of crosslinking with active energy rays, it is preferable to contain a thermal polymerization initiator.

The thermal polymerization initiator used in the present invention is not particularly limited, but includes azo initiators, peroxides, persulfates, and redox initiators.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-
2,4-Dimethylvaleronitrile) (VAZO 3
3), 2,2'-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,2
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), and 2,2'-azobis (methylisobutyrate)
(V-601) (available from Wako Pure Chemical Industries, Ltd.) and the like.

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 1
1) (available from Elf Atochem), t-butylperoxy-2-ethylhexanoate (Trig
onox 21-C50) (available from Akzo Nobel), and dicumyl peroxide.

Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.

Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; organic peroxidation. And tertiary amine based systems such as those based on benzoyl peroxide and dimethylaniline; and organic hydroperoxide and transition metal based systems such as cumene hydroperoxide and cobalt naphthate based systems.

Other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.

The preferable thermal radical initiator is selected from the group consisting of azo type initiators and peroxide type initiators. More preferred are 2,2'-azobis (methyl isobutyrate), t-butyl peroxypivalate,
And di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The thermal initiators used in the present invention are present in catalytically effective amounts, such amounts including, but not limited to,
Typically, from about 0.01 to 5 parts by weight, based on 100 parts by weight of the polymer having an acrylic functional group at at least one terminal of the present invention and the monomer and oligomer mixture added thereto. , More preferably about 0.025
~ 2 parts by weight. If a mixture of initiators is used, the total amount of the mixture of initiators is as if only one initiator was used.

The method for curing the thermosetting composition of the present invention is not particularly limited, but the temperature is usually 50, although it varies depending on the type of the thermal initiator, the polymer (I) and the compound to be added. Preferably in the range of ℃ to 250 ℃,
More preferably, it is in the range of 70 ° C to 200 ° C. The curing time varies depending on the polymerization initiator used, the monomer, the solvent, the reaction temperature, etc., but is usually in the range of 1 minute to 10 hours. <Adhesiveness imparting agent> A silane coupling agent or an adhesiveness imparting agent other than the silane coupling agent can be added to the composition of the present invention. When the adhesion-imparting agent is added, the risk of the sealing material peeling off from the adherend such as a siding board can be further reduced because the joint width and the like change due to external force. In some cases, it is not necessary to use a primer used for improving the adhesiveness, and it is expected that the construction work will be simplified. Specific examples of the silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and other isocyanate group-containing silanes; γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2- Aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl)
Aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-
Ureidopropyltrimethoxysilane, N-phenyl-
Amino group-containing silanes such as γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ- Mercapto group-containing silanes such as mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, Epoxy group-containing silanes such as γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-cal Carboxysilanes such as xyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyl Vinyl-type unsaturated group-containing silanes such as triethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; Tris ( Examples thereof include isocyanurate silanes such as trimethoxysilyl) isocyanurate. In addition, these are modified derivatives of amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones,
A silylated polyester or the like can also be used as the silane coupling agent.

The silane coupling agent used in the present invention is
Usually, it is used in the range of 0.1 to 20 parts with respect to 100 parts of the vinyl polymer. In particular, it is preferably used in the range of 0.5 to 10 parts. The effect of the silane coupling agent added to the curable composition of the present invention, various adherends, that is, glass, aluminum, stainless steel, zinc, copper, inorganic substrates such as mortar, vinyl chloride, acrylic, polyester, When it is used as an organic base material such as polyethylene, polypropylene or polycarbonate, it shows a remarkable effect of improving the adhesiveness under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving the adhesion to various adherends is particularly remarkable.

Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resin, phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate and the like.

The above-mentioned adhesion-imparting agents may be used alone or in combination of two or more. Addition of these adhesiveness-imparting agents can improve the adhesiveness to the adherend. Although not particularly limited, 0.1 to 20 parts by weight of a silane coupling agent is used among the above-mentioned adhesiveness-imparting agents in order to improve the adhesiveness, particularly the adhesiveness to a metal adhered surface such as an oil pan. Is preferred. <Plasticizer> In the curable composition of the present invention, various plasticizers may be used as necessary. When a plasticizer is used in combination with the below-mentioned filler, it is more advantageous because the elongation of the cured product can be increased and a large amount of filler can be mixed, but it is not always necessary to add. The plasticizer is not particularly limited, but for the purpose of adjusting physical properties, adjusting properties, and the like, for example, dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate,
Phthalates such as butylbenzyl phthalate; Non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate; Aliphatic esters such as butyl oleate and methyl acetylricinoleate Ester of polyalkylene glycol such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester; tricresyl phosphate;
Phosphoric acid esters such as tributyl phosphate; trimellitic acid esters; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; alkyldiphenyl, Hydrocarbon-based oils such as partially hydrogenated terphenyl; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and derivatives obtained by converting the hydroxyl groups of these polyether polyols into ester groups, ether groups, etc. Polyethers such as epoxidized soybean oil, epoxy plasticizers such as benzyl epoxystearate; dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid, and ethylene glycol Polyester plasticizers obtained from dihydric alcohols such as alcohol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol; obtained by polymerizing vinyl monomers including acrylic plasticizers by various methods. Examples thereof include vinyl polymers.

Among them, the number average molecular weight is 500 to 15,000.
By adding the polymer plasticizer, which is a polymer of
The viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted, and the plasticizer is a plasticizer containing no polymer component in the molecule. Compared to the case where a molecular plasticizer is used, the initial physical properties are maintained for a long period of time, and the dryability when the alkyd paint is applied to the cured product (also called paintability)
Can be improved. Although not limited, this polymer plasticizer may or may not have a functional group.

The number average molecular weight of the polymer plasticizer is 5 in the above.
Although described as 00 to 15000, preferably 800 to 1
It is 0000, and more preferably 1000 to 8000. If the molecular weight is too low, the plasticizer may flow out over time due to heat or rainfall, and the initial physical properties may not be maintained for a long time, and the alkyd coatability may not be improved. Further, if the molecular weight is too high, the viscosity becomes high and the workability becomes poor.

Of these polymeric plasticizers, those compatible with the vinyl polymer are preferred. Among them, vinyl polymers are preferable from the viewpoint of compatibility, weather resistance and heat resistance. Among vinyl polymers, (meth) acrylic polymers are preferable, and acrylic polymers are more preferable. Examples of the method for synthesizing this acrylic polymer include those obtained by conventional solution polymerization and solventless acrylic polymers. The latter acrylic plasticizer does not use a solvent or a chain transfer agent, and is a high-temperature continuous polymerization method (USP4414370, JP-A-59-6207, JP-B-5-58005, JP-A- 1-3).
13522, USP 5010166), which is more preferable for the purpose of the present invention. Examples thereof include, but are not particularly limited to, Toagosei UP series (see October 1999 issue of industrial material). Of course, a living radical polymerization method can also be mentioned as another synthetic method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, which is preferable. Further, the atom transfer radical polymerization method is more preferable, but the method is not limited thereto.

The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and 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 further preferable, 1.4 or less is particularly preferable, and 1.3 or less is most preferable.

The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more kinds, but it is not always necessary. If necessary, a high molecular weight plasticizer may be used, and a low molecular weight plasticizer may be further used in combination as long as the physical properties are not adversely affected.

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

The amount of the plasticizer used is not limited, but is 5 to 15 parts by weight per 100 parts by weight of the vinyl polymer.
The amount is 0 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. <Filler> In the curable composition of the present invention, various fillers may be used as necessary. The filler is not particularly limited, wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, chaff powder,
Reinforcing fillers such as graphite, diatomaceous earth, clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, silicic acid hydrate, etc.), carbon black; heavy calcium carbonate , Colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite,
Fillers such as organic bentonite, ferric oxide, red iron oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, glass fiber and glass filament, carbon fiber, Examples thereof include fibrous fillers such as Kevlar fiber and polyethylene fiber.

Among these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide,
Talc and the like are preferred.

In particular, when it is desired to obtain a cured product having high strength with these fillers, mainly fumed silica, precipitable silica, silicic acid anhydride, silicic acid hydrate, carbon black, surface-treated fine calcium carbonate, crystalline Silica, fused silica,
Fillers selected from calcined clay, clay and activated zinc white can be added. Above all, the specific surface area (according to the BET adsorption method) is 50 m ² / g or more, usually 50 to 400 m ² /
g, preferably 100 to 300 m ² / g of ultrafine powdery silica is preferable. Further, silica whose surface is previously subjected to hydrophobic treatment with an organosilicon compound such as organosilane, organosilazane, or diorganopolysiloxane is more preferable.

More specific examples of the silica-based filler having a high reinforcing property include, but are not particularly limited to, one of combustion method silica (fumed silica), Aerosil manufactured by Nippon Aerosil Co., Ltd., and precipitation method silica. Nipsil manufactured by Nippon Silica Co., Ltd. In particular, regarding fumed silica, it is more preferable to use fumed silica having an average primary particle size of 5 nm or more and 50 nm or less because the reinforcing effect is particularly high.

To obtain a cured product having a low strength and a large elongation, a filler selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. is added. it can. Generally, when the specific surface area of calcium carbonate is small, the effect of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product may not be sufficient. The larger the value of the specific surface area, the greater the effect of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product.

Furthermore, it is more preferable that the calcium carbonate has been surface-treated with a surface-treating agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved and the adhesiveness and weather resistance of the curable composition are improved as compared with the case of using the calcium carbonate that is not surface-treated. It is considered that the improvement effect is further improved. 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, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and other fatty acids. And salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids. Specific examples of the surfactant include polyoxyethylene alkyl ether sulfuric acid ester, long-chain alcohol sulfuric acid ester and the like, sulfuric acid ester type anionic surfactants such as sodium salt and potassium salt thereof, alkylbenzene sulfonic acid and alkylnaphthalene. Examples thereof include sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkyl sulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof. The surface treatment agent is preferably treated in an amount of 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on calcium carbonate. If the treatment amount is less than 0.1% by weight, the workability, adhesiveness and weather resistance may not be sufficiently improved. If it exceeds 20% by weight, the storage stability of the curable composition may be poor. It may decrease.

Although not particularly limited, when calcium carbonate is used, when it is expected that the thixotropy of the compound, the breaking strength, the breaking elongation of the cured product, the adhesiveness and the weather resistance are improved, the colloidal calcium carbonate is used. Is preferably used.

On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, and reducing the cost. Can be used.

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 as a pulverizing method, but a wet pulverized product is often not preferable because it often deteriorates the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes a product having various average particle sizes by classification. Although not particularly limited, in the case of expecting the effects of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product, those having a specific surface area of 1.5 m ² / g or more and 50 m ² / g or less are preferred. Preferably 2 m ² / g or more 5
0 m ² / g or less is more preferable, and 2.4 m ² / g or more 50
m ² / g or less is more preferable, 3 m ² / g or more and 50 m ² /
Particularly preferred is g or less. If 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 simply lowering the viscosity or only for the purpose of increasing the amount.

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

These fillers may be used alone or in combination of two or more, depending on the purpose and need. Although not particularly limited, for example, if a combination of heavy calcium carbonate having a specific surface area value of 1.5 m ² / g or more and colloidal calcium carbonate is combined as necessary, an increase in the viscosity of the composition is suppressed moderately and a cured product is obtained. The breaking strength, breaking elongation, improvement of adhesiveness and weather resistance can be expected. <Addition amount> When the filler is used, the addition amount is preferably in the range of 5 to 1000 parts by weight with respect to 100 parts by weight of the vinyl polymer, and in the range of 20 to 500 parts by weight. It is more preferably used, and particularly preferably used in the range of 40 to 300 parts by weight. If the blending amount is less than 5 parts by weight, the effects of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product may be insufficient.
If it exceeds 000 parts by weight, the workability of the curable composition may deteriorate. The filler may be used alone or 2
You may use together more than one kind. <Fine Hollow Particles> Further, fine hollow particles may be used in combination with these reinforcing fillers for the purpose of achieving weight reduction and cost reduction without causing significant deterioration in physical properties.

Such micro hollow particles (hereinafter referred to as “balloons”) are not particularly limited, but as described in “Latest Technology of Functional Fillers” (CMC), the diameter is 1 mm or less, preferably 500 μm or less. More preferably, a hollow body made of an inorganic or organic material having a diameter of 200 μm or less is used. In particular, the true specific gravity is 1.0 g /
It is preferable to use a minute hollow body having a size of ³ cm ³ or less,
Furthermore, it is preferable to use a minute hollow body having a weight of 0.5 g / cm ³ or less.

Examples of the inorganic balloons include silicic acid balloons and non-silicic acid balloons. Examples of the silicic acid balloons include shirasu balloon, perlite, glass balloon, silica balloon, fly ash balloon, and non-silicic acid balloons. Examples thereof include alumina balloons, zirconia balloons, carbon balloons and the like. Specific examples of these inorganic balloons include Shirasu balloons made by Idiji Kasei's Winlite, Sanki Kogyo's Sankilite, glass balloons made by Nippon Sheet Glass Caroon, Sumitomo 3M's Cellstar Z-28, EMERSON & CU.
MING made MICRO BALLON, PITTS
CERAMIC GL made by BURGE CORNING
ASSMODULES, 3M made GLASS BUBB
LES, Q-CEL made by Asahi Glass as silica balloon,
Taiheiyo Cement's E-SPHERES, PFAMARKETING's CE as fly ash balloon
ROSPHERES, FILLITE U. S. FILLITE made of A, BW made by Showa Denko as an alumina balloon, and HO made by ZIRCOA as a zirconia balloon.
LLOW ZIRCONIUM SPHEES, Kureha Chemical's Crecus Fair as carbon balloon, GENE
Car boss fairs made by RAL TECHNOLOGIES are commercially available.

Examples of the organic balloons include thermosetting resin balloons and thermoplastic resin balloons. Phenol balloons, epoxy balloons, urea balloons are used as the thermosetting balloons, and Saran balloons are used as the thermoplastic balloons. Examples thereof include polystyrene balloons, polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons. Further, balloons of crosslinked thermoplastic resin can also be used. The balloon as used herein may be a balloon after foaming, or may be a balloon obtained by blending a material containing a foaming agent and then foaming.

As specific examples of these organic balloons,
UC made of Union Carbide as a phenolic balloon
AR and PHENOLIC MICROBALLON
S, EMERSON & CUMI as epoxy balloon
ECCOSPHERES made by NG, ECCOSPHER made by EMERSON & CUMING as a urea balloon
ES VF-O, DOW CHE as Saran balloon
MICAL made SARAN MICROSPHERE
S, Nippon Filament Expancel, Matsumoto Yushi-Seiyaku Matsumoto Microspheres, and polystyrene balloon ARCOPOLYMERS DYLITE
EXPANDABLE POLYSTYRENE, BA
EXPANDABLE made by SF WYANDOTE
POLYSTYRENE BEADS, cross-linked styrene-acrylic acid balloon has SX863 made by Japan Synthetic Rubber
(P) is commercially available.

The above balloons may be used alone or 2
You may use it in mixture of 2 or more types. Furthermore, in order to improve the dispersibility and workability of the compound on the surface of these balloons with fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. Treated products can also be used. These balloons are used for reducing the weight and reducing the cost without deteriorating the flexibility, the elongation and the strength among the physical properties when the compound is cured.

The content of the balloon is not particularly limited, but is preferably 0.1% with respect to 100 parts by weight of the vinyl polymer.
It can be used in the range of 1 to 50 parts, more preferably 0.1 to 30 parts. When this amount is less than 0.1 part, the effect of weight reduction is small, and when it is 50 parts or more, a decrease in tensile strength may be observed among the mechanical properties when the composition is cured.
When the specific gravity of the balloon is 0.1 or more, 3 to 50 parts,
More preferably, it is 5 to 30 parts. <Physical Property Adjusting Agent> In the curable composition of the present invention, a physical property adjusting agent for adjusting the tensile properties of a cured product to be produced may be added, if necessary.

Although the physical property adjusting agent is not particularly limited,
For example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldi Alkylisopropenoxysilane such as isopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β
-Aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Examples thereof include alkoxysilanes having a functional group such as mercaptopropylmethyldimethoxysilane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, the hardness of the composition of the present invention when cured can be increased, or the hardness can be decreased and the elongation can be increased. The physical property modifiers may be used alone or in combination of two or more kinds. << Silanol-Containing Compound >> The silanol-containing compound used in the present invention is a compound having one silanol group in the molecule, and / or one silanol group in the molecule by reacting with water. A compound capable of forming a compound. Only one of these may be used, or both compounds may be used at the same time.

The compound having one silanol group in the molecule, which is one of the components used in the present invention, is not particularly limited, and the compounds shown below, (CH ₃ ) ₃ SiOH, (CH ₃ CH ₂ ) ₃ SiOH, (C
_{H 3 CH 2 CH 2) 3} SiOH, (n-Bu) 3 SiOH,
(Sec-Bu) ₃ SiOH, (t-Bu) ₃ SiOH,
(T-Bu) Si (CH 3) 2 OH, (C 5 H 11) 3 SiO
_{H, (C 6 H 13)} 3 SiOH, (C 6 H 5) 3 SiOH,
_{(C 6 H 5) 2 Si} (CH 3) OH, (C 6 H 5) Si (CH
₃ ) ₂ OH, (C ₆ H ₅ ) ₂ Si (C ₂ H ₅ ) OH, C ₆ H ₅ S
i (C ₂ H ₅ ) ₂ OH, C ₆ H ₅ CH ₂ Si (C ₂ H ₅ ) ₂ O
(R ″) ₃ SiOH such as H, C ₁₀ H ₇ Si (CH ₃ ) ₂ OH (wherein C ₆ H ₅ represents a phenyl group and C ₁₀ H ₇ represents a naphthyl group) in the above formula.
(Wherein R "is the same or different, substituted or unsubstituted alkyl group or aryl group),

[0225]

[Chemical 15] Cyclic polysiloxane compounds containing silanol groups, such as

[0226]

[Chemical 16] A chain polysiloxane compound containing silanol groups such as

[0227]

[Chemical 17] A compound in which a silanol group is bonded to the polymer terminal composed of silicon and carbon as the main chain, such as

[0228]

[Chemical 18] A compound in which a silanol group is bonded to the end of the main chain of polysilane, such as

[0229]

[Chemical 19] Examples thereof include compounds having a silanol group bonded to the polymer terminal whose main chain is composed of silicon, carbon, and oxygen. Among these, the compound represented by the following general formula (45) is preferable. (R ⁵⁸ ) ₃ SiOH (45) (In the formula, R ⁵⁸ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ⁵⁸ may be the same or different.) R ²⁷ is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group or a phenyl group, more preferably a methyl group.

Among them, (CH ₃ ) ₃ SiOH and the like having a small molecular weight are preferable from the viewpoint of easy availability and effect.

The above-mentioned compound having one silanol group in the molecule reacts with the crosslinkable silyl group of the vinyl polymer or the siloxane bond formed by the crosslinkage to reduce the number of crosslink points and to give a cured product. It is presumed to give flexibility to. It is also one of the components of the present invention,
The compound capable of forming a compound having one silanol group in the molecule by reacting with water is not particularly limited, but a compound having one silanol group in the molecule formed by reacting with water (hydrolysis The product) is preferably a compound represented by the above general formula (45). For example, a general formula (4
In addition to the compound represented by 6), the following compounds can be mentioned.

N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N-
Methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide,
(N, N-dimethylamino) trimethylsilane, (N,
N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyltrifluoromethanesulfonate, trimethylsilylphenoxide, trimethylsilyl compound of n-octanol, 2 - ethyl trimethylsilylated hexanol, glycerol tris (trimethylsilyl) ated, tris (trimethylsilyl) ated trimethylolpropane, tris (trimethylsilyl) ated pentaerythritol, pentaerythritol tetra (trimethylsilyl) ated product, (CH _{3) 3} 3SiNHSi ( C
_{H 3) 3, (CH 3} ) 3 SiNSi (CH 3) 2,

[0233]

[Chemical 20] And the like can be preferably used, but (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is particularly preferable in view of the amount of silanol groups contained in the hydrolysis product.

Further, the compound capable of forming a compound having one silanol group in the molecule by reacting with water, which is one of the components of the present invention, is not particularly limited, but in addition to the above compounds, The compound represented by the formula (46) is preferable. ((R ⁵⁸ ) ₃ SiO) _n R ⁵⁹ (46) (In the formula, R ⁵⁸ is the same as described above. N is a positive number, and R ⁵⁹ is a part or all of active hydrogen containing compounds. R ⁵⁸ is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group or a phenyl group, and more preferably a methyl group. The (R ⁵⁸ ) ₃ Si group is particularly preferably a trimethylsilyl group in which all three R ⁵⁸ are methyl groups. Also, n is 1
-5 are preferable.

The active hydrogen-containing compound from which R ⁵⁹ is derived is not particularly limited, but for example, methanol, ethanol, n-butanol, i-butanol, t-butanol, n-octanol, 2-ethylhexanol,
Alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, tetramethylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol; phenol, cresol, Bisphenol A,
Phenols such as hydroquinone; formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, behenic acid, acrylic acid, methacrylic acid, oleic acid, linoleic acid, linolenic acid, sorbic acid, oxalic acid, malonic acid,
Carboxylic acids such as succinic acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid and trimellitic acid;
Ammonia; amines such as methylamine, dimethylamine, ethylamine, diethylamine, n-butylamine and imidazole; acid amides such as acetamide and benzamide; ureas such as urea and N, N′-diphenylurea;
Examples include ketones such as acetone, acetylacetone, and 2,4-heptadione.

The compound capable of forming a compound having one silanol group in the molecule by reacting with water represented by the above general formula (46) is, for example, the above-mentioned active hydrogen-containing compound, trimethylsilyl chloride or Dimethyl (t
-Butyl) chloride and the like, which can be obtained by reacting a compound having a group capable of reacting with active hydrogen such as a halogen group together with a (R ⁵⁸ ) ₃ Si group also called a silylating agent, but is not limited thereto. However, R ⁵⁸ is the same as described above.

Specific examples of the compound represented by the above general formula (46) include allyloxytrimethylsilane, N,
O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-
Methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,
1,3,3-Tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyltrifluoromethanesulfonate, trimethylsilylphenoxide, n-octanol trimethylsilyl compound, 2-ethylhexanol trimethylsilyl compound, glycerin tris (trimethylsilyl) compound Examples thereof include, but are not limited to, trimethylolpropane tris (trimethylsilyl) compound, pentaerythritol tris (trimethylsilyl) compound, pentaerythritol tetra (trimethylsilyl) compound, and the like. These may be used alone or in combination of two or more.

In addition, the general formula (((R⁶⁰)₃SiO) (R
⁶¹O)_s)_tA compound that can be represented by Z, CH₃
O (CH₂CH (CH₃) O)_FiveSi (CH₃)₃, CH₂=
CHCH₂(CH₂CH (CH₃) O)_FiveSi (CH₃)₃,
(CH₃)₃SiO (CH₂CH (CH₃) O)_FiveSi (C
H₃)₃, (CH₃)₃SiO (CH₂CH (CH₃) O) ₇
Si (CH₃)₃ (In the formula, R⁶⁰Are the same or different substituted or unsubstituted
Monovalent hydrocarbon group or hydrogen atom, R⁶¹Has 1 to 8 carbon atoms
A divalent hydrocarbon group, s and t are positive integers, and s is 1 to
6, s × t is 5 or more, Z is a monovalent to hexavalent organic group) Etc. can also be used suitably. These may be used alone,
You may use 2 or more types together.

Among the compounds capable of forming a compound having one silanol group in the molecule by reacting with water, storage stability, weather resistance and the like are not adversely affected.
Active hydrogen compounds generated after hydrolysis are phenols,
Acid amides and alcohols are preferable, and phenols and alcohols in which the active hydrogen compound is a hydroxyl group are more preferable.

Among the above compounds, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, trimethylsilylphenoxide, n
-Octanol trimethylsilyl compound, 2-ethylhexanol trimethylsilyl compound, glycerin tris (trimethylsilyl) compound, trimethylolpropane tris (trimethylsilyl) compound, pentaerythritol tris (trimethylsilyl) compound, pentaerythritol tetra (trimethylsilyl) compound, etc. Is preferred.

By reacting with this water, 1
A compound capable of forming a compound having one silanol group reacts with moisture during storage, curing, or after curing to generate a compound having one silanol group in the molecule. The compound having one silanol group in the molecule thus produced reacts with the crosslinkable silyl group of the vinyl polymer or the siloxane bond produced by the crosslinking as described above to reduce the number of crosslinking points. It is presumed that the amount is decreased and the cured product is given flexibility.

The addition amount of the silanol-containing compound can be appropriately adjusted according to the expected physical properties of the cured product. The silanol-containing compound was added in an amount of 0.
1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 10 parts by weight can be added. If it is less than 0.1 parts by weight, the effect of addition will not be exhibited, and if it exceeds 50 parts by weight, crosslinking will be insufficient and the strength and gel fraction of the cured product will be too low.

The timing of adding the silanol-containing compound to the vinyl polymer is not particularly limited, and may be added during the production of the vinyl polymer or during the production of the curable composition. <Thixotropy imparting agent (anti-sagging agent)> To the curable composition of the present invention, a thixotropy-imparting agent (anti-sagging agent) is added in order to prevent sagging and improve workability, if necessary. Is also good.

The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps such as calcium stearate, aluminum stearate and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. <Regarding photocurable substance> The curable composition of the present invention includes
A photocurable substance may be added if necessary. The photocurable substance is a substance in which the molecular structure undergoes a chemical change in a short time due to the action of light to cause a change in physical properties such as curing. By adding this photocurable substance, the tackiness (also referred to as residual tack) on the surface of the cured product when the curable composition is cured can be reduced. This photo-curable substance is a substance that can be cured by exposing it to light, but a typical photo-curable substance is, for example, that the photo-curable substance should be left at room temperature for one day at a position where it is exposed to sunlight (near the window). It is a substance that can be cured by. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as compounds of this type, and the type thereof is not particularly limited,
For example, unsaturated acrylic compounds, polyvinyl cinnamate, azide resins, etc. may be mentioned.

The unsaturated acrylic compound is a monomer or oligomer having an unsaturated group represented by the following general formula (47) or a mixture thereof. ^{_{CH 2 = CHR 62 CO (O}} ) - (47) wherein, R ⁶² are the same as those described above.

Specific examples of the unsaturated acrylic compound include (meth) acrylic acid esters of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and neopentyl alcohol; bisphenol A and isocyanuric acid. (Meth) acrylic acid esters of alcohols obtained by modifying the above low molecular weight alcohols such as acids with ethylene oxide or propylene oxide; polyether polyols whose main chain has a hydroxyl group at the end, and polyethers whose main chain is a polyether A polymer polyol obtained by radically polymerizing a vinyl-based monomer in a certain polyol,
(Meth) acrylic acid esters such as a polyester polyol having a polyester main chain and a hydroxyl group at the terminal, a polyol having a hydroxyl group in the main chain and having a hydroxyl group in the main chain; bisphenol A
-Type or novolac-type epoxy resins and epoxy acrylate oligomers obtained by reacting (meth) acrylic acid; in the molecular chain obtained by reacting polyols, polyisocyanates, hydroxyl group-containing (meth) acrylates, etc. Examples thereof include urethane acrylate-based oligomers having a urethane bond and a (meth) acrylic group.

Polyvinyl cinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group, and includes not only those obtained by esterifying polyvinyl alcohol with cinnamic acid but also many polyvinyl cinnamate derivatives.

The azide resin is known as a photosensitive resin having an azido group as a photosensitive group, and is usually a "photosensitive resin" in addition to a rubber photosensitive solution containing an azide compound as a photosensitizer.
(Published March 17, 1972, Published by The Printing Society Press, 9
There are detailed examples on pages 3 to 106 to pages 117 to), and these can be used alone or in combination, and a sensitizer can be added if necessary.

Among the above photocurable substances, unsaturated acrylic compounds are preferable because they are easy to handle.

The photocurable substance is preferably added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the vinyl polymer. If it is less than 0.01 parts by weight, the effect is small, and if it exceeds 20 parts by weight, the physical properties may be adversely affected. The effect may be enhanced by adding a sensitizer such as a ketone or a nitro compound or an accelerator such as an amine. <About Air Oxidation Curable Substance> An air oxidation curable substance may be added to the curable composition of the present invention, if necessary. The air oxidation curable substance is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By adding this air oxidation curable substance, the tackiness (also referred to as residual tack) on the surface of the cured product when the curable composition is cured can be reduced. The air-oxidation curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of reacting with oxygen in the air to be cured. A typical air oxidative curable substance can be cured, for example, by allowing it to stand in a room for one day in the air.

Examples of air-oxidation-curable substances include dry oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these dry oils; acrylic polymers modified with dry oil, epoxy resins, Silicone resin; 1,
2-polybutadiene, 1,4-polybutadiene, C5
Specific examples thereof include polymers and copolymers of C8 to C8 diene, and various modified products (maleated modified products, boil oil modified products, etc.) of the polymers and copolymers. Of these, tung oil, liquids of diene polymers (liquid diene polymers) and modified products thereof are particularly preferable.

Specific examples of the liquid diene polymer include butadiene, chloroprene, isoprene and 1,3-
A liquid polymer obtained by polymerizing or copolymerizing a diene-based compound such as pentadiene, or a copolymer such as acrylonitrile or styrene having copolymerizability with these diene-based compounds so that the diene-based compound is the main component. Examples include polymers obtained by polymerization such as NBR and SBR, and various modified products thereof (maleated modified products, boil oil modified products, etc.). These may be used alone or in combination of two or more. Among these liquid diene compounds, liquid polybutadiene is preferable.

The air oxidative curable substance may be used alone or in combination of two or more kinds. Further, the effect may be enhanced by using a catalyst that accelerates the oxidative curing reaction and a metal dryer together with the air oxidative curable substance. As these catalysts and metal dryers, cobalt naphthenate,
Examples include metal salts such as lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, amine compounds, and the like.

The air-oxidation-curable substance is vinyl polymer 1
It is preferable to add 0.01 to 20 parts by weight to 100 parts by weight. If it is less than 0.01 parts by weight, the effect is small, and if it exceeds 20 parts by weight, the physical properties may be adversely affected. Other Additives Various additives may be added to the curable composition of the present invention, if necessary, for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, flame retardants, curability modifiers, antioxidants, radical inhibitors, UV absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, phosphorus-based peroxides. Examples thereof include oxide decomposing agents, lubricants, pigments, foaming agents, and photocurable resins. These various additives may be used alone or in combination of two or more.

Specific examples of such additives are, for example,
Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928,
JP-A-63-254149, JP-A-64-22904
It is described in each specification of the issue.

The curable composition of the present invention may be prepared as a one-component type in which all the compounding ingredients are previously compounded and hermetically sealed and then cured by the humidity in the air after the construction. You may mix | blend the ingredients, such as a material, a plasticizer, and water, and adjust it as a two-component type which mixes this compounding material and a polymer composition before use. When the two-component type is used, a colorant can be added when the two components are mixed. For example, when providing a sealing material that matches the color of the siding board, it is possible to make abundant color alignment with limited stock. This makes it possible to easily cope with the demand for multiple colors in the market, which is preferable for low-rise buildings. For the colorant, for example, a pigment and a plasticizer, and in some cases, a filler mixed to form a paste is used, which facilitates the work. Further, the curing rate can be finely adjusted at the work site by adding a retarder when the two components are mixed. << Cured Product >><Use> The curable composition of the present invention is not limited,
Elastic sealing materials for construction Sealants for sealants and sealing materials for double glazing, electrical / electronic component materials such as solar cell backside encapsulation materials, electrical insulating materials such as insulation coatings for electric wires and cables, adhesives, adhesives , Elastic adhesive,
Paints, powder paints, coating materials, foams, sealing materials for can lids, electric and electronic potting agents, films, gaskets, casting materials, various molding materials, artificial marble, and
It can be used for various applications such as rustproof / waterproof sealant for mesh glass and laminated glass end face (cutting part), liquid sealant used in automobile parts, electric parts, various machine parts and the like.

[0257]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples.

In the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively.

In the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight and number average molecular weight)"
Is gel permeation chromatography (GP
It was calculated by the standard polystyrene conversion method using C).
However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; Showa Denko KK) was used, and chloroform was used as the GPC solvent. (Production Example 1) (Synthesis of carboxylic acid salt having alkenyl group) Methanol (250 mL) was charged with 10-undecenoic acid (150 g,
0.814 mol) and potassium-tert-butoxide (91.3 g, 0.814 mol) were added, and the mixture was stirred at 0 ° C. The volatile matter was distilled off under reduced pressure to obtain potassium undecenoate represented by the following formula. _{CH 2 = CH- (CH 2)} 8 -CO 2 - + K (BA semibatch polymerization -1 kg) under a nitrogen atmosphere in a glass reaction vessel of 2L, cuprous bromide (8.39g, 0.0585mol), acetonitrile ( 112 mL) was charged and the mixture was heated at 70 ° C. for 60 minutes.
Butyl acrylate (224mL, 1.56mo
l) Diethyl 2,5-dibromoadipate (17.6)
g, 0.0488 mol) was added and the mixture was further stirred for 30 minutes. Add pentamethyldiethylenetriamine (0.4
1 mL, 1.95 mmol) was added to initiate polymerization.
Then, the reaction solution was sampled to trace the reaction, and pentamethyldiethylenetriamine (5.66 m
L, 27.1 mmol) was added and 55
After minutes, butyl acrylate (895 mL, 6.24 mo)
l) was added over 140 minutes. Heating was continued for an additional 170 minutes after the addition of butyl acrylate. At this time, the consumption rate of butyl acrylate was 92.9% according to the GC measurement. After the mixture was diluted with toluene and treated with activated alumina, the volatile matter was heated under reduced pressure and evaporated to give a colorless transparent polymer [P
1] was obtained. The number average molecular weight of the obtained polymer [P1] was 21,000, and the molecular weight distribution was 1.1.

The polymer [P1] (0.35 kg), potassium undecenoate (8.85 g) and dimethylacetamide (350 mL) were added to a glass container, and the mixture was heated with stirring at 70 ° C. for 3 hours under a nitrogen atmosphere. The volatile components of the reaction solution were removed under reduced pressure heating, then diluted with toluene and filtered.
The filtrate was evaporated under reduced pressure to remove volatile components, and the solution was concentrated. Aluminum silicate (Kyowa Chemical Co., Ltd., KYOWARD 70
0 PEL) was added to the polymer in an amount of 20 wt% to obtain 100
The mixture was heated and stirred at ℃ for 3 hours. The reaction solution was diluted with toluene and filtered, and the volatile matter was distilled off from the filtrate under reduced pressure heating to obtain an alkenyl group-terminated polymer (polymer [P2]). ^{By 1} H-NMR measurement, the number of alkenyl groups introduced per polymer molecule was 1.9.

Polymer [P2] (35
0 g), trimethoxysilane (15.0 mL), methyl orthoformate (3.6 mL), and zero-valent platinum 1,1,
A 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of platinum catalyst used was 5 × 10 ⁻⁴ equivalent in molar ratio with respect to the alkenyl group of the polymer. After the reaction mixture was heated and reacted, the volatile matter of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P3]). The number average molecular weight of the obtained polymer was 26000 and the molecular weight distribution was 1.2. The average number of silyl groups introduced per molecule of polymer is ¹ H
The number was 1.4 as determined by NMR analysis.

Similarly, the polymer [P2] was placed in a 1 L pressure resistant reactor.
And trimethoxysilane, methyl orthoformate, and 0
After charging 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of valent platinum and reacting it with sufficient heating, the volatile matter of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl-based polymer. A polymer (polymer [P4]) was obtained. The number average molecular weight of the obtained polymer was 26000 and the molecular weight distribution was 1.2. The average number of silyl groups introduced per molecule of the polymer was 2.0 as determined by ¹ H NMR analysis.

Similarly, the polymer [P2] was placed in a 1 L pressure resistant reactor.
And dimethoxymethylhydrosilane, methyl orthoformate, and zero-valent platinum 1,1,3,3-tetramethyl-
After charging the 1,3-divinyldisiloxane complex and reacting it with heating, the volatile components of the mixture were distilled off under reduced pressure.
A silyl group-terminated vinyl polymer (polymer [P5]) was obtained. The number average molecular weight of the obtained polymer was 26000 and the molecular weight distribution was 1.2. The average number of silyl groups introduced per molecule of the polymer was 1.4 as determined by ¹ H NMR analysis. (Production Example 2) CuBr (8.39 g, 0.0585 m) was placed in a 2 L separable flask equipped with a reflux tube and a stirrer.
ol) was charged and the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (112 mL) was added, and the mixture was placed in an oil bath at 70 ° C for 3 times.
Stir for 0 minutes. Butyl acrylate (224m
L) diethyl 2,5-dibromoadipate (23.4
g, 0.0650 mol) and pentamethyldiethylenetriamine (0.500 mL, 0.244 mmol) (hereinafter referred to as triamine) were added to start the reaction. 7
While heating and stirring at 0 ° C, butyl acrylate (895m
L) was continuously added dropwise over 150 minutes. Triamine (2.50 mL, 12.0 mL) was added during the dropwise addition of butyl acrylate.
mmol) was added. After 310 minutes from the start of the reaction, 1,7-octadiene (288 mL, 1.95 mo
l), triamine (4.0 mL, 0.0195 mol)
Was added, and the mixture was continuously heated and stirred at 70 ° C. for 240 minutes. The reaction mixture was diluted with hexane, passed through an activated alumina column, and the volatile matter was distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [P6]). The polymer [P6] had a number average molecular weight of 20,000 and a molecular weight distribution of 1.3. In a 2 L separable flask with a reflux tube, add the polymer [P
6] (1.0 kg), potassium benzoate (34.8)
g), N, N-dimethyl acetic acid amide (1 L) was charged,
The mixture was heated and stirred at 70 ° C. for 15 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under heating and reduced pressure, the mixture was diluted with toluene. Solid components insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatile components of the filtrate were distilled off under reduced pressure to remove the polymer [P].
7] was obtained.

[0264] The polymer [P
7] (1 kg), aluminum silicate (200 g, manufactured by Kyowa Chemical,
(Kyoward 700 PEL) and toluene (1 L) were charged, and the mixture was heated with stirring at 100 ° C. for 5.5 hours under a nitrogen stream. After removing aluminum silicate by filtration, the toluene of the filtrate was distilled off under reduced pressure to obtain a polymer [P8].

Polymer [P8] (72
0 g), trimethoxysilane (31.7 mL), methyl orthoformate (8.1 mL), and zero-valent platinum 1,1,
A 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of platinum catalyst used was 5 × 10 ⁻⁴ equivalent in molar ratio with respect to the alkenyl group of the polymer. After the reaction mixture was reacted by heating, the volatile matter of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P9]). The number average molecular weight of the obtained polymer was 2300 as measured by GPC (in terms of polystyrene).
0, the molecular weight distribution was 1.4. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ HNMR analysis to be 1.7.

[0266] Similarly, the polymer [P
8], trimethoxysilane, dimethoxymethylhydrosilane, methyl orthoformate, and zero-valent platinum 1,1,
A 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the input amount of trimethoxysilane and dimethoxymethylhydrosilane was 70: 3 in a molar ratio.
It was set to 0. After the reaction mixture was heated and reacted, the volatile matter of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P10]). The number average molecular weight of the obtained polymer was 23,000 as measured by GPC (in terms of polystyrene), and the molecular weight distribution was 1.4. The average number of silyl groups introduced per molecule of polymer is ¹ H NM
As determined by R analysis, the trimethoxy group was 1.2
And 0.5 dimethoxymethyl groups.

Similarly, the polymer [P
8], dimethoxymethylhydrosilane, methyl orthoformate, and zero-valent platinum 1,1,3,3-tetramethyl-
After charging the 1,3-divinyldisiloxane complex and reacting it with heating, the volatile components of the mixture were distilled off under reduced pressure.
A silyl group-terminated vinyl polymer (polymer [P11]) was obtained. The number average molecular weight of the obtained polymer was 23,000 as measured by GPC (in terms of polystyrene), and the molecular weight distribution was 1.4.
Met. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis.
It was seven. (Production Example 3) CuBr (251.82 g, 1.76 mol) was charged into a 50 L polymerization machine equipped with a reflux tower and a stirrer, and the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (3
(360 mL) was added, and the mixture was stirred at 68 ° C. for 20 minutes. Butyl acrylate (6.80 L), diethyl 2,5-dibromoadipate (526.70 g, 1.46 mo)
l), pentamethyldiethylenetriamine (12.0 m
L, 0.0585 mmol) (hereinafter referred to as triamine) was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (26.80 L) was continuously added dropwise over 204 minutes. Triamine (36.0 mL, 0.176 mmol) was added during the dropwise addition of butyl acrylate. After 397 minutes from the start of the reaction, 1,7-octadiene (8640 mL, 58.5 mol) and triamine (120 mL, 0.585 mol) were added, and the mixture was heated at 80 ° C. for 2 minutes.
The mixture was heated and stirred for 40 minutes. Then triamine (80 mL,
0.390 mol) was added, and the mixture was heated and stirred at 90 ° C. for 240 minutes.

The reaction mixture was diluted with toluene, the insoluble copper complex was removed using a separator plate type centrifugal settler, and the mixture was passed through an activated alumina column, and then the volatile component was distilled off under reduced pressure to give an alkenyl group-terminated polymer. (Polymer [P12]) was obtained.
The polymer [P12] had a number average molecular weight of 24,000 and a molecular weight distribution of 1.21. In a 10 L separable flask equipped with a reflux tube, the polymer [P12] (3.0 kg), potassium acetate (24.5 g), N, N-dimethylacetamide (3
L) was charged and heated and stirred at 100 ° C. for 10 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under heating and reduced pressure, the mixture was diluted with toluene. Solid components insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. Volatile components of the filtrate were distilled off under reduced pressure to obtain a polymer [P13].

In a 10 L round bottom flask equipped with a reflux tube, the polymer [P13] (3 kg) and hydrotalcite (450
g, manufactured by Kyowa Kagaku Co., Ltd., Kyoward 500SH, Kyoward 700SL) and xylene (0.6 L) were charged, and the mixture was heated and stirred at 130 ° C. for 5.0 hours under a nitrogen stream. After removing the aluminum silicate by filtration, the filtrate was distilled off under reduced pressure to obtain a polymer [P14].

Polymer [P14] (100
0 g), trimethoxysilane (52 mL), methyl orthoformate (13.3 mL), and zero-valent platinum 1,1,
A 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. A platinum catalyst and trimethoxysilane were added during the reaction. The total amount of trimethoxysilane used was 69 mL, and the total amount of platinum catalyst used was 1 × 10 ⁻³ equivalent in molar ratio with respect to the alkenyl groups of the polymer. After the reaction by heating, the volatile matter of the mixture is distilled off under reduced pressure to give a silyl group-terminated vinyl polymer (polymer [P
15]) was obtained. The number average molecular weight of the obtained polymer is GP.
The C measurement (in terms of polystyrene) was 28500, and the molecular weight distribution was 1.4. The average number of silyl groups introduced per molecule of the polymer was 2.5 as determined by ¹ H NMR analysis.

Similarly, the polymer [P14] was placed in a 2 L reaction vessel,
3-mercaptopropyltrimethoxysilane, 2,2 '
-Preparation of azobis-2-methylbutyronitrile, heating reaction, and sufficient removal of the volatile components of the mixture under reduced pressure (without leaving unreacted 3-mercaptopropyltrimethoxysilane) to remove the silyl group. A vinyl polymer having a terminal group (polymer [P16]) was obtained. The number average molecular weight of the obtained polymer was 2 by GPC measurement (polystyrene conversion).
8500, the molecular weight distribution was 1.4. The average number of silyl groups introduced per polymer molecule is determined by ¹ H NMR.
It was 2.8 as determined by analysis.

Similarly, the polymer [P14] was placed in a 2 L reaction vessel.
(1000 g), dimethoxymethylhydrosilane (45
mL), methyl orthoformate (13.3 mL), and 0
A 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of valent platinum was charged. The polymer [P1
5] Similarly, a platinum catalyst and dimethoxymethylhydrosilane were added during the reaction. After sufficiently reacting by heating, the volatile matter of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P17]). The number average molecular weight of the obtained polymer was 28,500 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.4. Polymer 1
The average number of silyl groups introduced per molecule is ¹ H N
The number was 2.5 as determined by MR analysis. (Production Example 4) Based on the method described in Example 2 of JP-A-11-080249, hydroxyethyl-2-bromopropionate was used as an initiator, and cuprous bromide and 2,2-bipyridyl were used as polymerization catalysts. As a polymer of poly (n-butyl acrylate), poly (acrylic acid) -n having a hydroxyl group at the terminal by adding 2-hydroxyethyl methacrylate at the final stage of the polymerization.
-Butyl (polymer [P18]) was obtained. The number average molecular weight of the obtained polymer was 6100 as measured by GPC (in terms of polystyrene), and the molecular weight distribution was 1.3. The average number of silyl groups introduced per molecule of polymer is ¹ H NM
The number was 3.3 as determined by R analysis.

Isocyanatopropyltrimethoxysilane was added to this to carry out a urethanization reaction, and the terminal hydroxyl group was converted to a trimethoxysilyl group to give a vinyl-based polymer having a mean number of trimethoxysilyl groups of 3.3. Combined [P19]) was obtained. (Production Example 5) CuBr (22.4 g, 0.156 mo) was placed in a 2 L separable flask equipped with a reflux tube and a stirrer.
1) was charged and the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (112 mL) was added, and the mixture was placed in an oil bath at 70 ° C for 30 minutes.
Stir for minutes. Butyl acrylate (0.20k
g), methyl 2-bromopropionate (86.9 g,
0.520 mol), triamine (0.19 mL, 0.
18 g, 1.04 mmol) was added to start the reaction.
While heating and stirring at 70 ° C, butyl acrylate (0.8
0 kg) was continuously added dropwise over 150 minutes. During the dropwise addition of butyl acrylate, triamine (1.81 mL, 1.
71 g, 9.88 mmol) was added. Continue to 70
The mixture was heated and stirred at 230C for 230 minutes. The reaction mixture was diluted with toluene, passed through an activated alumina column, and the volatile component was distilled off under reduced pressure to give an alkenyl group-terminated polymer (polymer [P
20]) was obtained. The number average molecular weight of the polymer [P20] is 2
The molecular weight distribution was 600 and the molecular weight distribution was 1.18. 2L with reflux pipe
The polymer [P20] (0.937) was placed in a separable flask.
kg), potassium acetate (73.5 g), N, N-dimethylacetic acid amide (0.8 L) were charged, and the temperature was 70 ° C. under a nitrogen stream.
The mixture was heated and stirred for 5 hours. After removing N, N-dimethylacetic acid amide under heating and reduced pressure, the mixture was diluted with toluene. Solid components insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatile components of the filtrate were distilled off under reduced pressure to obtain a polymer [P21]. Comparative Examples 1-2) Polymers [P2], [P8], [P11] and [P] obtained in Production Examples 1 to 4
15] and [P16] are mixed with various antioxidants and light stabilizers. For the blending of the polymers [P11] and [P15], respectively, a tetravalent Sn catalyst (dibutyltin diacetylacetonate) is used. 2 for combination [P16]
Using a valent Sn catalyst (tin octylate) and a curing accelerator (laurylamine), the mixture was allowed to stand at room temperature for 2 days and then cured at 50 ° C. for 3 days. Regarding the blending of the polymers [P2] and [P8], platinum (0) -divinyltetramethyldisiloxane complex was used as a curing catalyst, and chain siloxane was used as a curing agent (average of 5 hydrosilyl groups and average of 5 in the molecule). Containing an α-methyl styrene group of Si.
0 mmol / g), and an amount of Si—H groups to be 1.8 equivalents of the alkenyl groups of the polymer was added, and 150 ° C., 10
It was cured for 0 minutes. Each of the cured products was formed into a sheet having a size of about 2 mm. A 2 (1/3) type dumbbell type test piece was punched out from the cured product after curing and curing, and tensile properties (using Shimadzu autograph, measurement temperature: 23 ° C., tensile speed: 200 mm / se)
c) was evaluated. Further, the cured product was stored in a dryer at 150 ° C., taken out after heat resistance of 200 hours and 1000 hours, and subjected to a tensile test in the same manner as in the initial stage. The composition and the results are shown in Table 1.

[0274]

[Table 1] Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant: C1 ... Irganox 1010, C2 ... Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part), Cat. C ... Platinum (0) -divinyltetramethyldisiloxane complex (5 ×
10 ⁻⁴ equivalent) → However, at this time, a chain siloxane as a curing agent (containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule. Si—H group amount 3.70).
mmol / g), and added in an amount such that the Si-H group becomes 1.8 equivalents of the alkenyl group of the polymer. (Examples 8 to 18 and Comparative Examples 3 to 5) Production Examples 1 to 4
Each of the polymers [P3] to [P19] obtained in 1 above is mixed with 1 part of each of various antioxidants and light stabilizers, and each of them is a tetravalent Sn catalyst (dibutyltin diacetylacetonate) or divalent S.
Curing was performed at room temperature using an n catalyst (tin octylate) and a curing accelerator (lauryl amine), and the skin tension time was evaluated.
The skin tension time in the present invention was evaluated by the time until the composition exhibited rubber elasticity and did not reach the metal spatula. The formulations and the results are shown in Table 2.

[0275]

[Table 2] Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant: C1 ... Irganox 1010, C2 ... Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part) (Examples 19 to 30 and Comparative Examples 6 to 8) Production Examples 1 to 1
Polymers [P3] to [P19] obtained in No. 4 are 10
To 0 parts, 120 parts of colloidal calcium carbonate (Shirakanka CCR: Shiraishi Kogyo) and heavy calcium carbonate (Nanox 25
A: made by Maruo Calcium) 30 parts, plasticizer 50 parts, various kinds of antioxidants and light stabilizers 1 part each, and 4 parts air oxidation curable substance, 3 parts photocurable substance, 2 parts silanol-containing compound After mixing and further thoroughly mixing using three paint rolls, curing was carried out in the same manner as in Example 1 using a curing catalyst. After the skin tension time at that time was evaluated, it was cured and cured in a room for 2 days and then at 50 ° C. for 3 days to obtain a cured product. The residual tack of each cured product was evaluated. Furthermore, the surface of the cured product after irradiating the cured product for 5000 hours with a xenon weather meter (Suga tester SX120 type, radiant intensity 180W, black panel temperature 63 ° C, rainfall 18 minutes during irradiation 2 hours), and Torikai, Settsu City, Osaka Prefecture The appearance of the surface of the cured product was visually observed after installation for 2 months outdoors in the west. The composition and the results are shown in Table 3.

[0276]

[Table 3] Residual tack: Good ← ○ ＞ △ ＞ × → Poor (sticky) Surface weather resistance: Good ← ○ ＞ △ ＞ × → Poor (with cracks and whitening) Contamination: Good ← ○ ＞ △ ＞ × → Blackening (adhered matter) Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant: C1 ... Irganox 1010, C2 ...
Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part) Air-oxidation curable substances: C ... Tung oil, D ... Flaxseed oil, E ...
1,2-Polybutadiene photocurable substance: F ... Pentaerythritol triacrylate, G ... Trimethylolpropane triacrylate Plasticizer: H ... P11, I ... PN-260 (polyester type: Asahi Denka Kogyo), J ... DOP (dioctyl) Phthalate: manufactured by Kyowa Fermentation), silanol compound: K ... Hexamethyldisilazane, L
Trimethylphenoxysilane, M ... Tris (trimethylsilyl) compound of trimethylolpropane (Examples 31 to 32 and Comparative Examples 9 to 10) Production Example 1
To the polymers [P9] to [P17] obtained in Examples 4 to 4 were blended in the same manner as in Examples 19 to 30 and Comparative Examples 6 to 8 and thoroughly dehydrated before adding the curing catalyst. A tetravalent Sn catalyst was added in an anhydrous state, and further 2 parts of vinyltrimethoxysilane was added as a dehydrating agent to obtain a one-part blend.
Cured products were prepared in the same manner as in Examples 19 to 30 and Comparative Examples 6 to 8, and the same evaluation was performed. Further, various alkyd paints were applied to the cured product, which was allowed to stand in the room for one day, and then the coated surface was touched with a finger to determine the degree of cure. The respective formulations and the results are shown in Table 4.

[0277]

[Table 4] Residual tack: Good ← ○ ＞ △ ＞ × → Poor (sticky) Surface weather resistance: Good ← ○ ＞ △ ＞ × → Poor (cracks and whitening) Contamination: Good ← ○ ＞ △ ＞ × → Blackening (with) A lot of kimono) Alkyd coatability (1 day after application): ○ ... Complete cure, △ ...
There is tack (stickiness), x uncured ... Alkyd paint:
Ruby AZ (manufactured by Akzo) Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant: C1
Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part) Air-oxidation curable substances: C ... Tung oil, D ... Flaxseed oil, E ...
1,2-Polybutadiene photo-curable substance: F ... Pentaerythritol triacrylate, G ... Trimethylolpropane triacrylate Plasticizer: H ... P11, I ... PN-260 (polyester type: Asahi Denka Kogyo), J ... DOP (dioctyl) Phthalate: manufactured by Kyowa Fermentation), silanol compound: K ... Hexamethyldisilazane, L
Trimethyl (phenoxysilane), M ... Tris (trimethylsilyl) dehydrate of trimethylolpropane Dehydrating agent: N ... Vinyltrimethoxysilane (Examples 33 to 39 and Comparative Examples 11 to 12) Polymers obtained in Production Examples 1 to 4 [ P2], [P8],
[P11], [P15], and [P16] are blended with various antioxidants and light stabilizers, and polymer [P11],
Regarding the compounding of [P15], a polymer [P16] was prepared by using a tetravalent Sn catalyst (dibutyltin diacetylacetonate).
For the compounding, a divalent Sn catalyst (tin octylate) and a curing accelerator (laurylamine) were used, the mixture was allowed to stand at room temperature for 2 days, and then cured at 50 ° C. for 3 days. Regarding the blending of the polymers [P2] and [P8], platinum (0) -divinyltetramethyldisiloxane complex was used as a curing catalyst.
Chain siloxane as a curing agent (containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule.
Si-H group amount 3.70 mmol / g) was used, and Si-
The H group was added in an amount equivalent to 1.8 equivalents of the alkenyl group of the polymer and cured at 150 ° C. for 100 minutes. Each of the cured products was a test body specified in JIS A 5758-1992. Initial tensile properties (using Shimadzu autograph, measurement temperature: 23 ° C, tensile speed: 200 mm / sec) were evaluated, and xenon weather meter (Suga Test Instruments S
X120 type, irradiance 180W, black panel temperature 6
The cured product irradiated for 200 hours and 1000 hours at 3 ° C. for 2 hours of irradiation and 18 minutes of rainfall was measured in the same manner as in the initial stage. The composition and the results are shown in Table 5.

[0278]

[Table 5] Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant: C1 ... Irganox 1010, C2 ... Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part), Cat. C ... Platinum (0) -divinyltetramethyldisiloxane complex (5 ×
10 ⁻⁴ equivalent) → However, at this time, a chain siloxane as a curing agent (containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule. Si—H group amount 3.70).
mmol / g), and added in an amount such that the Si-H group becomes 1.8 equivalents of the alkenyl group of the polymer. (Examples 40 to 50 and Comparative Examples 13 to 14) Each of the polymers [P3] to [P19] obtained in Production Examples 1 to 4 was mixed with 1 part of each of various antioxidants and light stabilizers. Value S
An n catalyst (dibutyltin diacetylacetonate) or a divalent Sn catalyst (tin octylate) and a curing accelerator (laurylamine) were used to cure at room temperature, and the skin tension time was evaluated. The skin tension time in the present invention was evaluated by the time until the composition exhibited rubber elasticity and did not reach the metal spatula. The composition and the results are shown in Table 6.

[0279]

[Table 6] Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant: C1 ... Irganox 1010, C2 ... Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part) (Examples 51 to 62 and Comparative Examples 16 to 18) 100 parts of each of the polymers [P3] to [P19] obtained in Production Examples 1 to 4. In addition, colloidal calcium carbonate (white luster CC
R: Shiraishi Kogyo) 120 parts, heavy calcium carbonate (Nanox 25A: Maruo calcium) 30 parts, plasticizer 50
Parts, 1 part of each of various antioxidants and light stabilizers, 4 parts of air-oxidation-curable substance, 3 parts of photo-curable substance, 2 parts of silanol-containing compound are mixed, and further 3 rolls of paint are used. After mixing, curing was performed in the same manner as in Example 33 using the curing catalyst. After the skin tension time at that time was evaluated, it was cured and cured in a room for 2 days and then at 50 ° C. for 3 days to obtain a cured product. The residual tack of each cured product was evaluated. Further, the cured product is treated with a xenon weather meter (Suga Testing Machine SX1
20 type, radiation intensity 180W, black panel temperature 63
The appearance of the surface of the cured product after irradiation for 5000 hours at a temperature of 2 hours for 18 minutes of rainfall for 2 hours, and the appearance of the surface of the cured product after being placed outdoors at Torikai Nishi, Settsu City, Osaka Prefecture for 2 months were observed. The formulations and the results are shown in Table 7.

[0280]

[Table 7] Residual tack: Good ← ○ ＞ △ ＞ × → Poor (sticky) Surface weather resistance: Good ← ○ ＞ △ ＞ × → Poor (with cracks and whitening) Contamination: Good ← ○ ＞ △ ＞ × → Blackening (adhered matter) Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant: C1 ... Irganox 1010, C2 ...
Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part) Air-oxidation curable substances: C ... Tung oil, D ... Flaxseed oil, E ...
1,2-Polybutadiene photocurable substance: F ... Pentaerythritol triacrylate, G ... Trimethylolpropane triacrylate Plasticizer: H ... P11, I ... PN-260 (polyester type: Asahi Denka Kogyo), J ... DOP (dioctyl) Phthalate: manufactured by Kyowa Fermentation), silanol compound: K ... Hexamethyldisilazane, L
Trimethylphenoxysilane, M ... Tris (trimethylsilyl) compound of trimethylolpropane (Examples 63 to 64 and Comparative Examples 19 to 20) Using the polymers [P9] to [P17] obtained in Production Examples 1 to 4,
Blends were blended in the same manner as in Examples 51-62 and Comparative Examples 16-18, thoroughly dehydrated before adding the curing catalyst, and then the tetravalent Sn catalyst was added in an anhydrous state, and vinyltrimethoxy was used as a dehydrating agent. Two parts of silane were added to obtain a one-part formulation. Cured products were prepared in the same manner as in Examples 51 to 62 and Comparative Examples 16 to 18, and the same evaluation was performed. Further, various alkyd paints were applied to the cured product, which was allowed to stand in the room for one day, and then the coated surface was touched with a finger to determine the degree of cure. The respective formulations and the results are shown in Table 8.

[0281]

[Table 8] Residual tack: Good ← ○ ＞ △ ＞ × → Poor (sticky) Surface weather resistance: Good ← ○ ＞ △ ＞ × → Poor (with cracks and whitening) Contamination: Good ← ○ ＞ △ ＞ × → Blackening (with) A lot of kimono) Alkyd coatability (1 day after application): ○ ... Complete cure, △ ...
There is tack (stickiness), uncured ... Alkyd paint: Rubol AZ (manufactured by Akzo) Light stabilizer: A1 ... Sanol LS765, A2 ... Sanol LS2626, B1 ... Tinuvin 144, B2 ... Tinuvin 213, B3 ... Tinuvin 326 Antioxidant Agent: C1 ... Irganox 1010, C2 ...
Irganox 245 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part) Air-oxidation curable substances: C ... Tung oil, D ... Flaxseed oil, E ...
1,2-Polybutadiene photocurable substance: F ... Pentaerythritol triacrylate, G ... Trimethylolpropane triacrylate Plasticizer: H ... P11, I ... PN-260 (polyester type: Asahi Denka Kogyo), J ... DOP (dioctyl) Phthalate: manufactured by Kyowa Fermentation), silanol compound: K ... Hexamethyldisilazane, L
Trimethyl (phenoxysilane), M ... Tris (trimethylsilyl) dehydrate of trimethylolpropane Dehydrating agent: N ... Vinyltrimethoxysilane (Example 65) Using the polymer [P15] obtained in Production Example 3, Examples 51 to 62. In addition, the same formulation as in Comparative Examples 16 to 18 was blended, thoroughly dehydrated before adding the curing catalyst, then the tetravalent Sn catalyst was added in an anhydrous state, and further vinyltrimethoxysilane and aminosilane were added, and 1 A liquid formulation was obtained. Examples 51-62 and Comparative Examples 16-18
A cured product was produced in the same manner as in Example 1 and the same evaluations as in Examples 33 to 39 and Comparative Examples 11 to 12 were performed. The respective formulations and the results are shown in Table 9.

[0282]

[Table 9] Light stabilizer: A1 ... Sanol LS765, B2 ... Tinuvin 213 Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts) Other compounding agents: Colloidal calcium carbonate (150 parts): Shiratsuka CCR (manufactured by Shiraishi Industry) Heavy calcium carbonate (20 parts): Nanox 25A (manufactured by Maruo Calcium) ) Air oxidation curable substance (2 parts): Tung oil photocurable substance (2 parts): Trimethylolpropane triacrylate plasticizer (80 parts): Polymer [P11] Silanol compound (2 parts): Trimethylphenoxysilane adhesion imparting Agent (1 part): N- (β-aminoethyl) -γ-
Aminopropyltrimethoxysilane dehydrating agent (2 parts): vinyltrimethoxysilane

[0283]

The present invention has the following two components: a vinyl polymer (I) having at least one crosslinkable functional group, and
Curable composition containing antioxidant (II), and vinyl having a crosslinkable silyl group in which a is 3 among crosslinkable silyl groups represented by the general formula (1) It is composed of a curable composition containing a polymer, and has excellent heat resistance and weather resistance, and excellent curability. —SiY _a R _3-a (1) (wherein R represents 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, or ( R ') ₃ SiO- (R' has 1 to 2 carbon atoms
A monovalent hydrocarbon group of 0, and three R ′ may be the same or different) and represents a triorganosiloxy group represented by They may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 1, 2, or 3. )

Claims (37)

[Claims] 1. A curable composition containing the following two components: a vinyl polymer (I) having at least one crosslinkable functional group, and an antioxidant (II). 2. The curable composition according to claim 1, containing the vinyl polymer (I) having a molecular weight distribution of less than 1.8. 3. The main chain is a (meth) acrylic monomer,
Containing a vinyl polymer (I) produced mainly by polymerizing a monomer selected from the group consisting of an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer. A curable composition according to claim 1 or 2. 4. The curable composition according to claim 3, wherein the main chain contains a vinyl polymer (I) which is a (meth) acrylic polymer. 5. The curable composition according to claim 4, wherein the main chain contains a vinyl polymer (I) which is an acrylic polymer. 6. The curable composition according to claim 5, wherein the main chain contains a vinyl polymer (I) which is an acrylic ester polymer. 7. The crosslinkable functional group of the vinyl polymer (I) is a crosslinkable silyl group.
6. The curable composition according to any one of 6. 8. The crosslinkable functional group of the vinyl polymer (I) is an alkenyl group.
Curable composition as described in any one of these. 9. The curable composition according to any one of claims 1 to 6, wherein the crosslinkable functional group of the vinyl polymer (I) is a hydroxyl group. 10. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an amino group. 11. The crosslinkable functional group of the vinyl polymer (I) is a group having a polymerizable carbon-carbon double bond, according to any one of claims 1 to 6. Curable composition. 12. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an epoxy group. 13. The curable composition according to claim 1, wherein the main chain contains a vinyl polymer produced by a living radical polymerization method. . 14. The curable composition according to claim 13, wherein the living radical polymerization contains a vinyl polymer which is atom transfer radical polymerization. 15. A vinyl-based heavy-weight catalyst in which atom transfer radical polymerization is catalyzed by a complex selected from transition metal complexes whose central metal is an element of Group 7, 8, 9, 10, or 11 of the periodic table. The curable composition according to claim 14, wherein the curable composition contains a coalescence. 16. A metal complex used as a catalyst is copper, nickel,
16. The curable composition according to claim 15, containing a vinyl polymer which is a complex selected from the group consisting of ruthenium and iron complexes. 17. The metal complex used as a catalyst contains a vinyl polymer which is a copper complex.
The curable composition according to. 18. A curable resin having a crosslinkable functional group comprising a vinyl polymer, which is a crosslinkable silyl group represented by the general formula (1), wherein a is 3 and curability is improved. The curable composition according to any one of claims 1 to 17, characterized in that. —SiY _a R _3-a (1) (wherein R represents 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, or ( R ') ₃ SiO- (R' has 1 to 2 carbon atoms
A monovalent hydrocarbon group of 0, and three R ′ may be the same or different) and represents a triorganosiloxy group represented by They may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 1, 2, or 3. ) 19. The curable composition according to claim 18, which contains a vinyl polymer having a crosslinkable silyl group at a main chain terminal. 20. A vinyl-based polymer contains a vinyl-based polymer containing only a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1). The curable composition according to any one of claims 1 to 19. 21. A part or all of the vinyl-based polymer,
Among the crosslinkable silyl groups represented by the general formula (1), a crosslinkable silyl group in which a is 3 and in the crosslinkable silyl group represented by the general formula (1), a is 1 or 2 The curable composition according to any one of claims 1 to 20, which comprises a vinyl polymer that is a polymer having both silyl groups. 22. The vinyl polymer is a polymer having a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1), and is represented by the general formula (1). 21. The crosslinkable silyl group according to claim 1, which contains both vinyl-based polymers having a crosslinkable silyl group in which a is 1 or 2. Curable composition. 23. The vinyl polymer is a polymer having a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1), and is represented by the general formula (1). 21. The vinyl-based polymer according to claim 1, wherein the vinyl-based polymer is a polymer having only a crosslinkable silyl group in which a is 1 or 2 among the crosslinkable silyl groups. Curable composition. 24. The vinyl polymer contains only a vinyl polymer having only a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1). The curable composition according to any one of claims 1 to 20. 25. A vinyl polymer having only a crosslinkable silyl group represented by the general formula (1) in which a is 3 among the crosslinkable silyl groups represented by the general formula (1); It has both a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented and a crosslinkable silyl group in which a is 1 or 2 among the crosslinkable silyl groups represented by the general formula (1). 21. The curable composition according to any one of claims 1 to 20, which contains both vinyl-based polymers that are polymers. 26. A vinyl polymer represented by the general formula (1), wherein the vinyl polymer has only a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1). 21. A polymer having a crosslinkable silyl group in which a is 1 or 2 among the crosslinkable silyl groups contained in both vinyl-based polymers. Curable composition. 27. The vinyl polymer is a polymer having only a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1), and a vinyl polymer represented by the general formula (1). 21. A vinyl polymer having both crosslinkable silyl groups in which a is 1 or 2 among the crosslinkable silyl groups. The curable composition described. 28. The curable composition according to any one of claims 1 to 27, wherein the antioxidant (II) is an antioxidant (III). 29. The curable composition according to any one of claims 1 to 28, wherein the antioxidant (III) is a hindered phenol type. 30. The curable composition according to claim 1, further comprising a light stabilizer (IV). 31. The light stabilizer (IV) is one or more selected from the group consisting of hindered amine light stabilizers, benzoate light stabilizers, benzotriazole light stabilizers, and benzophenone light stabilizers. The curable composition according to any one of claims 1 to 30, wherein the curable composition is a curable composition. 32. The antiaging agent (II) is a light stabilizer (I).
V ') is a curable composition as described in any one of Claims 1-27. 33. The curable composition according to any one of claims 1 to 27 or 32, wherein the light stabilizer (IV ′) is an ultraviolet absorber. 34. The light stabilizer (IV ′) is one or two selected from the group consisting of a hindered amine light stabilizer, a benzoate light stabilizer, a benzotriazole light stabilizer, and a benzophenone light stabilizer. It is the above thing, It is characterized by the above-mentioned 1-27 thru | or 32,3.
Curable composition as described in any one of 3. 35. The curable composition according to any one of claims 1 to 27 or 32 to 34, wherein an ultraviolet absorber and a hindered amine type are combined as the light stabilizer (IV ′). . 36. An antioxidant (III ′) is further added, which is characterized in that: 1-27 or 32-35.
Curable composition as described in any one of these. 37. The antioxidant (III ′) is a hindered phenol-based compound.
Or a curable composition according to any one of 32 to 36.