JP2003327852A - Curing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide curing compositions containing vinyl-based polymers which do not deteriorate heat resistance and oil resistance of cured products of the compositions and have cross-linking functional groups, so as to obtain the cured products having higher tensile strength at breakage than ever, by being scarcely affected on the good heat resistance nor oil resistance. <P>SOLUTION: One of the curing compositions contains (A1) a vinyl-based polymer which has at least one cross-linking functional group and (B1) furnace carbon black as essential ingredients. Another curing composition contains (A2) another vinyl-based polymer which has at least one cross-linking functional group and of which the cured product has such oil resistance that any one of items of the oil resistance against a lubricating oil of 3 class 5 type used in land-based vehicles specified in JIS K 2215 in an immersion test specified JIS K 6258 is higher than that of a cured product of an butyl acrylate homopolymer having the same structure and (B2) carbon black as essential ingredients. The other curing composition contains (A1) the vinyl-based polymer having at least one crossliking functional group, (B2) the carbon black, and (C) an adhesion-giving agent as essential ingredients. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, a curable composition containing a vinyl-based polymer having at least one crosslinkable functional group and furnace carbon black, or at least one crosslinkable functional group, and the oil resistance of the cured product is , JIS K 2
JI for land type 3 No. 5 lubricating oil specified in 215
In any one of the SK 6258 immersion tests, a curable composition containing a vinyl polymer and carbon black, which is more than a cured product of a butyl acrylate homopolymer having the same structure, or a crosslinkable functional group. It relates to a curable composition containing a vinyl-based polymer having at least one of the above, carbon black, and an adhesiveness-imparting agent.

[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 the number average molecular weight to the 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 hydroxyl group bonded to a silicon atom 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. A coalesced product or a cured product obtained from the composition thereof is excellent in heat resistance or weather resistance, and is not limited, but a sealing material such as a building elastic sealing material sealant or a double-layer glass sealing material,
Electric / electronic component materials such as solar cell backside encapsulant, electric wires, etc.
Electrical insulation materials such as insulation coating materials for cables, adhesives, adhesives, elastic adhesives, paints, powder coatings, coating materials,
It can be used for various applications such as foams, potting agents for electric and electronic products, films, gaskets, casting materials, various molding materials, and rust-proof / water-proof encapsulation materials for meshed glass and laminated glass end faces (cuts). Is.

It can also be used for sealing automobile parts, electric parts, various machine parts and the like.

[0010]

Among these applications,
For example, a liquid gasket or the like used around the engine of an automobile or the like is required to have a sealing property even under the condition that it is exposed to a heated high temperature atmosphere or exposed to a high temperature engine oil. At that time, for the purpose of cost reduction and reinforcement, in a curable composition containing calcium carbonate that is generally used in sealants for general construction, etc., the cured product obtained by curing the composition is in air or oil. Continuing to be exposed to a high temperature, the mechanical properties of the cured product would be significantly higher in modulus and lower in elongation than before heating, and the sealing property might be incomplete. Therefore, the object of the present invention is to obtain a cured product having sufficient strength at break and high elongation for practical use even at room temperature, heating the cured product,
It is an object of the present invention to provide a curable composition having a vinyl polymer having a crosslinkable functional group that causes little change in mechanical properties of a cured product even when immersed in a heated oil.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and by adding carbon black to this vinyl polymer, the breaking strength can be further improved.
The inventors have found that a cured product having a high elongation at break and good heat resistance and oil resistance can be maintained, and solved the above problems to reach the present invention.

[0012]

DETAILED DESCRIPTION OF THE INVENTION

(A1) A curable composition comprising a vinyl polymer (B1) furnace carbon black having at least one crosslinkable functional group as an essential component. (A2) At least one crosslinkable functional group, and the oil resistance of the cured product thereof is 3 for land specified in JISK 2215.
A vinyl polymer that exceeds the cured product of a butyl acrylate homopolymer having the same structure in any one item of the immersion test of JIS K 6258 with respect to the lubricating oil of species 5. (B2) A curable composition containing carbon black as an essential component. The present invention relates to a curable composition containing (A1) a vinyl polymer having at least one crosslinkable functional group (B2) carbon black (C) as an adhesiveness-imparting agent.

The curable composition of the present invention will be described in detail below. << (A1) Vinyl-Based Polymer >><MainChain> The inventors have heretofore described a vinyl-based polymer having various crosslinkable functional groups at the polymer terminal, a process for producing the same, a curable composition, And various inventions have been carried out with respect to its use (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 of the present invention is not particularly limited, but all of the polymers disclosed in the invention exemplified above can be preferably used.

The vinyl-based monomer constituting the main chain of the vinyl-based polymer of the present invention is not particularly limited, and various types 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,
Tolyl (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, perfluoroethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, permethacrylate acrylate Fluoroethyl perfluorobutylmethyl, 2- (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meta 2,2-perfluoro methyl ethyl acrylate, (meth) acrylic acid perfluoromethyl perfluoroethyl methyl (meth) acrylate, 2
Perfluoromethyl-2-perfluoroethylethyl,
2- (meth) acrylic acid 2-perfluorohexylmethyl,
2-perfluorohexylethyl (meth) acrylate,
2- (meth) acrylic acid 2-perfluorodecylmethyl,
2-perfluorodecylethyl (meth) acrylate,
(Meth) acrylic monomers such as 2-perfluorohexadecylmethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methylstyrene, chlorostyrene,
Aromatic vinyl monomers such as styrene sulfonic acid and salts thereof; Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, Maleimide-based monomers such as dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; acrylonitrile such as acrylonitrile and methacrylonitrile. Triyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of them may be copolymerized.

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. Acrylic acid ester monomers and methacrylic acid ester monomers are more preferable, and acrylic acid ester monomers are particularly preferable. For applications such as general construction, low viscosity of compound, low modulus of cured product,
A butyl acrylate-based monomer is more preferable because physical properties such as high elongation, weather resistance and heat resistance are required. On the other hand, in applications where oil resistance and the like are required such as automobiles, a copolymer mainly containing ethyl acrylate is more preferable. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). It can be replaced. However, as the ratio of butyl acrylate increases, its good oil resistance is impaired, so for applications requiring oil resistance, the ratio is preferably 40% or less, and further 30% or less. More preferably. Further, it is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the alkyl group of the side chain in order to improve low-temperature characteristics and the like without impairing oil resistance.
However, since heat resistance tends to be poor due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. It is possible to obtain a suitable polymer by changing the ratio in consideration of the required physical properties such as oil resistance, heat resistance, low temperature characteristics, etc. according to various uses and required purposes. For example, but not limited to, examples of excellent physical property balance such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40 to 50/20 by weight ratio). 30/30 to 20) copolymer.

In the present invention, these preferred monomers may be copolymerized with other monomers, and further may be block copolymerized, in which case, 40% by weight of these preferred monomers are contained. Is preferred. 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> The synthesis method of the vinyl polymer of the present invention 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. It can be classified into a "controlled radical polymerization method" in which a specific functional group can be introduced at a controlled position such as a terminal.

The "general radical polymerization method" is a simple method, but in this method, a monomer having a specific functional group is stochastically introduced into the polymer. 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. It 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.

Unlike 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 by 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.

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).

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, 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 for 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.

[0037]

[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 can be 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 above radical scavenger such as 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 the above formula, R ¹ is a hydrogen atom or a carbon number of 1 to 1).
20 alkyl groups, aryl groups, or aralkyl groups,
Examples of X include chlorine, bromine, and 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 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 1. ^{R 4 R 5 C (X)} -R 6 -R 7 -C (R 3) = CH 2 (1) ( 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 group of the formulas 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 ,

[0043]

[Chemical 2] (In the above formula, X is chlorine, bromine, or iodine,
n is 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 ,

[0044]

[Chemical 3] (In the above formula, X is chlorine, bromine, or iodine,
(n is an integer of 1 to 20 and m is an integer of 0 to 20) o, m, p-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 the above formula, X is chlorine, bromine, or iodine,
(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 the above formula, X is chlorine, bromine, or iodine,
(n is an integer of 1 to 20 and m is an integer of 0 to 20) o, m, p-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 the above formula, X is chlorine, bromine, or iodine,
(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 the above formula, X is chlorine, bromine, or iodine,
(n is an integer of 1 to 20 and m is an integer of 0 to 20) Further as an organic halide having an alkenyl group
Examples thereof include compounds represented by general formula 2. H₂C = C (R³) -R⁷-C (R^Four) (X) -R⁸-R^Five  (2) (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) R is 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 (the above formula, X is chlorine, bromine or iodine,
Examples of R include alkyl groups having 1 to 20 carbon atoms, aryl groups, and aralkyl groups).

[0046] 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, (wherein X is chlorine, bromine, or iodine,
n is an integer of 0 to 20) and the like.

Organic halogen having the crosslinkable silyl group
The compound is not particularly limited, and may be, for example, a compound represented by the general formula 3.
Those having a structure are exemplified. 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  (3) (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 the above formula, X is chlorine, bromine, iodine, and n is 0.
~ An integer from 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 the above formula, X is chlorine, bromine, iodine, and n is 1
To an integer of 20 and m is an integer of 0 to 20) 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 the above formula, X is chlorine, bromine, or iodine)
Etc.

Further examples of the organic halide having a crosslinkable silyl group include those having a structure represented by the general formula (4). ^{_{(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) 8 -R 5 (4)} ( wherein ^{-R, 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 (the above formula, X is chlorine, bromine or iodine,
Examples of R include alkyl groups having 1 to 20 carbon atoms, aryl groups, and aralkyl groups).

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 above formulas, X is chlorine, bromine or iodine,
R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, n is an integer of 1 to 20) The organic halide having the above amino group or a sulfonyl halide compound is not particularly limited, The following is exemplified. In _{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X) ( the above formulas, X is chlorine, bromine or iodine,
R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, 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, The following is exemplified.

[0050]

[Chemical 4] (In the above formula, X is chlorine, bromine, or iodine,
R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20) In order to obtain a polymer having two or more terminal structures in the present invention An organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. To give a concrete example,

[0051]

[Chemical 5]

[0052]

[Chemical 6] Etc.

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

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably No. 7 of the Periodic Table.
It is a metal complex complex having a group metal, a group 8, a group 9, a group 10, or a group 11 element as a central metal. More preferably,
A complex of 0-valent copper, 1-valent copper, 2-valent ruthenium, 2-valent iron or 2-valent nickel can be mentioned. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate. is there. When a copper compound is used, in order to enhance the catalytic activity, 2,2'-bipyridyl and its derivative, 1,10-phenanthroline and its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. The polyamine and other ligands are added. Further, trivalent triphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ )
Is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Further, divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistriphenylphosphine complex (NiCl
₂ (PPh ₃ ) ₂ ) and bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ ) are also suitable as the catalyst.

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. The polymerization is not limited, but is 0.
C. to 200.degree. C., preferably 5
It is 0 to 150 ° C. <Functional group> The crosslinkable functional group of the vinyl polymer is not limited, but a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, a polymerizable carbon-carbon double bond, an epoxy group and the like are preferable.

All of these crosslinkable functional groups can be used properly according to the use / purpose.

The vinyl-based polymer has at least one crosslinkable functional group on average. From the viewpoint of curability of the composition, it is preferable to have more than one, more preferably 1.1 to 4.0 on average, and still more preferably 1.2 to 3.5 on average. Position of Crosslinkable Functional Group When the cured product of the curable composition of the present invention is required to have rubber-like properties, the molecular weight between crosslinking points, which greatly affects rubber elasticity, can be increased, and thus the crosslinkable functional group can be obtained. It is preferred that at least one of these is 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 molecular end, 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 (5); - [Si ( R 9) 2-b (Y) b O] m -Si (R 10) 3-a (Y) a (5) {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.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3;
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 ^{(6) -Si (R 10)} 3-a (Y) a (6) ( 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, a compound having three a's (eg, trimethoxy functional group) has a faster curability than two compounds' (eg, dimethoxy functional group), but two compounds have better 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 5 (CH 3), - C 6 H 5 (C
_{H 3) 2, - (CH} 2) n -C 6 H 5, - (CH 2) n -C 6 H 5
_{(CH 3), - (CH} 2) n -C 6 H 5 (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, it is preferable that the alkenyl group of the polymer 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 main chain of the polymer is not particularly limited, but it may be bonded via a carbon-carbon bond, an ester bond, an ester 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 —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 of synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a hydrosilane compound having a crosslinkable silyl group in a vinyl polymer having at least one alkenyl group,
Method of adding in the presence of a hydrosilylation catalyst; (B) 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 Method; (C)
When synthesizing a vinyl polymer by radical polymerization, 1
A method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in the molecule; (D) a method of using a chain transfer agent having a crosslinkable silyl group when synthesizing a vinyl polymer by radical polymerization; (E) a method of reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a compound having a crosslinkable silyl group and a stable carbanion in one molecule; and the like.

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 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.

(Ad) 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) An 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 highly reactive carbon-halogen bond 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 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.

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

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

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

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 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 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.

Examples of the method for producing the vinyl polymer having at least one hydroxyl group used in the methods (B) and (A-g) to (A-j) include the following methods. 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 and 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, Japanese Unexamined Patent Publication No. 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.

(B-d) 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.

(Bg) 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 a halogen. how to. ^{M + C - (R 18)} (R 19) -R 20 -OH (16) ( ^{wherein, R 18, R 19, R} 20, are the same) R ^18, R ¹⁹
The electron-withdrawing _{group, -CO 2 R, -C (O} ) having a R and -CN structures are particularly preferred.

(Bh) A vinyl polymer having at least one highly reactive carbon-halogen bond 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.

(B-i) 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 is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl radical is used by a living radical polymerization method. 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 a 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.

Examples of 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 include 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, JP-B-3.
-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 method of 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, 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 general formula (22), R26 has 1 or more carbon atoms which may include one or more ether bonds or ester bonds.
A divalent organic group of 20, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, but like an aralkylene group having 7 to 20 carbon atoms, -C ₆ H ₄ - R ²⁷ - (wherein, C ₆ H ₄ is a phenylene group, R ²⁷ represents a divalent organic group direct bond or one or more ether bonds or carbon atoms, which may contain an ester bond 1-14 Or a —C (O) —R ²⁸ — (wherein R ²⁸ is a direct bond or has 1 to 19 carbon atoms which may include one or more ether bonds or ester bonds).
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 preferably sodium ion or potassium ion. 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 (25 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.

Various solvents may be used as the solvent used for the substitution reaction of the polymer terminal halogen. 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 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 the organic halide described above,
Alternatively, it is produced by a method of polymerizing a vinyl monomer using a halogenosulfonyl compound as an initiator and a transition metal complex as a catalyst, or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but 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. Although the temperature at which the reaction is carried out is not limited, it is generally from 0 to 150 ° C, and preferably from 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-based polymer having a hydroxyl group at the terminal is preferably a method of polymerizing a vinyl-based monomer using the above-mentioned organic halide or sulfonyl halide 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 ## STR1 ## 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) 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. Optionally represents a divalent organic group having 1 to 20 carbon atoms. A compound having R ³³ as an ester group is a (meth) acrylate compound, and a compound having R ³³ as a phenylene group is a styrene compound. There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, but if rubber-like properties are expected, the second step may be carried out at the end of the polymerization reaction or after the completion of a predetermined monomer reaction. It is preferable to react as a monomer of .

(B) When synthesizing a vinyl polymer by living radical polymerization, 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) obtained by atom transfer radical polymerization is prepared by a method as disclosed in JP-A-4-132706. 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-based 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 that stabilize the 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 polymer end, preferably at least one halogen represented by the general formula (27), and 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.

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), the control is easier ( 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, hexamethyldiisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; 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. << (A2) Vinyl-Based Polymer >> The vinyl-based polymer (A2) of the present invention preferably has “at least one crosslinkable functional group, and the cured product thereof has oil resistance of JIS
In any one item of the immersion test of JIS K 6258 with respect to the land 3 type 5 lubricating oil specified in K 2215, the oil resistance of a polymer cured product in which the repeating unit of the main chain is changed to butyl acrylate alone More than sex '; or
“Has at least one crosslinkable functional group, and the oil resistance of the cured product thereof is 3 types for land 5 defined in JIS K 2215.
JIS K 6258 immersion test for lubricating oil of No. 50, the rate of change in mass before and after immersion is 50% or less ”; or for lubricating oil of land type 3 No. 5 specified in JIS K 2215 In the immersion test of JIS K 6258, the mass change before and after the immersion is smaller than that of a polymer cured product in which the repeating unit of the main chain is changed to butyl acrylate alone ”; or“ JIS K
In the immersion test of JIS K 6258 for the land type 3 No. 5 lubricating oil stipulated in 2215, the volume change before and after the immersion was the curing of a polymer in which the repeating unit of the main chain was changed to butyl acrylate alone. It's smaller than the thing. "

The “polymer in which the repeating unit of the main chain is changed to butyl acrylate alone” in the present invention means that the functional group involved in crosslinking is essentially the same as that of the vinyl polymer of the present invention, and its molecular weight is Is 0.5 to 0.5 of the vinyl polymer of the present invention.
It means a homopolymer of butyl acrylate having a molecular weight distribution of 1.5 times and a value of molecular weight distribution of 0.5 to 1.5 times that of the vinyl polymer of the present invention.

The "land 3 type 5 lubricating oil defined in JIS K 2215" in the present invention is a lubricating oil for a land internal combustion engine to which an antioxidant and a detergent are added, and has a flash point of 200 ° C. As described above, kinematic viscosity of 16.3 mm ² / s or more 21.
It has properties such as less than 9 mm ² / s, a viscosity index of 85 or more, and a pour point of −5 ° C. or less.

The "JIS K 6258 immersion test" in the present invention is the dimension before and after immersion of the entire surface of the cured product of the vinyl polymer in the lubricating oil.
It measures changes in mechanical properties such as mass, volume, surface area and tensile strength.

The phrase "exceeds oil resistance" means that the rate of change in mass, the rate of change in volume, the rate of change in mechanical properties before and after immersion are smaller. In the above immersion test, the mass change rate before and after immersion is preferably 50% or less, more preferably 40% or less, and further preferably 30% or less.

The rate of change in volume and the rate of change in mechanical properties before and after immersion are preferably 50% or less, more preferably 40% or less, and further preferably 30% or less.

As described above, the vinyl polymer of the present invention having the above properties is particularly excellent in oil resistance. << Regarding Carbon Black >> Carbon black is roughly classified into a channel type, a furnace type, a thermal type, and an acetylene type according to a manufacturing method.

The channel type is a method in which natural gas is incompletely burned in a combustion chamber made of iron and a flame is made to impinge on the surface of the channel made of steel.

The furnace method is a method in which a gas, oil, or a mixture thereof is sent into a specially designed combustion furnace together with a certain amount of air and incompletely combusted to manufacture.

The thermal method is a method of producing natural gas by pyrolyzing it in a combustion furnace.

The acetylene method is a method in which acetylene gas is fed into a heated furnace to cause thermal decomposition, and the acetylene gas is produced.

The products produced by these are generally called channel black, furnace black, thermal black and acetylene black.

Furnace black carbon blacks such as Show Black N-219 and Show Black N-
220 (Showa Cabot), Niteron # 200, # 3
00, HTC # SL (manufactured by Shin Nikka Carbon), Asahi # 12
0, Asahi # 60, Asahi # 70 (Made by Asahi Carbon), Seast S
(Tokai Carbon), Diablack SA, Diablack N234 (Mitsubishi Chemical), Statex N121 (Columbia Carbon Japan), etc. are exemplified.

Examples of thermal blacks include Asahi Thermal, Asahi # 15 (Asahi Carbon), HTC # 20 (Nippon Nihon Carbon), and Huber N-907 (Huber).

Examples of acetylene black include electrified acetylene black (electrochemical).

The carbon black in the present invention is not particularly limited, and any of the above-mentioned types may be used, but it is preferable to use furnace black carbon from the viewpoints of variety, availability, cost and the like.

On the other hand, the amount of carbon black added is not particularly limited, but it is 0. 0 with respect to 100 parts by weight of the vinyl polymer.
1 to 500 parts by weight, preferably 0.5 to 100 parts by weight,
It is particularly preferable to use 1 to 50 parts by weight. If the blending amount is less than 0.1 part by weight, the effect of improving the breaking strength of the cured product may not be sufficient, and if it exceeds 500 parts by weight, the workability of the curable composition may be deteriorated or the cured product thereof. The physical properties of may deteriorate. The carbon black of the present invention may be used alone or in combination of two or more kinds. << Regarding Adhesion Providing Agent >> A silane coupling agent or an adhesion 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 joint width changes due to external force,
It is possible to further reduce the risk of the sealing material peeling from the adherend such as a siding board. 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, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, 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-γ-aminopropyltrimethoxysilane,
Amino group-containing silanes such as N-benzyl-γ-aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ- Mercapto group-containing silanes such as mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,3
Epoxy group-containing silanes such as 4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl- Carboxysilanes such as γ-aminopropyltrimethoxysilane; containing vinyl type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-acroyloxypropylmethyltriethoxysilane Examples thereof include silanes; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. Further, modified derivatives of these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters can also be used as silane coupling agents. .

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. If the added amount is too large, the rubber elasticity of the cured product obtained by curing the curable composition may be lost and the sealant may not function. In addition, when it is added to the two-component type described later, it is preferable that the total amount added to both of the two components be within the above range. The effect of the silane coupling agent added to the curable composition of the present invention, various adherends, that is, glass,
When used for inorganic base materials such as aluminum, stainless steel, zinc, copper, mortar, and organic base materials such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, non-primer conditions or primer treatment conditions give outstanding adhesion. Show improvement effect. 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 include, but are not limited to, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like.

The above-mentioned adhesiveness-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. << 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 Monoalkyltins such as tin compounds and monooctyltin compounds; titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organics such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminumethylacetoacetate Aluminum compounds; bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, carboxylic acid Carboxylic acids such as nickel, cobalt carboxylate, zinc carboxylate and aluminum carboxylate (2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, sodium (Tenic acid, etc.) metal salts, or reaction products and mixtures of these with amine compounds such as laurylamine described below; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; methylamine, ethylamine, propylamine , Isopropylamine, butylamine, amylamine, hexylamine, octylamine,
Aliphatic primary amines such as 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctyl. Aliphatic secondary amines such as amine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; triamylamine, trihexylamine, Aliphatic tertiary amines such as trioctylamine; triallylamine, oleylamine,
Aliphatic unsaturated amines such as; aromatic amines such as laurylaniline, stearylaniline and triphenylamine; and other amines such as monoethanolamine, diethanolamine, triethanolamine,
Diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,
Diethylaminopropylamine, xylylenediamine,
Ethylenediamine, hexamethylenediamine, 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, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N-
(Β-aminoethyl) aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminopropyltriethoxysilane, N- (β-aminoethyl) aminopropylmethyldiethoxysilane, N- (β-aminoethyl) amino Propyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ
-Aminopropyltrimethoxysilane, N-benzyl-
γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane and the like can be mentioned. In addition, silanol condensation of amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, silane coupling agents having amino groups such as phenylamino long-chain alkylsilanes, aminosilylated silicones; Examples of the catalyst include known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

These catalysts may be used alone,
You may use 2 or more types together. The amount of the condensation catalyst blended is such that the vinyl polymer 1 having at least one crosslinkable silyl group is used.
About 0.1 to 20 parts is preferable with respect to 00 parts (parts by weight, the same applies hereinafter), and 1 to 10 parts is more preferable. If the 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 the curable composition of the present invention, in order to further enhance the activity of the condensation catalyst, R ³⁸ _a Si (OR ³⁹ ) _4-a (37) of the general formula (37) (wherein R ³⁸ and R ³⁹ are each 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 general formula (37) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and triphenylmethoxysilane. R ^{38 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 content of the silicon compound is preferably about 0.01 to 20 parts, and preferably 0.1 to 10 parts, relative to 100 parts of the vinyl polymer having at least one crosslinkable silyl group.
Parts are more preferred. 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); R⁴⁰ ₃SiO- [Si (R⁴⁰)₂O]_a-[Si (H) (R⁴¹) O]_b-[Si (R ⁴¹ ) (R⁴²) O]_c-SiR⁴⁰ ₃    (38) HR⁴⁰ ₂SiO- [Si (R⁴⁰)₂O]_a-[Si (H) (R⁴¹) O]_b-[Si ( R⁴¹) (R⁴²) O]_c-SiR⁴⁰ ₂H (39) (In the formula, R⁵¹And R⁵²Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁴²Is 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);

[0156]

[Chemical 7] (In the formula, R⁴³And R⁴⁴Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁴⁵Is 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 combination 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 R ⁴⁶ 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. )

[0158]

[Chemical 8] (In the formula, R ⁴⁶ 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, the following compounds are preferable in consideration of availability of raw materials, easiness of removing excess siloxane, and compatibility of the component (A) with the polymer.

[0160]

[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. 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 and heating the two components, but a hydrosilylation catalyst can be added to accelerate the reaction. 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.

Further, the transition metal catalyst is not particularly limited, and examples thereof include platinum solid, alumina, silica, carbon black or the like in which platinum solid is dispersed, 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 it is preferable to use it in the range of 10 ^-1 to 10 ^-8 mol, preferably 10 ^-3 to 10 ^-6 mol, per 1 mol of the alkenyl group of the vinyl polymer. Good to use. If it is less than 10 ^-8 mol, curing will not proceed sufficiently. Moreover, since the hydrosilylation catalyst is expensive, 10 ^-1 m
It is preferable not to use more than ol.

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. 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
Examples thereof include polyvalent isocyanate compounds having two or more isocyanate groups in one molecule, aminoplast resins such as methylolated melamine and its alkyl ethers or low condensation products, polyfunctional carboxylic acids and halides thereof. 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.

The crosslinking reaction 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 anion-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 monomer include (meth) acrylate-based monomers, cyclic acrylates, and 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.

[0169]

[Chemical 10]

[0170]

[Chemical 11]

[0171]

[Chemical 12]

[0172]

[Chemical 13]

[0173]

[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.

As the polyfunctional monomer, neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate and bisphenol A are used.
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, and 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, fluorein, 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

Further, 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 added is not particularly limited, since it is sufficient to slightly photofunctionalize the system, but 0.001 to 10 parts by weight relative to 100 parts by weight of the polymer of this composition. Is preferred.

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.

As a method of crosslinking the polymer having a polymerizable carbon-carbon double bond, it is preferable to use 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 an azo initiator, a peroxide, a persulfate, and a redox initiator.

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 ° C. to 250 ° C., although it varies depending on the type of thermal initiator, polymer, compound added and the like. ℃ is preferable, 70 ℃
It is more preferably within the range of to 200 ° C. The curing time varies depending on the polymerization initiator, the monomer, the solvent, the reaction temperature, etc. used, but it is usually in the range of 1 minute to 10 hours. <Plasticizer> In the curable composition of the present invention, various plasticizers are used as necessary. The plasticizer is not particularly limited, but for the purpose of adjusting physical properties and properties, for example, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate; dioctyl adipate , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylricinoleate; diethylene glycol dibenzoate
Polyethylene glycol esters such as triethylene glycol dibenzoate and pentaerythritol ester; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; polystyrenes such as polystyrene and poly-α-methylstyrene Polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene glycol, polypropylene glycol, polytetramethylene glycol And other polyether polyols and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols into ester groups, ether groups, etc .; Soybean oil, epoxy plasticizers such as benzyl epoxystearate; dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid, and 2 such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol Polyester-based plasticizers obtained from polyhydric alcohols; vinyl-based polymers obtained by polymerizing vinyl-based monomers such as acrylic plasticizers by various methods are used alone or in combination of two or more. But you can
It is not always necessary. It should be noted that these plasticizers can be added at the time of polymer production.

The acrylic plasticizer described above is not particularly limited, and examples thereof 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-59-62).
07, Japanese Patent Publication No. 5-58005, Japanese Patent Laid-Open No. 1-31352
2, 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).

The amount of the plasticizer used is not limited, but is 150 parts by weight or less, preferably 120 parts by weight or less, and more preferably 100 parts by weight or less with respect to 100 parts by weight of the vinyl polymer. 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> The filler that can be mixed is not particularly limited, but may be used in combination to the extent that the effect of the carbon black of the present invention is not impaired. The filler is not particularly limited, wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, chaff powder, graphite, diatomaceous earth, clay, fumed silica, precipitated silica Reinforcing fillers such as crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid; ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide,
Bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white,
Fillers such as zinc dust and shirasu balloons; fibrous fillers such as asbestos, glass fibers and filaments, and the like. Among these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, calcium carbonate, titanium oxide, talc and the like are preferable. Especially when it is desired to obtain a cured product having high strength with these fillers, mainly fumed silica, precipitated silica,
A filler selected from silicic acid anhydride, hydrous silicic acid, surface-treated fine calcium carbonate, crystalline silica, fused silica, calcined clay, clay, activated zinc white, and the like can be added.
When it is desired to obtain a cured product having a low strength and a large elongation, a filler mainly selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. 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 breaking strength of the cured product,
The effect of improving the elongation at break, the adhesiveness and the weather-resistant adhesiveness becomes greater. 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,
Examples thereof include fatty acids such as palmitic acid, stearic acid, behenic acid, and oleic acid, 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.
When it exceeds the weight%, the storage stability of the curable composition may decrease. <Addition amount> When the filler is used, the addition amount may be such that the effect of carbon black is not impaired. The fillers may be used alone or in combination of two or more. <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.

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. <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, metal soaps such as calcium stearate, aluminum stearate, barium stearate, and the like. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. <Antioxidant> An antioxidant may be added to the curable composition of the present invention, if necessary. Various kinds of antioxidants are known, and they are described in, for example, "Antioxidant Handbook" issued by Taisei Co., Ltd., "Degradation and Stabilization of Polymer Materials" (235-242) issued by CMC. There are a variety of things, including but not limited to.

For example, MARK PEP-36, MAR
Thioethers such as K AO-23 (all of which are manufactured by ADEKA A-GAS CHEMICAL CO., LTD.), Irgafos38, Irgaf
Examples thereof include phosphorus-based antioxidants such as os168 and IrgafosP-EPQ (all of which are manufactured by Nippon Ciba Geigy). 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.

In terms 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 antioxidant may be used in combination with a light stabilizer which will be described later, and when used in combination, the effect can be further enhanced.
Particularly, heat resistance may be improved, which is particularly preferable. Tinuvin C35 premixed with antioxidant and light stabilizer
3, TINUVIN B75 (all of which are manufactured by Japan Ciba Geigy) or the like may be used.

The amount of the antioxidant used is 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, the effect is not so different and it is economically disadvantageous. <Light Stabilizer> The curable composition of the present invention includes
You may add a light stabilizer as needed. Various types of light stabilizers are known, and for example, they are described in "Handbook of Antioxidants" published by Taisei Co., Ltd., "Degradation and Stabilization of Polymer Materials" (235-242), published by CMC. There are a variety of things, including but not limited to.

Although not particularly limited, among the light stabilizers, an ultraviolet absorber is preferred, and specifically, tinuvin P, tinuvin 234, tinuvin 320, tinuvin 32.
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 benzoate compounds and the like.

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, 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 thus is not particularly limited, but may be used in combination, and it is preferable to use in combination.

The light stabilizer may be used in combination with the above-mentioned antioxidant, and by using the light stabilizer in combination, the effect can be further enhanced.
Particularly, weather resistance may be improved, which is particularly preferable. Tinuvin C35 premixed with light stabilizer and antioxidant
3, TINUVIN B75 (all of which are manufactured by Japan Ciba Geigy) or the like may be used.

The amount of the light stabilizer used is the vinyl polymer 10
It is preferably in the range of 0.1 to 10 parts by weight with respect to 0 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, the effect is not so different and it is economically disadvantageous. Other Additives Various additives may be added to the curable composition of the present invention, if necessary, for the purpose of adjusting various 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 compounding ingredients are previously compounded and hermetically sealed and then cured by the moisture in the air after the construction, or as a curing agent, a separate curing catalyst, You may mix | blend components, such as a filler, a plasticizer, and water, and adjust it as a two-component type which mixes this compounding material and a polymer composition before use. <Mechanical Properties of Cured Product> Although not particularly limited, the curable composition of the present invention is preferably a curable composition having a breaking strength of 0.8 MPa or more when the cured product obtained by curing the curable composition is 1 A curable composition having a pressure of 0.2 MPa or more is more preferable. Moreover, although not particularly limited, a curable composition having an elongation at break of 50% or more is preferable, and a curable composition having an elongation at break of 100% or more is more preferable.

The curable composition of the present invention is not particularly limited, but the reinforcing effect of the addition of the carbon black of the present invention exhibits a breaking strength of 1.5 times or more as compared to when it is not added. It is preferable that the curable composition is a curable composition exhibiting a doubling ratio. <Use> The curable composition of the present invention is not limited,
Sealing materials for elastic sealing materials for construction and sealing materials for double glazing, electrical / electronic component materials such as solar cell backside encapsulation materials, electrical insulating materials such as electric wire / cable insulation coating materials, adhesives, adhesives, Elastic adhesives, paints, powder paints, coating materials, foams, potting materials for electric and electronic use, films, gaskets, casting materials, artificial marble,
Various molding materials, as well as anticorrosion and waterproofing of meshed glass and laminated glass end faces (cut parts), automobile parts, electric parts,
It can be used for various purposes such as various machine parts and sealing materials.

[0212]

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, two GPC columns packed with polystyrene cross-linked gel (shodex GPC K-80
2.5; Showa Denko KK) (shodex GPC
K-804; Showa Denko KK)
Chloroform was used as the GPC solvent.

Further, in this example and the comparative example, (a)
The stress change rate (%) at 50% stretching of the cured product, (b) modulus change rate (%), and (c) breaking elongation change rate (%) are determined as follows. (B) Rate of change in stress when the cured product is stretched by 50% (%) =
[(P−Q) / Q] × 100 Here, Q is a dumbbell test piece (2 (1 / (1)) obtained by punching out the sheet-like cured product obtained in Examples 1 to 15.
3) No. 3) stress at 50% stretching, and 1 of Comparative Example 2
Dumbbell test pieces (2 (1
/ 3) type) stress at 50% stretching. Where P
Is the dumbbell test piece (2 (1/3) type) 150
The stress at the time of 50% stretching of the ones heated at 70 ° C. for 70 hours [Examples 16 to 27 below] and at 150 ° C. of Comparative Example 2 70
Dumbbell test piece after heating for 2 hours (2 (1/3) type)
Is the stress at 50% stretching. (B) Modulus change rate (%) = [(R−S) / S] ×
100 Here, S is a dumbbell test piece (2 (1 / (1)) obtained by punching out the sheet-like cured product obtained in Example 1 and Comparative Example 1.
3) No. 3) is the stress (M50) at 50% stretching. Here, R is 5 of the dumbbell test piece of Example 28 and Comparative Example 3 after being immersed in engine oil at 150 ° C. for 70 hours.
It is the stress (M50) at 0% stretching. (C) Breaking elongation change rate (%) = [(T−U) / U] × 1
00 Here, U is used for the measurement of the rate of change (%) in stress at the time of 50% stretching of the (a) cured product and (b) the rate of change in modulus (b) before heating test or to engine oil. It is the breaking elongation of the dumbbell test piece (No. 2 (1/3) type) before the immersion test. Here, T is used for the measurement of the stress change rate (%) at the time of 50% stretching of the (a) cured product, and (b) modulus change rate (%) after heating or after immersion in engine oil. It is the breaking elongation of the dumbbell test piece (No. 2 (1/3) type). (Production Example 1) CuBr (36.02 g, 0.251) was placed in a 10 L separable flask equipped with a reflux tube and a stirrer.
(1 mol) was charged, and the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (618 mL) was added, and the temperature in an oil bath was 70 ° C.
And stirred for 15 minutes. Butyl acrylate (360
mL, 2.51 mol), ethyl acrylate (500 m
L, 4.62 mol), 2-methoxyethyl acrylate (375 mL, 2.91 mol), diethyl 2,5-dibromoadipate (150.68 g, 0.419 mo).
l), pentamethyldiethylenetriamine (2.18 m
L (1.81 g, 10.46 mmol) (hereinafter referred to as triamine) was added to start the reaction. While heating and stirring at 70 ° C., a mixed solution of butyl acrylate (1440 mL), ethyl acrylate (2002 mL), and 2-methoxyethyl acrylate (1498 mL) was continuously added dropwise over 210 minutes. Triamine (7.63 mL, 6.33 g, 36.5 mmol) was added during the dropping of the monomer. 330 minutes after the start of the reaction, 1,7-octadiene (1236 mL, 922 g, 8.37 mol),
Triamine (26.16 mL, 21.71 g, 0.12
5 mol) was added, and the mixture was continuously heated and stirred at 70 ° C. for 250 minutes.

The reaction mixture was diluted with toluene, passed through an activated alumina column, and the volatile matter was distilled off under reduced pressure to obtain an alkenyl-terminated copolymer {alkenyl-terminated poly (butyl acrylate, ethyl acrylate, methoxy acrylate) Ethyl) copolymer: copolymer [1]} was obtained.

In a 10 L separable flask equipped with a reflux tube, the copolymer [1] (2.87 kg) and potassium acetate (79.
57 g) and N, N-dimethylacetic acid amide (2.9 L) were charged, and the mixture was heated with stirring at 100 ° C. for 8 hours under a nitrogen stream. After removing N, N-dimethylacetamide under heating and reduced pressure,
Diluted with toluene. Solids insoluble in toluene (KBr
And excess potassium acetate) was filtered through an activated alumina column. A volatile component of the filtrate was distilled off under reduced pressure to obtain a copolymer [2].

In a 10 L separable flask equipped with a reflux tube, the copolymer [2] (2.87 kg) and acidic aluminum silicate (14
3g, Kyowa Chemical, Kyoward 700SL), basic aluminum silicate (287g, Kyowa Chemical, Kyoward 50)
0 SH) and xylene (0.57 L) were charged, and the mixture was heated with stirring at 130 ° C. for 5 hours under a nitrogen stream. After removing the aluminum silicate by filtration, the toluene of the filtrate was distilled off under reduced pressure to obtain a vinyl group-terminated copolymer (copolymer [3]).
The number average molecular weight of the obtained copolymer was 17,000 as measured by GPC (polystyrene conversion), and the molecular weight distribution was 1.16.
Met. The average number of vinyl groups introduced per molecule of the copolymer was determined by ¹ H NMR analysis to be about 2.2.

Copolymer [3] (71
8.80 g), dimethoxymethylhydrosilane (27.
55 mL, 0.223 mol), methyl orthoformate (8.14 mL, 0.074 mmol), and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of 0-valent platinum were charged. However, the amount of platinum catalyst used is 5 × 1 in molar ratio with respect to the alkenyl group of the copolymer.
It was set to 0 ^-4 equivalent. The reaction mixture was heated at 100 ° C. for 4 hours, and the volatile matter of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated copolymer (copolymer [4]). The number average molecular weight of the obtained copolymer was 20,000 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 the copolymer was 2.1 as determined by ¹ H NMR analysis. Example 1 100 parts of the polymer [4] obtained in Production Example 1, 50 parts of furnace carbon black (N762: Showa Cabot) and an acrylic plasticizer (UP-1020:
Toagosei) 40 parts, antioxidant (Irganox 101)
0) 3 parts were mixed and further thoroughly mixed with 3 paint rolls, and then cured with 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) for 2 days in a room, and then at 50 ° C. for 3 days for curing and curing. Then, a sheet-like cured product having a thickness of about 2 mm was obtained. (Example 2) 50 parts of furnace carbon black (F200: Asahi carbon), 40 parts of an acrylic plasticizer (UP-1020: Toagosei Co., Ltd.), 100 parts of the polymer [4] obtained in Production Example 1 and antioxidant Agent (Irganox 1010)
After mixing 3 parts and further thoroughly mixing using 3 rolls of paint, about 2 mm was prepared in the same manner as in Example 1 using 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate).
A thick sheet sheet-like cured product was obtained. (Example 3) 100 parts of the polymer [4] obtained in Production Example 1, 50 parts of furnace carbon black (# 70: Asahi carbon), 40 parts of an acrylic plasticizer (UP-1020: Toagosei), and oxidation Inhibitor (Irganox 1010)
After mixing 3 parts and further thoroughly mixing using 3 rolls of paint, about 2 mm was prepared in the same manner as in Example 1 using 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate).
A thick sheet sheet-like cured product was obtained. (Example 4) 100 parts of the polymer [4] obtained in Production Example 1 was mixed with 50 parts of furnace carbon black (HTC # SL: Nikko Carbon) and an acrylic plasticizer (UP-102).
0: Toagosei Co., Ltd. 40 parts, antioxidant (Irganox 1
010) 3 parts were mixed and further thoroughly mixed using a three-roll paint roll, and then 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used to prepare a sheet having a thickness of about 2 mm in the same manner as in Example 1. A cured product was obtained to obtain a sheet-shaped cured product. (Example 5) 100 parts of the polymer [4] obtained in Production Example 1, 50 parts of furnace carbon black (N550-G: Showa Cabot) and an acrylic plasticizer (UP-102) were used.
0: Toagosei Co., Ltd. 40 parts, antioxidant (Irganox 1
010) 3 parts were mixed and further thoroughly mixed using a 3-roll paint roll, and then a sheet having a thickness of about 2 mm was prepared in the same manner as in Example 1 using 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate). A cured product was obtained. (Example 6) 100 parts of the polymer [4] obtained in Production Example 1, 50 parts of furnace carbon black (SEAST S: Tokai Carbon) and an acrylic plasticizer (UP-1020:
Toagosei) 40 parts, antioxidant (Irganox 101)
0) 3 parts were mixed and further thoroughly mixed using 3 paint rolls, and then 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used to prepare about 2 parts in the same manner as in Example 1.
A sheet-shaped cured product having a thickness of mm was obtained. (Example 7) 100 parts of the polymer [4] obtained in Production Example 1, 50 parts of furnace carbon black (SEAST 3: Tokai Carbon) and an acrylic plasticizer (UP-1020:
Toagosei) 40 parts, antioxidant (Irganox 101)
0) 3 parts were mixed and further thoroughly mixed using 3 paint rolls, and then 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used to prepare about 2 parts in the same manner as in Example 1.
A sheet-shaped cured product having a thickness of mm was obtained. (Example 8) In 100 parts of the polymer [4] obtained in Production Example 1, 50 parts of furnace carbon black (MA600: Mitsubishi carbon) and an acrylic plasticizer (UP-1020:
Toagosei) 40 parts, antioxidant (Irganox 101)
0) 3 parts were mixed and further thoroughly mixed using 3 paint rolls, and then 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used to prepare about 2 parts in the same manner as in Example 1.
A sheet-shaped cured product having a thickness of mm was obtained. (Example 9) 100 parts of the polymer [4] obtained in Production Example 1, 50 parts of furnace carbon black (MA220: Mitsubishi carbon) and an acrylic plasticizer (UP-1020:
Toagosei) 40 parts, antioxidant (Irganox 101)
0) 3 parts were mixed and further thoroughly mixed using 3 paint rolls, and then 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used to prepare about 2 parts in the same manner as in Example 1.
A sheet-shaped cured product having a thickness of mm was obtained. (Example 10) Polymer [4] 100 obtained in Production Example 1
50 parts of furnace carbon black (# 60UG: Asahi Carbon) and acrylic plasticizer (UP-1020:
Toagosei) 40 parts, antioxidant (Irganox 101)
0) 3 parts were mixed and further thoroughly mixed using 3 paint rolls, and then 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used to prepare about 2 parts in the same manner as in Example 1.
A sheet-shaped cured product having a thickness of mm was obtained. (Example 11) Polymer [4] 100 obtained in Production Example 1
50 parts of furnace carbon black (HTC # SH: Showa Cabot) and acrylic plasticizer (UP-10)
20: Toagosei Co., Ltd.) 40 parts, and an antioxidant (Irganox 1010) 3 parts are mixed and further thoroughly mixed by using three paint rolls, and then 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) is used. Then, in the same manner as in Example 1, a sheet-shaped cured product having a thickness of about 2 mm was obtained. (Example 12) Polymer [4] 100 obtained in Production Example 1
50 parts of furnace carbon black (SEAST V: Tokai Carbon) and acrylic plasticizer (UP-102)
0: Toagosei Co., Ltd. 40 parts, antioxidant (Irganox 1
010) 3 parts were mixed and further thoroughly mixed using a 3-roll paint roll, and then a sheet having a thickness of about 2 mm was prepared in the same manner as in Example 1 using 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate). A cured product was obtained. (Example 13) Polymer [4] 100 obtained in Production Example 1
50 parts of furnace carbon black (# 66: Asahi carbon), 40 parts of acrylic plasticizer (UP-1020: Toagosei), antioxidant (Irganox 1010).
After mixing 3 parts and further thoroughly mixing using 3 rolls of paint, about 2 mm was prepared in the same manner as in Example 1 using 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate).
A thick sheet-like cured product was obtained. (Example 14) Polymer [4] 100 obtained in Production Example 1
50 parts of furnace carbon black (SEAST S: Tokai Carbon) and acrylic plasticizer (UP-102)
0: Toagosei 20 parts, antioxidant (Irganox 1
010) 3 parts were mixed and further thoroughly mixed by using three paint rolls, and then the mixture was thoroughly dehydrated, and 2 parts vinyltrimethoxysilane (A-171: Nippon Unicar) as a dehydrating agent in an anhydrous state, adhesiveness 2 parts of aminopropyl methoxysilane (A-1120: Nippon Unicar) as an imparting agent,
Tetravalent Sn catalyst (dibutyltin diacetylacetonate) 2
Parts were added and mixed to obtain a one-part formulation. Thereafter, the one-pack composition was stored at room temperature for one week, and then a sheet-like cured product having a thickness of about 2 mm was obtained in the same manner as in Example 1. The one-pack formulation did not cure even after storage for one week at room temperature and had sufficient workability. (Example 15) Polymer [4] 100 obtained in Production Example 1
50 parts of furnace carbon black (SEAST V: Tokai Carbon) and acrylic plasticizer (UP-102)
0: Toagosei 20 parts, antioxidant (Irganox 1
010) 3 parts were mixed and further thoroughly mixed using 3 paint rolls, then the mixture was thoroughly dehydrated, and 2 parts vinyltrimethoxysilane (A-171: Nippon Unicar) as a dehydrating agent in an anhydrous state, adhesiveness 2 parts of aminopropyl methoxysilane (A-1120: Nippon Unicar) as an imparting agent,
Tetravalent Sn catalyst (dibutyltin diacetylacetonate) 2
Parts were added and mixed to obtain a one-part formulation. Thereafter, the one-pack composition was stored at room temperature for one week, and then a sheet-like cured product having a thickness of about 2 mm was obtained in the same manner as in Example 1. The one-pack formulation did not cure even after storage for one week at room temperature and had sufficient workability. (Comparative Example 1) A sheet-like cured product having a thickness of about 2 mm was obtained in the same manner as in Example 1 except that carbon black was not added to the polymer [4] obtained in Production Example 1. (Evaluation 1) In each of Examples 1 to 15 and Comparative Example 1, a (2 (1/3) type) dumbbell test piece was punched from the sheet-shaped cured product, and a tensile test of the cured product was performed. The tensile test was carried out using an autograph manufactured by Shimadzu (measurement condition: 23
C, 200 mm / min). The cured products of Examples 1 to 12 with respect to the cured product of Comparative Example 1 did not impair break elongation,
The breaking strength was more than double.

[0220]

[Table 1] (Example 16) The dumbbell test piece (No. 2 (1/3) type) obtained in Example 1 was heated at 150 ° C for 70 hours. (Example 17) The dumbbell test piece (No. 2 (1/3) type) obtained in Example 2 was heated at 150 ° C for 70 hours. (Example 18) The (2 (1/3) type) dumbbell test piece obtained in Example 3 was heated at 150 ° C for 70 hours. (Example 19) The dumbbell test piece (No. 2 (1/3) type) obtained in Example 4 was heated at 150 ° C for 70 hours. (Example 20) The dumbbell test piece (No. 2 (1/3) type) obtained in Example 5 was heated at 150 ° C for 70 hours. (Example 21) The dumbbell test piece (No. 2 (1/3) type) obtained in Example 6 was heated at 150 ° C for 70 hours. (Example 22) The (2 (1/3) type) dumbbell test piece obtained in Example 7 was heated at 150 ° C for 70 hours. (Example 23) The (2 (1/3) type) dumbbell test piece obtained in Example 8 was heated at 150 ° C for 70 hours. (Example 24) The (2 (1/3) type) dumbbell test piece obtained in Example 9 was heated at 150 ° C for 70 hours. (Example 25) Obtained in Example 10 (type 2 (1/3))
The dumbbell test piece was heated at 150 ° C. for 70 hours. (Example 26) Obtained in Example 11 (2 (1/3) type)
The dumbbell test piece was heated at 150 ° C. for 70 hours. (Example 27) Obtained in Example 12 (type 2 (1/3))
The dumbbell test piece was heated at 150 ° C. for 70 hours. (Comparative Example 2) 100 parts of the polymer [4] obtained in Production Example 1 was mixed with 10 parts of calcium carbonate (Shiragaku CCR: manufactured by Shiraishi Kogyo Co., Ltd.).
0 parts and acrylic plasticizer (UP-1020: Toagosei)
40 parts and 3 parts of antioxidant (Irganox 1010) were mixed, and further thoroughly mixed by using three paint rolls, and then a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used, and the same procedure as in Example 1 was carried out. A sheet-shaped cured product was obtained by punching out a (2 (1/3) type) dumbbell test piece from the sheet-shaped cured product, and heated at 150 ° C. for 70 hours. (Evaluation 2) Tensile tests were performed on the dumbbell test pieces of Examples 17 to 27 and Comparative Example 2, and the values after 50 hours at 150 ° C. for 50 hours.
The rate of change in stress (M50) during% stretching and the rate of change in elongation at break were determined. Compared to Comparative Example 2, Examples 17 to 27 have 150
The rates of change in modulus and elongation after heating at 70 ° C. for 70 hours were low.

[0221]

[Table 2] (Example 28) Engine oil (commercial name GEOMA, SJ grade, 5W-30: JOMO) obtained by heating the (2 (1/3) type) dumbbell test piece obtained in Example 1 to 150 ° C.
Manufactured) and soaked for 70 hours. (Comparative Example 3) Engine oil (commercial name GE) obtained by heating the (2 (1/3) type) dumbbell obtained in Comparative Example 1 to 150 ° C.
OMA, SJ grade, 5W-30: made by JOMO) and soaked for 70 hours. (Evaluation 3) A tensile test was performed on the dumbbell test pieces of Example 28 and Comparative Example 3, and the rate of change in stress (M50) and the rate of elongation at break at 50% stretching after immersion in engine oil for 70 hours at 150 ° C. were evaluated. I asked. In comparison with Comparative Example 3, Example 2
No. 8 had a low rate of change in modulus and elongation after immersion in engine oil for 70 hours at 150 ° C.

[0222]

[Table 3] From the above results, it was found that by using carbon black, it is possible to obtain a curable composition in which good heat resistance and oil resistance are not significantly affected and the breaking strength of the cured product is improved.

[0223]

INDUSTRIAL APPLICABILITY According to the present invention, by adding carbon black to a vinyl polymer having a crosslinkable functional group, the breaking strength of a cured product is improved without significantly affecting good heat resistance and oil resistance. A curable composition is obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 BC041 BC101 BD121 BG021                       BG101 BQ001 DA036 FD342                       FD347

Claims (36)

[Claims] 1. A curable composition comprising the following two components: (A1) vinyl polymer (B1) furnace carbon black having at least one crosslinkable functional group as an essential component. 2. The following two components: (A2) At least one crosslinkable functional group, the cured product of which has an oil resistance of 3 for land use specified in JIS K 2215.
A vinyl polymer that exceeds the cured product of a butyl acrylate homopolymer having the same structure in any one item of the immersion test of JIS K 6258 with respect to the lubricating oil of species 5. (B2) A curable composition containing carbon black as an essential component. 3. A curable composition comprising the following three components: (A) a vinyl polymer having at least one crosslinkable functional group (B2) carbon black (C) an adhesiveness-imparting agent. 4. The vinyl polymer has a molecular weight distribution of 1.8.
The curable composition according to any one of claims 1 to 3, which is less than. 5. The main chain of the vinyl polymer is a monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. Claim 1 in the case of being mainly produced by polymerization
4. The curable composition according to claim 4. 6. The curable composition according to any one of claims 1 to 5, wherein the vinyl polymer is a (meth) acrylic polymer. 7. The curable composition according to any one of claims 1 to 6, wherein the vinyl polymer is an acrylic polymer. 8. The curable composition according to claim 7, wherein the vinyl-based polymer is an acrylic acid ester-based polymer. 9. The curable composition according to claim 8, wherein the vinyl-based polymer is an ethyl acrylate-based polymer. 10. The crosslinkable functional group of the vinyl polymer is
It is a crosslinkable silyl group, The curable composition as described in any one of Claims 1-9 characterized by the above-mentioned. 11. The crosslinkable functional group of the vinyl polymer is
It is an alkenyl group, The curable composition as described in any one of Claims 1-9 characterized by the above-mentioned. 12. The crosslinkable functional group of the vinyl polymer is
It is a hydroxyl group, The curable composition as described in any one of Claims 1-9 characterized by the above-mentioned. 13. The crosslinkable functional group of the vinyl polymer is
It is an amino group, The curable composition as described in any one of Claims 1-9 characterized by the above-mentioned. 14. The crosslinkable functional group of the vinyl polymer is
The curable composition according to any one of claims 1 to 9, which is a group having a polymerizable carbon-carbon double bond. 15. The crosslinkable functional group of the vinyl polymer is
It is an epoxy group, The curable composition in any one of Claims 1-9 characterized by the above-mentioned. 16. The curable composition according to claim 1, wherein the vinyl polymer main chain is produced by a living radical polymerization method. 17. The curable composition according to claim 16, wherein the living radical polymerization is atom transfer radical polymerization. 18. The atom transfer radical polymerization is characterized by using as a catalyst a complex selected from transition metal complexes having a central metal of an element of Group 7, 8, 9, 10, or 11 of the periodic table. The curable composition according to claim 17. 19. The curable composition according to claim 18, wherein the metal complex used as a catalyst is a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes. 20. The curable composition according to claim 19, wherein the metal complex used as a catalyst is a copper complex. 21. The vinyl polymer has at least one crosslinkable functional group, and the cured product thereof has oil resistance according to JIS.
In any one item of the immersion test of JIS K 6258 with respect to the land 3 type 5 lubricating oil specified in K 2215, the oil resistance of a polymer cured product in which the repeating unit of the main chain is changed to butyl acrylate alone 21. The curable composition according to any one of claims 1 to 20, which is more than a composition. 22. The oil resistance of the cured product is JIS K 2
JI for land type 3 No. 5 lubricating oil specified in 215
The curable composition according to claim 21, wherein a mass change rate before and after the immersion is 50% or less in an immersion test of SK 6258. 23. A cured product JIS K 6 for land 3 type 5 lubricating oil specified in JIS K 2215.
In the immersion test of No. 258, a vinyl polymer whose mass change before and after immersion is smaller than a cured product of a polymer in which the repeating unit of its main chain is changed to butyl acrylate alone is an essential component. 23. The curable composition according to claim 22. 24. JIS K 6 for a land-use type 3 No. 5 lubricating oil specified in JIS K 2215 of a cured product
In the immersion test of No. 258, the volume change before and after the immersion is smaller than that of a cured product of a polymer in which the repeating unit of the main chain is changed to butyl acrylate alone, as an essential component. The curable composition according to any one of claims 1 to 20. 25. The breaking strength of the cured product of the curable composition is 0.8 MPa or more.
4. The curable composition according to claim 4. 26. The curable composition according to claim 25, wherein the cured product of the curable composition has a breaking strength of 1.2 MPa or more. 27. The curable composition according to claim 1, wherein the cured product of the curable composition has a breaking elongation of 50% or more. 28. The curable composition according to claim 27, wherein the cured product of the curable composition has an elongation at break of 100% or more. 29. The carbon black contained in the curable composition, the breaking strength of the cured product is 1.5 times or more as compared with the one not containing it. The curable composition according to any one of 1. 30. The curable composition according to claim 29, wherein the curable composition contains carbon black, and the breaking strength of the cured product is at least twice as high as that of the composition without the curable composition. Sex composition. 31. When the curable composition contains carbon black and an adhesiveness-imparting agent, breaking strength of the cured product is 1.5 times or more as compared with that of the curable composition. The curable composition according to any one of claims 1 to 28. 32. The carbon black and the adhesion-imparting agent are contained in the curable composition, so that the breaking strength of the cured product is at least twice as high as that of the composition without the curable composition. The curable composition according to any one of 1 to 31. 33. A cured product of the curable composition is prepared in air 1
By heating at 50 ° C for 70 hours, 5
33. The curable composition according to any one of claims 1 to 32, wherein a change rate of the stress at 0% stretching is 150% or less as compared with that before heating to 150 ° C. 34. A cured product of the curable composition is prepared in air 1
By heating at 50 ° C for 70 hours, 5
34. The curable composition according to claim 33, wherein the change rate of the stress at 0% stretching is 100% or less as compared with that before heating to 150 ° C. 35. A cured product of a curable composition is dried in air at 1
By heating at 50 ° C for 70 hours, the breaking elongation of the cured product is within the range of -20 to 60% as compared with that before heating at 150 ° C. 34. The curable composition according to any one of items 34 to 34. 36. A cured product of a curable composition is dried in air at 1
By heating to 50 ° C., the elongation at break of the cured product is −10 as compared with that before heating to 150 ° C.
36. The curable composition according to claim 35, which is within 50%.