JP2003082192A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition comprising a vinylic polymer bearing a crosslinkable functional group, which composition is more inexpensive than that obtained by using a conventional filler and gives a cured product without lowering tensile characteristics while permitting weight-saving of a curable composition. SOLUTION: This curable composition comprises the vinylic polymer (I) bearing at least one crosslinkable functional group and a fine hollow body (II). The composition solves the problems above, permits improvement in stringing (spatula cuttability) of a compound containing the same and is expected to bring about heat insulation effects, soundproofing effects, endothermic effects, and the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, it relates to a curable composition containing a vinyl polymer having at least one crosslinkable functional group and a micro hollow body.

[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,
Foams, potting agents for electrical and electronic products, films, gaskets, casting materials, various molding materials, and rustproof / waterproof encapsulants for meshed glass and laminated glass end faces (cut parts),
It can be used for various purposes such as automobile parts, electrical parts, and various machine parts.

The curable composition of this polymer used for such various uses may be mixed with a filler for the purpose of cost reduction or the like depending on the use. However, the addition of the filler may cause problems such as an increase in the weight of the cured product and a cost reduction not expected. Further, depending on the filler, mechanical properties such as tensile properties of the cured product may be deteriorated. In recent years, due to problems such as transportability and workability, it has been desired that the curable composition be made lighter in weight (lower in specific gravity) without significantly affecting physical properties such as tensile properties.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to be less expensive than the case of using a conventional filler and to realize a reduction in weight of a curable composition while not lowering the tensile properties of the cured product. A curable composition having a vinyl polymer having a crosslinkable functional group is provided.

[0011]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest studies in view of the above-mentioned situation, and as a result, found that the above-mentioned problems can be solved by using a minute hollow body as a filler.

That is, according to the present invention, the vinyl polymer (I) having at least one crosslinkable functional group and the micro hollow body (I) are used.
A curable composition comprising I).

The main chain of the vinyl polymer (I) is not particularly limited, but comprises a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer. It is preferably produced mainly by polymerizing a monomer selected from the group, more preferably a (meth) acrylic monomer, further preferably an acrylic monomer, more preferably an acrylic ester monomer, and most preferably a butyl acrylate monomer. It is preferably produced by polymerization using a monomer.

The main chain of the vinyl polymer (I) is preferably, but not limited to, produced by living radical polymerization, more preferably atom transfer radical polymerization. Further, atom transfer radical polymerization includes, but is not limited to, Groups 7, 8, 9 of the Periodic Table,
It is preferable to use a complex selected from transition metal complexes having a Group 10 or Group 11 element as a central metal as a catalyst, and copper,
A complex selected from the group consisting of nickel, ruthenium, or iron complexes is more preferable, and a copper complex is particularly preferable.

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

The crosslinkable functional group of the vinyl polymer (I) is not limited, but includes crosslinkable silyl group, alkenyl group, hydroxyl group, amino group, polymerizable carbon-carbon double bond,
Epoxy groups and the like are preferred.

The position of the crosslinkable functional group of the vinyl polymer (I) is not limited, but the terminal is preferable. Other than that, the main chain may have the same functional group, but it is preferable to have the functional group only at the terminal when rubber elasticity is required for the crosslinked cured product.

The number of crosslinkable functional groups of the vinyl polymer (I) is not particularly limited, but in order to obtain a cured product having higher crosslinkability, the average number is 1 or more, preferably 1.2. As described above, more preferably 1.5 or more.

The micro hollow body (II) has a true specific gravity of 1.0 g / c.
It is preferably m ³ or less. Further, the surface thereof is preferably coated with an inorganic fine powder so as to be easily compatible with the resin constituting the curable composition and to exert its effect, and further, calcium carbonate, surface-treated calcium carbonate, titanium oxide. It is preferably coated with an inorganic compound consisting of at least one selected from the group consisting of silicon oxide, talc, clay and carbon black. Above all, it is preferable to use a micro hollow body coated with calcium carbonate which is surface-treated with a fatty acid ester or the like, because the curable composition can further impart thixotropy. On the other hand, it is easily compatible with the resin constituting the curable composition, in order to easily exert its effect, it is preferable that the micro hollow body is an organic polymer, further, vinylidene chloride resin, vinylidene chloride and acrylonitrile and An organic polymer formed from at least one selected from the group consisting of a copolymer of acrylonitrile, a methacrylonitrile, and a terpolymer of vinylidene chloride, acrylonitrile, and divinylbenzene. It is more preferable.

The content of the hollow microparticles (II) is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the vinyl polymer (I). preferable.

By using this micro hollow body, effects such as heat insulation, soundproofing, and heat absorption can be expected. Furthermore,
Formulations using this micro hollow body are stringy (sparing)
Is improved.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a vinyl polymer (I) having at least one crosslinkable functional group and a micro hollow body (I).
A curable composition comprising I), which is less expensive than the case of using a conventional filler, and realizes weight reduction of the curable composition, without deteriorating tensile properties of the cured product. Regarding the curable composition having a vinyl polymer having a crosslinkable functional group, the curable composition of the present invention will be described in detail below. << About Vinyl Polymer (I) >><MainChain> The inventors have heretofore described a vinyl polymer having various crosslinkable functional groups at the polymer terminals, a method 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 (I) of the present invention is not particularly limited, but all the polymers disclosed in the invention exemplified above can be preferably used.

The vinyl-based monomer constituting the main chain of the vinyl-based polymer (I) of the present invention is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
(Meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) Acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl,
Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid-2- Methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (Meta)
2-Aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth)
2-perfluoroethyl acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, (meth) acrylic (Meth) acrylic monomers such as 2-perfluorohexylethyl acid acid, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene,
Aromatic vinyl monomers such as α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; Vinyltrimethoxysilane, vinyltriethoxysilane Silicon-containing vinyl monomers such as; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butyl Maleimide-based monomers such as maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; acrylonite Acrylonitrile monomers such as vinyl chloride and methacrylonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; ethylene, Examples thereof include alkenes such as propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of them may be copolymerized.

The main chain of the vinyl polymer (I) is (meth)
It is preferably produced by mainly polymerizing at least one monomer selected from the group consisting of an acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer. Here, “mainly” means that 50 mol% or more, preferably 70% or more of the monomer units constituting the vinyl polymer (I) are the above-mentioned monomers.

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

The molecular weight distribution of the vinyl polymer (I) of the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is Although not particularly limited,
It is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably It is preferably 1.3 or less. In the GPC measurement of the present invention, chloroform is usually used as the mobile phase, the measurement is carried out 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 (I) in the present invention is not limited, but controlled radical polymerization is preferable, living radical polymerization is more preferable,
Atom transfer radical polymerization is especially preferred. These will be described below. Controlled radical polymerization radical polymerization method is a "general radical polymerization method" in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized by using an azo compound, a peroxide or the like as a polymerization initiator. , A controlled radical polymerization method capable of introducing a specific functional group at a controlled position such as a terminal.

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

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

The "chain transfer agent method" is capable of obtaining a polymer having a high degree of functionalization, 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 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 studied 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 a cobalt porphyrin complex, 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 vinyl monomers are polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the "living radical polymerization method" described above. In addition to the features of the radical polymerization method, it has a halogen, etc., which is relatively advantageous for functional group conversion reactions at the terminal, and has a high degree of freedom in the design of initiators and catalysts. It is more preferable as a method for producing a coalescence. As this atom transfer radical polymerization method, for example, Mat
yjaszewski et al., Journal of American Chemical Society (J. Am. Chem. So
c. ) 1995, 117, 5614, Macromolecules 1995.
28, 7901, Science (Science)
e) 1996, 272, 866 pages, WO96 / 30
421 publication, WO97 / 18247 publication, WO98
/ 01480, WO98 / 40415, or Sawamoto et al., Macromolecules (M
acromolecules) 1995, 28, 1
Page 721, JP-A-9-208616, JP-A-8-
No. 41117 is cited.

In the present invention, which living radical polymerization method is used is not particularly limited, but the atom transfer radical polymerization method is preferable.

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 the vinyl polymer (I) described later, a chain transfer agent. The polymerization using is explained. 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.

As the radical generator, various compounds can be used, but 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.

[0044]

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

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

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

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

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

Specific examples of the organic halide having an alkenyl group represented by the general formula 1 include: XCH ₂ C (O) O (CH ₂ ) _n CH═CH ₂ , H ₃ CC
(H) (X) C (O) O (CH ₂ ) _n CH = CH ₂ , (H ₃
C) ₂ C (X) C (O) O (CH ₂ ) _n CH = CH ₂ , CH
₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n CH = CH
₂ ,

[0050]

[Chemical 2] (In each formula mentioned above, X is chlorine, bromine or iodine, n represents an integer of _{0~20,) XCH 2 C (O} ) O (CH 2) n O (CH 2) m CH = C
H ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (C
H ₂ ) _m CH = CH ₂ , (H ₃ C) ₂ C (X) C (O) O
(CH ₂ ) _n O (CH ₂ ) _m CH = CH ₂ , CH ₃ CH ₂ C
(H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m CH =
CH ₂ ,

[0051]

[Chemical 3] (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH₂-C₆H_Four-(CH₂)_n-CH = C
H₂, O, m, p-CH₃C (H) (X) -C₆H_Four-(C
H₂)_n-CH = CH₂, O, m, p-CH₃CH₂C
(H) (X) -C₆H_Four-(CH₂)_n-CH = CH₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH₂-C₆H
_Four-(CH₂)_n-O- (CH₂)_m-CH = CH₂, O,
m, p-CH₃C (H) (X) -C₆H_Four-(CH₂)_n−
O- (CH₂)_m-CH = CH₂, O, m, p-CH₃CH
₂C (H) (X) -C₆H_Four-(CH₂)_n-O- (CH₂)
_mCH = CH₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-CH
= CH₂, O, m, p-CH₃C (H) (X) -C₆H_Four−
O- (CH₂)_n-CH = CH₂, O, m, p-CH ₃CH
₂C (H) (X) -C₆H_Four-O- (CH₂)_n-CH = C
H₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer from 0 to 20) o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-O-
(CH₂)_m-CH = CH₂, O, m, p-CH₃C (H)
(X) -C₆H_Four-O- (CH₂)_n-O- (CH₂) _m-C
H = CH₂, O, m, p-CH₃CH₂C (H) (X)-
C₆H_Four-O- (CH ₂)_n-O- (CH₂)_m-CH = CH
₂, (In each of the above formulas, X is chlorine, bromine, or iodine.
(Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) Further as an organic halide having an alkenyl group
Examples thereof include compounds represented by 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) R⁶Is a direct bond or a divalent organic group having 1 to 20 carbon atoms
(May contain one or more ether bonds)
Is a direct bond, the halogen-bonded carbon
Vinyl group is bonded to the element,
is there. In this case, carbon-halogenation is caused by adjacent vinyl groups.
R is because the bond is activated.⁸As C (O) O
It is not always necessary to have a group or phenylene group, etc.
It may be a bond. R⁷Is not a direct bond, charcoal
In order to activate the elementary-halogen bond, R⁸As C
(O) O group, C (O) group and phenylene group are preferred.

To specifically exemplify the compound of the general formula 2, CH ₂ ═CHCH ₂ X, CH ₂ ═C (CH ₃ ) CH ₂ X, C
H ₂ ═CHC (H) (X) CH ₃ , CH ₂ ═C (CH ₃ ) C
(H) (X) CH ₃ , CH ₂ = CHC (X) (CH ₃ ) ₂ ,
CH ₂ = CHC (H) (X) C ₂ H ₅ , CH ₂ = CHC
(H) (X) CH ( CH 3) 2, CH 2 = CHC (H)
(X) C ₆ H ₅ , CH ₂ = CHC (H) (X) CH ₂ C
₆ H ₅ , CH ₂ = CHCH ₂ C (H) (X) -CO ₂ R, C
_{H 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R, CH 2
_{= CH (CH 2) 3 C} (H) (X) -CO 2 R, CH 2 = C
_{H (CH 2) 8 C (} H) (X) -CO 2 R, CH 2 = CHC
_{H 2 C (H) (X} ) -C 6 H 5, CH 2 = CH (CH 2) 2 C
_{(H) (X) -C 6} H 5, CH 2 = CH (CH 2) 3 C
_{(H) (X) -C 6} H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group,) and the like, etc. it can.

[0053] Specific examples of a halogenated sulfonyl compound having an alkenyl group, o-, m-, p-CH 2 = CH- (CH 2) n -C 6 H 4 -
_{SO 2 X, o-, m-,} p-CH 2 = CH- (CH 2) n -
O—C ₆ H ₄ —SO ₂ X, (in each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20) and the like.

Organic halogen having the 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 each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 0 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_mSi (OC
H₃)₃, H₃CC (H) (X) C (O) O (CH₂)_nO
(CH₂)_mSi (OCH₃)₃, (H₃C)₂C (X) C
(O) O (CH₂)_nO (CH₂)_mSi (OCH₃)₃, C
H₃CH₂C (H) (X) C (O) O (CH₂)_nO (CH
₂)_mSi (OCH₃)₃, XCH₂C (O) O (CH₂)_n
O (CH₂)_mSi (CH₃) (OCH₃)₂, H₃CC
(H) (X) C (O) O (CH₂)_nO (CH₂)_m-Si
(CH₃) (OCH₃)₂, (H₃C)₂C (X) C (O)
O (CH₂)_nO (CH₂)_m-Si (CH₃) (OCH₃)
₂, CH₃CH ₂C (H) (X) C (O) O (CH₂)_nO
(CH₂)_m-Si (CH₃) (OCH₃)₂, (In each of the above formulas, X is chlorine, bromine, iodine, and n is
1 to 20 integer, m is 0 to 20 integer) o, m, p-XCH₂-C₆H_Four-(CH₂)₂Si (OC
H₃)₃, O, m, p-CH₃C (H) (X) -C₆H_Four−
(CH₂)₂Si (OCH₃)₃, O, m, p-CH₃CH₂
C (H) (X) -C₆H_Four-(CH₂)₂Si (OC
H₃)₃, O, m, p-XCH₂-C₆H_Four-(CH₂)₃S
i (OCH₃)₃, O, m, p-CH₃C (H) (X)-
C₆H_Four-(CH₂)₃Si (OCH₃)₃, O, m, p-C
H₃CH₂C (H) (X) -C₆H_Four-(CH₂)₃Si (O
CH₃)₃, O, m, p-XCH₂-C₆H_Four-(CH₂)₂
-O- (CH₂)₃Si (OCH₃)₃, O, m, p-CH
₃C (H) (X) -C₆H_Four-(CH₂)₂-O- (CH₂)
₃Si (OCH₃)₃, O, m, p-CH₃CH₂C (H)
(X) -C₆H_Four-(CH₂)₂-O- (CH₂)₃Si (O
CH₃)₃, O, m, p-XCH₂-C₆H_Four-O- (C
H₂)₃Si (OCH₃)₃, O, m, p-CH₃C (H)
(X) -C₆H_Four-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃CH₂C (H) (X) -C₆H_Four-O-
(CH₂)₃-Si (OCH₃)₃, O, m, p-XCH₂
-C₆H_Four-O- (CH₂)₂-O- (CH₂)₃-Si (O
CH₃)₃, O, m, p-CH₃C (H) (X) -C₆H_Four
-O- (CH₂)₂-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃CH₂C (H) (X) -C₆H_Four-O-
(CH₂)₂-O- (CH₂)₃Si (OCH₃)₃, (In each of the above formulas, X is chlorine, bromine, or iodine.
And the like.

Examples of the organic halide having a crosslinkable silyl group further 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, Y is if the same) specifically illustrate such _{compounds, (CH 3 O) 3 SiCH} 2 CH 2 C (H) (X) C 6 H 5,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ C (H) (X)
_{C 6 H 5, (CH 3} O) 3 Si (CH 2) 2 C (H) (X) -
CO ₂ R, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₂ C
_{(H) (X) -CO 2} R, (CH 3 O) 3 Si (CH 2) 3
C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -CO 2 R, (CH 3 O) 3 S
_{i (CH 2) 4 C (} H) (X) -CO 2 R, (CH 3 O) 2
_{(CH 3) Si (CH 2} ) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO
₂ R, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₉ C (H)
_{(X) -CO 2 R, (} CH 3 O) 3 Si (CH 2) 3 C
_{(H) (X) -C 6} H 5, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -C 6 H 5, (CH 3 O) 3 Si
_{(CH 2) 4 C (H} ) (X) -C 6 H 5, (CH 3 O) 2 (C
_{H 3) Si (CH 2)} 4 C (H) (X) -C 6 H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, aryl Group, aralkyl group) and the like.

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

[0057]

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

[0058]

[Chemical 5]

[0059]

[Chemical 6] Etc.

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

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

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

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

The atom transfer radical polymerization of the present invention also includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates a radical, for example, Cu (II ′) when Cu (I) is used as a catalyst.
On the other hand, a general radical initiator such as a peroxide is allowed to act, and as a result, an equilibrium state similar to atom transfer radical polymerization is produced (Macromolecule
es 1999, 32, 2872). <Functional group> The crosslinkable functional group of the vinyl polymer (I) is not limited, but a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, a group having a polymerizable carbon-carbon double bond, Epoxy groups and the like are preferred.

All of these crosslinkable functional groups are used / purposed.
You can use them according to your needs. Number of crosslinkable functional groups The number of crosslinkable functional groups of the vinyl polymer (I) is particularly limited.
However, from the viewpoint of curability of the composition and physical properties of the cured product
Therefore, it is preferable to have one or more on average, and more preferable.
It is preferably 1.1 or more and 4.0 or less, more preferably
The number is 1.2 or more and 3.5 or less.Position of crosslinkable functional group The cured product obtained by curing the curable composition of the present invention is rubbery.
When special properties are required, rubber elasticity has a large effect.
Because the molecular weight between the cross-linking points that gives the sound is large, cross-linking
At least one of the functional groups is preferably at the end of the chain.
Good More preferably, all the crosslinkable functional groups have a molecular chain.
It has one at the end.

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 crosslinkable silyl group crosslinkable silyl group of the 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.

The hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a + Σ
The range of b) is preferably 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is 1 or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, a crosslinkable silyl group represented by the general formula 6-Si (R ¹⁰ ) _3-a (Y) _a (6) (wherein R ¹⁰ , Y and a are the same as above) is easily available. Therefore, it is preferable.

Although not particularly limited, a is preferably 2 or more in consideration of curability.

As such a vinyl polymer having a crosslinkable silyl group, a polymer having a hydrolyzable silicon group in which two hydrolyzable groups are bonded per silicon atom is often used. When the adhesive is used, or when it is used at low temperature, etc., especially when a very high curing rate is required, the curing rate is not sufficient, and if the flexibility after curing is desired, the crosslinking density should be adjusted. It must be reduced, and therefore the crosslink density is not sufficient, resulting in stickiness (surface tack).
Sometimes there was. In that case, it is preferable that a is 3 (for example, a trimethoxy functional group).

Further, those having three a's (for example, trimethoxy functional group) have faster curability than those having two (for example, dimethoxy functional group), but storage stability and mechanical properties (elongation, etc.)
As for the two, two may be better, so in order to balance the curability and mechanical properties, 2
One (eg dimethoxy functional group) and three (eg 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) (In the formula, R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) In the general formula 7, R ¹¹ is a hydrogen atom or 1 to 12 carbon atoms.
It is a hydrocarbon group of 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 -CH 3,} -C 6 H 5, -C 6 H 5 (CH 3), -
_{C 6 H 5 (CH 3)} 2, - (CH 2) n -C 6 H 5, - (C
_{H 2) n -C 6 H 5} (CH 3), - (CH 2) n -C 6 H 5 (C
H ₃ ) ₂ (n is an integer of 0 or more and the total number of carbon atoms in each group is 20 or less) Of these, a hydrogen atom is preferable.

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

The bond form between the alkenyl group and the 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 may be —NR ¹² ₂ (R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² may be the same or different. even if well, also connected to each other at the other end, but may form a cyclic structure) and the _{^{like, -. (NR 12 3)}} + X - (R 12 is the same .X as above ^- Is an anion.) There is no problem even if it is an ammonium salt shown in.

In the above formula, R ¹² is hydrogen or has 1 to 2 carbon atoms.
A monovalent organic group of 0, for example, hydrogen, carbon number 1 to 2
Examples thereof include an alkyl group having 0, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Two R ^12's may be the same or different from each other. Further, the other ends may be connected to each other to form a ring structure. Group Having 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) ( In the formula, R ¹³ is a group represented by hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and more preferably a group in which R ¹³ is hydrogen or a methyl group. Is.

In the general formula 8, R¹³As a concrete example of
There is no particular limitation, and for example, -H, -CH₃, -CH₂CH
₃,-(CH₂)_nCH₃(N represents an integer of 2 to 19),
-C ₆H_Five, -CH₂OH, -CN, etc. are mentioned, but
More preferably -H, -CH₃Is. <Method for introducing functional group> The vinyl polymer of the present invention is described below.
The method of introducing a functional group into (I) will be described, but the method is not limited to this.
It is not fixed.

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

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

(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a polymerizable alkenyl group and a low-polymerizable alkenyl group are both contained in one molecule as represented by the following general formula 9. A method of reacting a compound 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.

(A-d) A vinyl-based polymer having at least one highly reactive carbon-halogen bond has the general formula 1
A method of reacting a stabilized carbanion having an alkenyl group as described in 0 to substitute halogen. ^{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) 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. 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-based polymer having at least one highly reactive carbon-halogen bond is carried out by an atom transfer radical using the above-mentioned organic halide as an initiator and a transition metal complex as a catalyst. Examples of the polymerization method include, but are not limited to:

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

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

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

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

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

When an alkenyl group is introduced by converting the halogen of a 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 representative ones include compounds 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, a crosslinkable group represented by the general formula 14 H-Si (R ¹⁰ ) _3-a (Y) _a (14) (in the formula, R ¹⁰ , Y and a are the same as above) is particularly preferable. The compound having is preferable because it is easily available.

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

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 as a second compound. Method of reacting as a monomer. ^{_{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, JP-A-5-262808
A method of radically polymerizing a vinyl-based monomer by using a large amount of a chain transfer agent containing a hydroxyl group such as a polysulfide containing a hydroxyl group as shown in.

(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 added to the compound represented by the general formula 1
A method of reacting a stabilized carbanion having a hydroxyl group as described in 6 to substitute halogen. ^{M + C - (R 18)} (R 19) -R 20 -OH (16) as an electron withdrawing group ^{(wherein, R 18, R 19, R} 20, are the same) R ^18, R ¹⁹ are, -CO ₂ R, -C
Those having a structure of (O) R and —CN are particularly preferable.

(Bh) 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. A method of reacting aldehydes or ketones later.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with an oxyanion or carboxylate anion having a hydroxyl group as represented by the general formula 17 or 18, for example. To replace halogen. ^{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.

Although such a compound is not particularly limited, the compound represented by the general formula 19 and the like can be mentioned. ^{_{H 2 C = C (R 14}} ) -R 21 -OH (19) ( wherein, R ¹⁴ and R ²¹ are the same as those described above.) It is not particularly restricted but includes compounds represented by the general formula 19 Alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available. Etc.

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

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

The compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule is, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, Examples include γ-isocyanatopropyltriethoxysilane and the like, 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 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 living radical polymerization is expected to provide rubber-like properties. 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.

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

The method for synthesizing the vinyl polymer having at least one highly reactive carbon-halogen bond used in the method (E) uses the above-mentioned organic halide or the like 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 those 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;

Further, in the atom transfer radical polymerization, there may be mentioned 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. Amino Group As a method for producing a vinyl polymer having at least one amino group at the terminal of the main chain, the following steps can be mentioned. (1) A vinyl polymer having at least one halogen group at the terminal of the main chain is produced, and (2) terminal halogen is converted into a substituent having an amino group by using an amino group-containing compound.

The substituent having an amino group is not particularly limited, but the group represented by the general formula 22 is exemplified. —O—R ²⁶ —NR ¹² ₂ (22) (In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms, which may have one or more ether bonds or ester bonds. ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² may be the same or different from each other, and they are connected to each other at the other end to form a cyclic structure. In the above general formula 22, R ²⁶ has 1 to 20 carbon atoms which may include one or more ether bonds or ester bonds.
A divalent organic group of, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and 7 to 2 carbon atoms.
Such aralkylene group 0 but are ^{_{exemplified, -C 6 H 4 -R 27 -}} ( wherein, C ₆ H ₄ is a phenylene group, R ²⁷ is a direct bond or at least one ether bond or an ester bond Or a —C (O) —R ²⁸ — (wherein R ²⁸ represents a direct bond or one or more ether bond or ester bond). 1 to 19 carbon atoms that may be included
Represents a divalent organic group. ) Is preferred.

Conversion of terminal halogen of vinyl polymer
By doing so, it is possible to introduce an amino group at the polymer terminal.
Wear. The replacement method is not particularly limited, but the reaction is controlled.
Amino group-containing compounds are used as nucleophiles because they are easy to control.
Preferred is a nucleophilic substitution reaction. As such a nucleophile
For example, combining the hydroxyl group and the amino group represented by the general formula 23
Compounds that have. HO-R²⁶-NR¹² ₂  (23) (In the formula, R²⁶Is one or more ether linkages or esters
A divalent organic group having 1 to 20 carbon atoms which may contain a bond
Represents R¹²Is hydrogen or monovalent organic having 1 to 20 carbon atoms
Group, two R¹²May be the same or different
May also be connected to each other at the other end to form a ring structure.
May be formed. ) In the above general formula 23, R²⁶Is one or more ether linkages
1 to 20 carbon atoms which may include a compound or an ester bond
Is a divalent organic group of, for example, an alkyl group having 1 to 20 carbon atoms.
Ren group, arylene group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
And an aralkylene group of 0 and the like. These hydroxyl groups
Among the compounds that have both and an amino group, R ²⁶But, -C₆H_Four-R²⁷− (In the formula, C₆H_FourIs a phenylene group, R²⁷Is a direct bond or
Contains one or more ether or ester bonds
Represents a divalent organic group having 1 to 14 carbon atoms)
Aminophenols; -C (O) -R²⁸− (In the formula, R²⁸Is a direct bond or one or more ether bonds
1 to 19 carbon atoms which may contain a compound or an ester bond
Which represents a divalent organic group of).
Good

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. Although such a compound is not particularly limited, examples thereof include compounds represented by the general formula 24. 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 represents an alkali metal ion or a quaternary ammonium ion. As the alkali metal ion,
Lithium ion, sodium ion, potassium ion and the like can be mentioned, with preference given to 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 salts of aminophenols represented by the general formula 25 or the compounds represented by the general formula 26 are preferred because the substitution reaction is easily controlled and available. Amino acid salts are preferred. ^{_{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 Or may be linked to each other at the other end to form a cyclic structure. M ⁺ is the same as the above.) The compound having an oxyanion represented by the general formulas 24 to 26 is a compound represented by the general formula: It is easily obtained by reacting the compound shown in 23 with a basic compound.

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

Examples of the solvent used in reacting the above precursor with the above base include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated methylene chloride and chloroform. Hydrocarbon-based solvent; ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ethylene carbonate Carbonate solvents such as propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide. These may be used alone or in combination of two or more.

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

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

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

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

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

Further, a method of substituting the halogen terminal of the vinyl polymer with an azide anion and then reducing with LAH or the like can be mentioned. Group Having Polymerizable Carbon-Carbon Double Bond The method for introducing the group having a polymerizable carbon-carbon double bond into the polymer (I) of the present invention is not limited,
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) (In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal 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.) The diisocyanate compound is reacted with the vinyl polymer having
A method by reaction with a compound represented by: ^{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) (In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion. The vinyl-based polymer having a terminal structure represented by the general formula 27 is a method of polymerizing a vinyl-based monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or It is produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, and the former is preferable.

The compound represented by 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, etc., and is preferably -H, -CH _3. 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 1.2 equivalents, relative to the halogen group of the general formula 27. The solvent for carrying out this reaction is not particularly limited, but a polar solvent is preferable because it is a nucleophilic substitution reaction, and examples thereof include tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and hexamethylphosphoric. Triamide, acetonitrile, etc. are used. The temperature at which the reaction is carried out is not limited, but is generally 0 to 1
At 50 ° C., preferably at room temperature to 100 ° C. in order to retain the polymerizable end groups.

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, it is a -CH _3.

The vinyl polymer having a hydroxyl group, preferably at the terminal, is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a hydroxyl group. It is produced by a method of polymerizing a vinyl-based monomer using a compound having ## 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, a compound represented by the following general formula 31 having a polymerizable alkenyl group and a hydroxyl group in one molecule is used as a second monomer. How to make. ^{_{H 2 C = C (R 32}} ) -R 33 -R 34 -OH (31) ( wherein, R ³² is preferably a hydrogen or a methyl group with an organic group having 1 to 20 carbon atoms, being the same or different R ³³ represents —C (O) O— (ester group), or o-, m- or p-phenylene group, and R ³⁴ has a direct bond or has one or more ether bonds. Which represents a divalent organic group having 1 to 20 carbon atoms, wherein R ³³ is an ester group and is a (meth) acrylate compound, and R ³³ is a phenylene group is a styrene compound. Although there is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, especially in the case of expecting rubber-like properties, at the end of the polymerization reaction or after the reaction of a predetermined monomer, It is preferable to react as a monomer of 2. There.

(B) When synthesizing a vinyl polymer by living radical polymerization, 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. Although the compound represented by the general formula 32 is not particularly limited, alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

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

(D) A vinyl-based polymer having at least one carbon-halogen bond represented by the general formula 27 obtained by atom transfer radical polymerization, and having a hydroxyl group represented by the general formula 33. A method in which a carbanion is reacted to replace halogen. M ⁺ C ⁻ (R ³⁶ ) (R ³⁷ ) —R ³⁵ —OH (33) (In the formula, R ³⁵ is the same as described above. Both R ³⁶ and R ³⁷ are electrons for stabilizing carbanion C ^−. An attracting group, or one of them is an electron withdrawing group and the other is hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group.
^Examples of the electron withdrawing group for R ³⁶ and R ³⁷ include —CO ₂ R (ester group), —C (O) R (keto group), and —CON.
(R ₂₎ (amide group), - COSR (thioester group), - CN (nitrile group), - NO ₂ (nitro group), and the like. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms.
Is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ³⁶ and R ³⁷ , —CO ₂ R, —C (O) R and —CN are particularly preferable. ) (E) General formula 27 obtained by atom transfer radical polymerization
A vinyl-based polymer having at least one carbon-halogen bond represented by the following is reacted with a metal simple substance such as zinc or an organometallic compound to prepare an enolate anion, and then aldehydes or ketones are added. How to react.

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

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

The above method will be described. A vinyl-based polymer having a hydroxyl group is reacted with a diisocyanate compound to give a residual isocyanate group and a general formula 36
A method by reaction with a compound represented by: ^{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 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, it 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. << Micro Hollow Body (II) >> The micro hollow body (hereinafter referred to as a balloon) (II) contained in the composition of the present invention is described, for example, in "Latest Technology of Functional Filler" (CMC). And has a diameter of 1 mm or less, preferably 500 μ
It is a hollow body made of an inorganic or organic material having a particle size of m or less, more preferably 200 μm or less. In particular, it is preferable to use a minute hollow body having a true specific gravity of 1.0 g / cm ³ or less, and more preferably 0.5 g / cm ³ or less.

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

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

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

The above balloon may be used alone or 2
You may use it in mixture of 2 or more types. Furthermore, in order to improve the dispersibility and workability of the compound on the surface of these balloons with fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. Treated products can also be used. These balloons are used for weight reduction and cost reduction without impairing the flexibility and elongation / strength of the physical properties when the compound is cured. <Content> The content of the balloon (II) is not particularly limited, but is preferably 0.1 to 50 parts, more preferably 0.1 to 30 parts with respect to 100 parts by weight of the vinyl polymer (I).
Can be used in a range of parts. If this amount is less than 0.1 part, the effect of weight reduction is small, and if it is 50 parts or more, a decrease in tensile strength may be observed among the mechanical properties when the composition is cured. If the specific gravity of the balloon is 0.1 or more, 3
˜50 parts, and more preferably 5 to 30 parts. << 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 phthalate, dibutyltin diacetate, dibutyltin bisacetylacetonate, dibutyltin diethyl hexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin. Tin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin ditridecyl maleate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, Tetravalent tin compounds such as dioctyltin diethylmalate, dioctyltin diisooctylmalate, dibutyltin dimethoxide, dibutyltin bisnonylphenoxide, dibutenyltin oxide; Divalent tin compounds such as tin acid salt, tin naphthenate and tin stearate; monoalkyltin compounds such as monobutyltin compound such as monobutyltin trisoctoate and monobutyltin triisopropoxide; monoalkyltin compounds such as tetra Titanic acid esters such as butyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate Chelate compounds such as lead octylate;
Butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine. , 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N
-Amine compounds such as methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), or salts of these amine compounds with carboxylic acids and the like. A reactant or mixture of an amine compound and an organotin compound such as a reaction or mixture of laurylamine and tin octylate; a low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; excess polyamine and epoxy Reaction product with compound; γ-aminopropyltrimethoxysilane, N
A silane coupling agent having an amino group such as-(β-aminoethyl) aminopropylmethyldimethoxysilane;
And other 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 compounded is 0.1 to 100 parts (parts by weight, hereinafter the same) of the vinyl polymer (I) having at least one crosslinkable silyl group.
About 20 parts is preferable, 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, the general formula 37 R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (37) (wherein R ⁴⁹ and R ⁵⁰ 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 (1) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane. R ^{49 of} is an aryl group having 6 to 20 carbon atoms 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 this silicon compound is such that the vinyl polymer (I) 10 having at least one crosslinkable silyl group.
About 0.01 to 20 parts is preferable with respect to 0 parts, and 0.1
It is more preferably 10 parts. 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 or 3
A chain polysiloxane represented by 9; R⁵¹ ₃SiO- [Si (R⁵¹)₂O]_a-[Si (H) (R⁵²) O]_b-[Si (R ⁵² ) (R⁵³) O]_c-SiR⁵¹ ₃    (38) HR⁵¹ ₂SiO- [Si (R⁵¹)₂O]_a-[Si (H) (R⁵²) O]_b-[Si ( R⁵²) (R⁵³) O]_c-SiR⁵¹ ₂H (39) (In the formula, R⁵¹And R⁵²Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁵³Is alkyl having 1 to 10 carbons
Represents a group or an aralkyl group. a is 0 ≦ a ≦ 100, b
Is an integer satisfying 2 ≦ b ≦ 100 and c is an integer satisfying 0 ≦ c ≦ 100.
Show. ) A cyclic siloxane represented by the general formula 40;

[0151]

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

These may be used alone or in 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 cyclic siloxanes represented by the general formulas 43 and 44 are shown. Is preferred. _{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -S i (CH 3) 3 (41) (CH 3) 3 SiO- _{[Si (H) (CH 3} ) O] g - [Si (CH 3) {CH 2 C (H) (R 57) C 6 H 5} O] h -Si (CH 3) 3 (42) ( formula Wherein R ⁵⁷ represents hydrogen or a methyl group, and g is 2 ≦ g
≦ 100 and h are integers of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group. )

[0153]

[Chemical 8] (In the formula, R ⁵⁷ represents hydrogen or a methyl group. I is 2 ≦
i ≦ 10 and j are integers satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. ) Further, as the compound containing a hydrosilyl group, 2
A compound obtained by adding a hydrosilyl group-containing compound represented by the general formulas 38 to 44 to a low molecular weight compound having at least one alkenyl group so that a part of the hydrosilyl group remains after the reaction is used. You can also
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 can be 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 obtain the compound. . 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.

[0155]

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

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

The curing temperature is not particularly limited, but it is generally 0 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., and 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.

These crosslinking reactions will be described in detail below.

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

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

[0164]

[Chemical 10]

[0165]

[Chemical 11]

[0166]

[Chemical 12]

[0167]

[Chemical 13]

[0168]

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

Examples of the polyfunctional monomer include neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate and bisphenol A.
Polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) )
-5-ethyl-5-acryloyloxymethyl-1,3
-Dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and the like.

As the oligomer, an epoxy acrylate resin such as a bisphenol A type epoxy acrylate resin, a phenol novolac type epoxy acrylate resin, a cresol novolac type epoxy acrylate resin, a COOH group-modified epoxy acrylate type resin, a polyol (polytetramethylene glycol, ethylene) is used. Polyester diol of 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, hexamethyi Urethane resin obtained from diisocyanate, xylylene diisocyanate, etc.) is used as a hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Examples thereof include a urethane acrylate resin obtained by the reaction, a resin obtained by introducing a (meth) acrylic group into the above polyol via an ester bond, and a polyester acrylate resin.

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. preferable.

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

Further, 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-based 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, although it varies depending on the kind of the thermal initiator, the polymer (I) and the compound to be added. Preferably in the range of ℃ to 250 ℃,
More preferably, it is in the range of 70 ° C to 200 ° C. The curing time varies depending on the polymerization initiator used, the monomer, the solvent, the reaction temperature, etc., but is usually in the range of 1 minute to 10 hours. <Adhesiveness imparting agent> A silane coupling agent or an adhesiveness imparting agent other than the silane coupling agent may be added to the composition of the present invention as necessary. When the adhesion-imparting agent is added, the risk of the sealing material peeling off from the adherend such as a siding board can be further reduced because the joint width and the like change due to external force. In some cases, it is not necessary to use a primer used for improving the adhesiveness, and it is expected that the construction work will be simplified. Specific examples of the silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane. 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, N-
Benzyl-γ-aminopropyltrimethoxysilane, N
-Amino group-containing silanes such as vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxy. Mercapto group-containing silanes such as silane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as trimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane and β-carboxyethylphenylbis (2
-Methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane and other carboxysilanes; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ -Vinyl unsaturated group-containing silanes such as acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate Can be mentioned. 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. The effect of the silane coupling agent added to the curable composition of the present invention, various adherends, that is, glass, aluminum, stainless steel, zinc, copper, inorganic substrates such as mortar, vinyl chloride, acrylic, polyester, When it is used as an organic base material such as polyethylene, polypropylene or polycarbonate, it shows a remarkable effect of improving the adhesiveness under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving the adhesion to various adherends is particularly remarkable.

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

The above adhesion-imparting agents may be used alone or in combination of two or more. Addition of these adhesiveness-imparting agents can improve the adhesiveness to the adherend. Although not particularly limited, 0.1 to 20 parts by weight of a silane coupling agent is used among the above-mentioned adhesiveness-imparting agents in order to improve the adhesiveness, particularly the adhesiveness to a metal adhered surface such as an oil pan. Is preferred. <Plasticizer> In the curable composition of the present invention, various molecular plasticizers may be used as necessary. When a plasticizer is used in combination with the below-mentioned filler, the elongation of the cured product can be increased,
This is more advantageous because a large amount of filler can be mixed, but it is not always necessary to add. The plasticizer is not particularly limited, but for the purpose of adjusting physical properties 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, triethylene glycol dibenzoate, penta Esters of polyalkylene glycol such as erythritol ester; tricresyl phosphate,
Phosphoric acid esters such as tributyl phosphate; trimellitic acid esters; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; alkyldiphenyl Hydrocarbon oils such as partially hydrogenated terphenyl; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and the hydroxyl groups of these polyether polyols were converted to ester groups, ether groups, etc. Polyethers such as derivatives; Epoxidized soybean oil, epoxy plasticizers such as benzyl epoxystearate; Dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid and ethylene glycol Polyester plasticizers obtained from dihydric alcohols such as kohl, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; vinyls obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods. Examples thereof include polymers.

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

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

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

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

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

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

The amount of the plasticizer used is not limited, but may be 5 to 15 parts by weight with respect to 100 parts by weight of the vinyl polymer.
The amount is 0 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. <Filler> In the curable composition of the present invention, various fillers may be used as necessary. The filler is not particularly limited, wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, chaff powder,
Graphite, diatomaceous earth, clay, fumed silica,
Reinforcing fillers such as precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, carbon black; ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay Fillers such as talc, titanium oxide, bentonite, organic bentonite, ferric oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc dust and shirasu balloon; asbestos, glass fiber and glass filament, Fibrous fillers such as carbon fiber, Kevlar fiber, polyethylene fiber and the like can be mentioned. Among these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, 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, carbon black, surface-treated fine calcium carbonate, crystalline silica, fused silica, calcined clay, clay and activated zinc white can be added.

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

Further, 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 and various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and other fatty acids. And salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids. Specific examples of the surfactant include polyoxyethylene alkyl ether sulfuric acid ester, long-chain alcohol sulfuric acid ester and the like, sulfuric acid ester type anionic surfactants such as sodium salt and potassium salt thereof, alkylbenzene sulfonic acid and alkylnaphthalene. Examples thereof include sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkyl sulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof. The surface treatment agent is preferably treated in an amount of 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on calcium carbonate. If the treatment amount is less than 0.1% by weight, the workability, adhesiveness and weather resistance may not be sufficiently improved. If it exceeds 20% by weight, the storage stability of the curable composition may be poor. It may decrease.

Although not particularly limited, in the case of using calcium carbonate, when the effect of improving the thixotropy of the composition, the breaking strength, breaking elongation, adhesiveness and weather-adhesiveness of the cured product is particularly expected, colloidal calcium carbonate is used. Is preferably used.

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

Heavy calcium carbonate is mechanically ground and processed from natural chalk (chalk), marble, limestone and the like. There are a dry method and a wet method as a pulverizing method, but a wet pulverized product is often not preferable because it often deteriorates the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes a product having various average particle sizes by classification. Although not particularly limited, in the case of expecting the effects of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product, those having a specific surface area of 1.5 m ² / g or more and 50 m ² / g or less are preferred. Preferably 2 m ² / g or more 5
0 m ² / g or less is more preferable, and 2.4 m ² / g or more 50
m ² / g or less is more preferable, 3 m ² / g or more and 50 m ² /
Particularly preferred is g or less. If the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when simply lowering the viscosity or only for the purpose of increasing the amount.

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

These fillers may be used alone or in combination of two or more depending on the purpose and need. Although not particularly limited, for example, if a combination of heavy calcium carbonate having a specific surface area value of 1.5 m ² / g or more and colloidal calcium carbonate is combined as necessary, an increase in the viscosity of the composition is suppressed moderately and a cured product is obtained. The breaking strength, breaking elongation, improvement of adhesiveness and weather resistance can be expected.

When the micro hollow body (II) of the present invention is used in combination with these reinforcing fillers, the weight reduction is achieved without causing a large decrease in the physical properties, as compared with the case where a cured product is prepared from the micro hollow body alone. Therefore, cost reduction can be achieved. <Addition amount> When the filler is used, the addition amount is preferably in the range of 5 to 1000 parts by weight with respect to 100 parts by weight of the vinyl polymer, and in the range of 20 to 500 parts by weight. It is more preferably used, and particularly preferably used in the range of 40 to 300 parts by weight. If the blending amount is less than 5 parts by weight, the effects of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product may be insufficient.
If it exceeds 000 parts by weight, the workability of the curable composition may deteriorate. The filler may be used alone or 2
You may use together more than one kind. <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. <Silanol-containing compound> The curable composition of the present invention includes
A silanol-containing compound may be added as necessary such as changing the physical properties of the cured product. What is a silanol-containing compound?
A compound having one silanol group in the molecule and / or a compound capable of forming a compound having one silanol group in the molecule by reacting with water.
Only one of these may be used, or both compounds may be used at the same time.

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

[0210]

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

[0211]

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

[0212]

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

[0213]

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

[0214]

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

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

The above-mentioned compound having one silanol group in the molecule reacts with the crosslinkable silyl group of the vinyl polymer or the siloxane bond formed by the crosslinkage to reduce the number of crosslink points and to give a cured product. It is presumed to give flexibility to. It is also one of the components of the present invention,
The compound capable of forming a compound having one silanol group in the molecule by reacting with water is not particularly limited, but a compound having one silanol group in the molecule formed by reacting with water (hydrolysis The product) is preferably a compound represented by the above general formula (45). For example, although not particularly limited, the following compounds may be mentioned in addition to the compound represented by the general formula (46) described below.

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

[0218]

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

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

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

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

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

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

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

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

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

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

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

The anti-dripping agent is not particularly limited,
For example, polyamide waxes, hydrogenated castor oil and fatty acid derivatives, organic compounds such as 1,3,5-tris (trialkoxysilylalkyl) isocyanurate, calcium stearate, aluminum stearate, barium stearate, etc. Examples thereof include metal soaps, calcium carbonate surface-treated with these metal soaps, fatty acids, resin acids and the like, fine powder silica, carbon black and the like. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.

The fine powder silica referred to here means a natural or artificial inorganic filler containing silicon dioxide as a main component. Specifically, kaolin, clay, activated clay, silica sand, silica stone, diatomaceous earth, anhydrous aluminum silicate, hydrous magnesium silicate, talc, perlite, white carbon, fine powder of mica, bentonite, organic bentonite, etc. are exemplified. it can. <Regarding photocurable substance> The curable composition of the present invention includes
A photocurable substance may be added if necessary. The photocurable substance is a substance in which the molecular structure undergoes a chemical change in a short time due to the action of light to cause a change in physical properties such as curing. By adding this photocurable substance, the tackiness (also referred to as residual tack) on the surface of the cured product when the curable composition is cured can be reduced. This photo-curable substance is a substance that can be cured by exposing it to light, but a typical photo-curable substance is, for example, that the photo-curable substance should be left at room temperature for one day at a position where it is exposed to sunlight (near the window). It is a substance that can be cured by. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as compounds of this type, and the type thereof is not particularly limited,
For example, unsaturated acrylic compounds, polyvinyl cinnamate, azide resins, etc. may be mentioned.

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

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

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

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

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

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

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

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

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

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

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

The curable composition of the present invention may be prepared as a one-component type in which all the compounding ingredients are previously compounded and hermetically sealed and then cured by the moisture in the air after the construction. It is also possible to mix components such as wood, plasticizer and water in advance, and to prepare the two-component type in which the compound material and the polymer composition are mixed before use. When the two-component type is used, a colorant can be added when the two components are mixed. For example, when providing a sealing material that matches the color of the siding board, it is possible to make abundant color alignment with limited stock. This makes it possible to easily cope with the demand for multiple colors in the market, which is preferable for low-rise buildings. For the colorant, for example, a pigment and a plasticizer, and in some cases, a filler mixed to form a paste is used, which facilitates the work. Further, the curing rate can be finely adjusted at the work site by adding a retarder when the two components are mixed. << Cured Product >><Use> The curable composition of the present invention is not limited,
Sealing materials such as elastic sealing materials for construction and sealing materials for double glazing, electrical / electronic component materials such as solar cell backside sealing materials, electrical insulating materials such as insulation coating materials for electric wires and cables, adhesives, adhesives, Elastic adhesive, paint, powder paint,
Coating materials, foams, potting agents for electrical and electronic products,
For various applications such as films, gaskets, casting materials, various molding materials, and rustproof / waterproof sealants for meshed glass and laminated glass end faces (cut parts), automobile parts, electrical parts, various machine parts, etc. It is available.

[0243]

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

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

In the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight and number average molecular weight)"
Is gel permeation chromatography (GP
It was calculated by the standard polystyrene conversion method using C).
However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; Showa Denko KK), and chloroform was used as a GPC solvent. (Production Example 1) In a 50 L reaction kettle equipped with a reflux tower and a stirrer, CuBr (25
A suspension in which 1.82 g and 1.76 mol) were dispersed was charged, and the inside of the reaction vessel was sealed with nitrogen, followed by stirring at 65 ° C. for 30 minutes. Butyl acrylate (6.0 kg), 2,
Diethyl 5-dibromoadipate (526.70 g,
1.46 mol), acetonitrile (695 g), pentamethyldiethylenetriamine (12.0 mL, 58.
5 mmol) (hereinafter referred to as triamine) was added to start the reaction. Butyl acrylate (24.0 kg) was continuously added dropwise while heating and stirring at 80 ° C. During the dropwise addition of butyl acrylate, triamine (36.0 mL, 17
6 mmol) was added. Subsequently, after heating and stirring at 80 ° C, 1,7-octadiene (6.448 kg) and triamine (120.0 mL, 585 mmol) were added, and heating and stirring was further continued at 80 ° C for 4 hours. After that,
A reaction mixture containing the polymer [P1] (polymerization reaction mixture [P1] was added by adding triamine (80.0 mL, 390 mmol) and heating and stirring at 90 ° C. for 4 hours.
1 ']) was obtained. The reaction mixture [P1 ′] was diluted with toluene, passed through an activated alumina column, and the volatile matter was distilled off under reduced pressure to give an alkenyl group-terminated polymer (polymer [P1 ′]).
1]) was obtained. In a 10 L separable flask with a reflux tube,
Polymer [P1] (3.2 kg), potassium acetate (74.
1 g) and N, N-dimethylacetic acid amide (3.2 L) were charged, and the mixture was heated with stirring at 100 ° C. for 8 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under heating and reduced pressure, the mixture was diluted with toluene. Solid components insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatile components of the filtrate were distilled off under reduced pressure to obtain a polymer [P2].

[0246] The polymer was placed in a 10 L round bottom flask equipped with a reflux tube.
[P2] (3 kg), adsorbent (450 g, manufactured by Kyowa Chemical,
(Kyoward 500SH, Kyoward 700SL),
Charge xylene (0.6L) at 130 ° C under nitrogen stream.
The mixture was heated and stirred for 5.0 hours. The adsorbent was removed by filtration
Then, the filtrate was distilled off under reduced pressure to obtain a polymer [P3].
It was (Production Example 2) Polymer obtained in Production Example 1 in a 2 L reaction vessel
[P3] (1300 g), dimethoxymethylhydrosila
(58.5 mL), methyl orthoformate (17.3 m
L), and 1,1,3,3-tetramethyl of 0-valent platinum
A -1,3-divinyldisiloxane complex was charged. Na
The amount of platinum catalyst used is platinum conversion for 1 kg of polymer.
30 mg. After heating and reaction at 100 ° C for 3.5h, mix
The silyl group end vinyl is removed by distilling off the volatile components of the product under reduced pressure.
A nil polymer (polymer [P4]) was obtained. Polymerization obtained
The number average molecular weight of the body is measured by GPC (polystyrene conversion)
27,000 and the molecular weight distribution was 1.4. Polymer
The average number of silyl groups introduced per molecule is¹H
The number was 2.5 as determined by NMR analysis. (Production Example 3) Polymer obtained in Production Example 1 in a 2 L reaction vessel
[P3], 3-mercaptopropyltrimethoxysila
2,2'-azobis-2-methylbutyronitrile
After charging and reacting by heating, the volatile components of the mixture (unreacted
No 3-mercaptopropyltrimethoxysilane left
(So that the silyl group end)
An end vinyl polymer (polymer [P5]) was obtained. Got
The number average molecular weight of the polymer is measured by GPC (polystyrene conversion
According to the calculation, it was 28,000 and the molecular weight distribution was 1.4.
The average number of silyl groups introduced per molecule of polymer is
¹It was 2.7 as determined by 1 H NMR analysis.
It was (Production Example 4) Similarly obtained in Production Example 1 in a 2 L reaction vessel.
Polymer [P3] (1000 g), trimethoxysilane
(45 mL), methyl orthoformate (13.3 mL),
And zero-valent platinum 1,1,3,3-tetramethyl-1,3
Charged with the divinyldisiloxane complex. The polymer
As in [P4], the platinum catalyst and dimethoxymethylsilane were
I added it on the way. After sufficiently heating and reacting, volatilize the mixture.
The silyl group-terminated vinyl system
A polymer (polymer [P6]) was obtained. Number of polymers obtained
The average molecular weight is 2 by GPC measurement (polystyrene conversion)
The molecular weight distribution was 7,000. 1 molecule of polymer
The average number of silyl groups introduced per ¹1 H NMR
It was 2.5 as determined by analysis. (Production Example 5) 10 L of separa equipped with a reflux tube and a stirrer
In a bull flask, add CuBr (36.02 g, 0.251
(1 mol) was charged, and the inside of the reaction vessel was replaced with nitrogen. Asse
Trinitrile (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) 2,5-dibromoa
Diethyl dipinate (150.68g, 0.419mo
l), pentamethyldiethylenetriamine (2.18 m
L, 1.81 g, 10.46 mmol)
(Denoted as amine) was added to start the reaction. Heat at 70 ° C
While stirring, butyl acrylate (1440 mL),
Ethyl acrylate (2002 mL), acrylic acid 2-meth
A mixture of xylethyl (1498 mL) over 210 minutes
It was dripped continuously. Triamine during the dropping of the monomer
(7.63 mL, 6.33 g, 36.5 mmol)
Added 330 minutes after the start of the reaction, 1,7-octa
Diene (1236 mL, 922 g, 8.37 mol),
Triamine (26.16 mL, 21.71 g, 0.12
(5 mol) and then heated and stirred at 70 ° C for 250 minutes.
did.

The reaction mixture was diluted with toluene, passed through an activated alumina column, and volatile components were distilled off under reduced pressure to give an alkenyl-terminated copolymer {alkenyl-terminated poly (butyl acrylate, ethyl acrylate, methoxy acrylate) Ethyl) copolymer: copolymer [P7]} was obtained.

In a 10 L separable flask equipped with a reflux tube, the copolymer [P7] (2.87 kg) and potassium acetate (7
9.57 g), N, N-dimethyl acetic acid amide (2.9
L) was charged, and the mixture was heated and stirred at 100 ° C. for 12 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under heating and reduced pressure, the mixture was diluted with toluene. Solids insoluble in toluene (KBr and excess potassium acetate) were filtered through an activated alumina column. The volatile component of the filtrate was distilled off under reduced pressure to obtain a copolymer [P8].

Into a 10 L separable flask equipped with a reflux tube, the copolymer [P8] (2.87 kg) and acidic aluminum silicate (1
43 g, Kyowa Chemical Co., Ltd., Kyoward 700 SL), hydrotalcites (143 g, Kyowa Chemical Co., Kyoward 500 SH), and toluene (5.2 L) were charged, and the mixture was heated and stirred at 100 ° C. for 7 hours under a nitrogen stream. After removing the adsorbent by filtration, toluene in the filtrate was distilled off under reduced pressure to obtain a vinyl group-terminated copolymer (copolymer [P9]). The number average molecular weight of the obtained copolymer was 18,000 as measured by GPC (in terms of polystyrene), and the molecular weight distribution was 1.
It was 24. The average number of vinyl groups introduced per molecule of the copolymer was determined by ¹ H NMR analysis to be 2.2. (Example 1) Polymer [P4] 100 obtained in Production Example 2
In the part, colloidal calcium carbonate (Sealet 200: 100 parts made by Maruo calcium, MC-5: 50 made by Maruo calcium)
Part) 150 parts, heavy calcium carbonate (Nanox 25
A: made by Maruo calcium) 15 parts, plasticizer (DIDP) 7
0 parts, 5 parts MFL80GCA (primary particle size 20 μm: manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) as a micro hollow body (generally referred to as micro hollow particles), 2 parts dehydrating agent (A-171: manufactured by Nippon Unicar), silane cup 1 part of a ring agent (A-1120: manufactured by Nippon Unicar Co., Ltd.) was mixed based on the following composition table, and a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was used to obtain a sheet-shaped cured product having a thickness of about 2 mm. The curing and curing conditions were indoors for 3 days and then at 50 ° C. for 4 days. (Example 2) Micro hollow body MFL80G used in Example 1
A cured product was obtained by preparing a test body in the same manner as in Example 1 except that 10 parts of CA was used and 10 parts of Nanox 25A was used instead. The specific gravity of this cured product was 1.09. (Example 3) Micro hollow body MFL80G used in Example 1
Instead of CA, MFL100CA (primary particle size 20-40
μm: manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was used to prepare a test body in the same manner as in Example 1 except that the same amount (5 parts) was used to obtain a cured product. (Example 4) Micro hollow body MFL80G used in Example 1
A test piece was prepared in the same manner as in Example 1 except that 10 parts of SL75 (manufactured by Taiheiyo Cement) was used in place of CA, and the amount of nanox 25A was further reduced to 10 parts to obtain a cured product. (Example 5) Polymer [P5] 100 obtained in Production Example 3
A part was obtained in the same manner as in Example 1 to obtain a sheet-shaped cured product having a thickness of about 2 mm. (Example 6) Micro hollow body MFL80G used in Example 5
Instead of CA, MFL100CA (primary particle size 20-40
μm: Matsumoto Yushi-Seiyaku Co., Ltd.) was used to prepare a test body in the same manner as in Example 5 except that the same amount (5 parts) was used to obtain a cured product. (Example 7) Polymer [P6] 100 obtained in Production Example 4
A part was obtained in the same manner as in Example 1 to obtain a sheet-shaped cured product having a thickness of about 2 mm. (Example 8) Micro hollow body MFL80G used in Example 7
Instead of CA, MFL100CA (primary particle size 20-40
μm: manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was used to prepare a test body in the same manner as in Example 7 except that the same amount (5 parts) was used to obtain a cured product. (Example 9) Polymer [P3] 100 obtained in Production Example 1
Part of a chain siloxane (containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule: S
An i-H group amount of 3.70 mmol / g) was added so that the SiH group of the chain siloxane would be equivalent to 1.8 equivalents of the alkenyl group of the copolymer [P3], and MFL80GCA as a micro hollow body. 5 parts (primary particle diameter 20 μm: manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) were added and mixed. Furthermore, after adding 3,5-dimethyl-1-hexyn-3-ol and tetramethylethylenediamine (TMEDA) and mixing them well, bis (1,3-divinyl-1,1,3,3-tetra) Methyldisiloxane) platinum complex catalyst (1.32 × 10 ^-5
mmol / μl, xylene solution) was added in an amount of 10 ⁻³ mol equivalent of the alkenyl group of the copolymer [P3] in terms of platinum, and the mixture was further uniformly mixed. The curable composition thus obtained was thoroughly defoamed in a vacuum oven at 50 ° C., and then applied to a sheet having a thickness of about 2 mm at 150 ° C.
It was cured for 0 minutes. (Example 10) Micro hollow body MFL80 used in Example 9
Instead of GCA, MFL100CA (primary particle size 20-4
0 μm: manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was used to prepare a test sample in the same manner as in Example 9 except that the same amount (5 parts) was used to obtain a cured product. (Example 11) Polymer [P9] 10 obtained in Production Example 5
In the same manner as in Example 9, 0 part was obtained to obtain a sheet-shaped cured product having a thickness of about 2 mm. (Example 12) Micro hollow body MFL8 used in Example 11
MFL100CA (primary particle size 20-
40 μm: Matsumoto Yushi-Seiyaku Co., Ltd.) was used to prepare a test sample in the same manner as in Example 11 except that the same amount (5 parts) was used to obtain a cured product. (Comparative Example 1) Without adding the micro hollow body used in Example 1,
Instead, a cured product was produced in the same manner as in Example 1 except that the amount of Nanox 25A was increased to 20 parts. The specific gravity of this cured product was 1.21. (Evaluation 1) The stringiness at the time of producing each cured product was evaluated. The results are shown in Table 1.

[0250]

[Table 1] (Evaluation 2) 2 (1/3) type dumbbell type test pieces were punched out from the sheet-shaped cured products obtained in Examples 1 to 12 and Comparative Example 1, and tensile properties were measured using Shimadzu autograph. (Measuring environment: 23 ° C, pulling speed: 200 mm / m
in) The results are shown in Table 2.

[0251]

[Table 2]

[0252]

The present invention has at least one crosslinkable functional group.
It is composed of a curable composition comprising a vinyl polymer (I) and a micro hollow body (II) each of which has an individual number, is less expensive than the case of using a conventional filler, and does not significantly lower the tensile properties of the cured product. It is possible to reduce the weight of the curable composition. In addition, effects such as heat insulation, soundproofing, and heat absorption can be expected, and the stringiness (sparing property) of the compound is improved.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 BC001 BD102 BD121 BG001                       BG031 BG041 BG051 BG061                       BG071 BG101 BG102 CD191                       FB072 FD010 FD020 FD200                       FD340                 4J015 CA00

Claims (24)

[Claims] 1. A curable composition containing the following two components: (A) a vinyl polymer (I) having at least one crosslinkable functional group, and (B) a micro hollow body (II). 2. The molecular weight distribution of the vinyl polymer (I) is 1.
The curable composition according to claim 1, which is less than 8. 3. The main chain of the vinyl polymer (I) is (meth)
Claim 1 when produced mainly by polymerizing a monomer selected from the group consisting of acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers.
Or the curable composition according to 2. 4. The curable composition according to any one of claims 1 to 3, wherein the vinyl polymer (I) is a (meth) acrylic polymer. 5. The curable composition according to any one of claims 1 to 3, wherein the vinyl polymer (I) is an acrylic polymer. 6. The curable composition according to claim 5, wherein the vinyl polymer (I) is an acrylic acid ester polymer. 7. The curable composition according to claim 6, wherein the vinyl polymer (I) is a butyl acrylate polymer. 8. The crosslinkable functional group of the vinyl polymer (I),
A curable composition according to any one of claims 1 to 7, which is a crosslinkable silyl group. 9. The crosslinkable functional group of the vinyl polymer (I),
It is an alkenyl group, The curable composition as described in any one of Claims 1-7 characterized by the above-mentioned. 10. The curable composition according to any one of claims 1 to 7, wherein the crosslinkable functional group of the vinyl polymer (I) is a hydroxyl group. 11. The curable composition according to any one of claims 1 to 7, wherein the crosslinkable functional group of the vinyl polymer (I) is an amino group. 12. The crosslinkable functional group of the vinyl polymer (I) is a group having a polymerizable carbon-carbon double bond, according to any one of claims 1 to 7. Curable composition. 13. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an epoxy group. 14. The curable composition according to claim 1, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. . 15. The curable composition according to claim 14, wherein the living radical polymerization is atom transfer radical polymerization. 16. Atom transfer radical polymerization is carried out according to the seventh table of the periodic table.
16. The curable composition according to claim 15, wherein a complex selected from the group consisting of transition metal complexes having a group metal, group 8, group 9, group 10 or group 11 element as a central metal is used as a catalyst. 17. The curable composition according to claim 16, wherein the metal complex used as a catalyst is a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes. 18. The curable composition according to claim 17, wherein the metal complex used as a catalyst is a copper complex. 19. The silanol condensation catalyst (III) is further included as an essential component when the crosslinkable functional group of the vinyl polymer (I) is a crosslinkable silyl group. The curable composition according to any one of 1. 20. The true specific gravity of the micro hollow body (II) is 1.0.
The curable composition according to any one of claims 1 to 19, which is a micro hollow body having a g / cm ³ or less. 21. The curable composition according to claim 1, wherein the fine hollow body (II) is a fine hollow body whose surface is coated with an inorganic fine powder. 22. The surface of the micro hollow body (II) is coated with at least one inorganic compound selected from the group consisting of calcium carbonate, surface-treated calcium carbonate, titanium oxide, silicon oxide, talc, clay and carbon black. The curable composition according to any one of claims 1 to 21, wherein the curable composition is a curable composition. 23. The curable composition according to claim 1, wherein the micro hollow body (II) is an organic polymer. 24. The micro hollow body (II) comprises a vinylidene chloride resin, a copolymer of vinylidene chloride and acrylonitrile, a copolymer of acrylonitrile and methacrylonitrile, and vinylidene chloride, acrylonitrile and divinylbenzene. 24. The curable composition according to claim 23, which is an organic polymer formed of at least one selected from the group consisting of terpolymers.