JP2002294022A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in weather resistance and having storage stability without impairing high elongation derived from a polyether-based polymer having at least one crosslinkable functional group. SOLUTION: This curable composition has three components of a vinyl-based polymer (I) having at least one crosslinkable functional group, a polyether-based polymer (II) having at least one crosslinkable functional group and a compatibilizing agent (III) which, when added to a mixture of the vinyl-based polymer (I) with the polyether-based polymer (II), compatibilizes the component (I) and the component (II) and is selected from a group consisting of an organic compound which is not a polymer, a polymer obtained by polymerizing a monomer other than vinyl-based monomer and a polymer obtained by polymerizing a vinyl-based monomer alone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition. More specifically, a vinyl polymer (I) having at least one crosslinkable functional group, a polyether polymer (II) having at least one crosslinkable functional group, and a vinyl polymer having at least one crosslinkable functional group Organic compound that is compatible with a polyether polymer having at least one crosslinkable functional group and a polyether polymer, or a polymer obtained by polymerizing a non-vinyl monomer, or a single vinyl compound The present invention relates to a curable composition containing a compatibilizer (III) selected from the group consisting of polymers obtained by polymerizing a system monomer.

[0002]

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

[0003] If a vinyl polymer having an alkenyl group at a molecular chain terminal can be obtained by a simple method, a cured product having excellent cured properties can be obtained as compared with a product having a crosslinkable group in a side chain. it can. Therefore, many researchers have studied the production method, but it is not easy to produce them industrially. For example, JP-A-1-
JP-A-247403 and JP-A-5-255415 disclose a method of synthesizing a (meth) acrylic polymer having an alkenyl group at a terminal using an alkenyl group-containing disulfide as a chain transfer agent.

Japanese Patent Application Laid-Open No. 5-262808 discloses that a vinyl polymer having a hydroxyl group at both terminals is synthesized using a disulfide having a hydroxyl group, and the vinyl polymer having a hydroxyl group at both ends is further utilized by utilizing the reactivity of the hydroxyl group. A method for synthesizing a (meth) acrylic polymer having an alkenyl group is disclosed.

JP-A-5-212922 discloses that a vinyl polymer having hydroxyl groups at both ends is synthesized by using a polysulfide having a hydroxyl group, and furthermore, by utilizing the reactivity of the hydroxyl groups, a vinyl polymer having a hydroxyl group at both ends is obtained. A method for synthesizing a (meth) acrylic polymer having a silyl group is disclosed.

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

[0007] In contrast to such conventional techniques, the inventors have made numerous inventions on vinyl polymers having various crosslinkable functional groups at their terminals, their production methods, curable compositions, and uses. (Japanese Unexamined Patent Application Publication No. 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, JP-A-11-08
0570, JP-A-11-130931, JP-A-11-1
00433, JP-A-11-116763, JP-A-9-2
No. 72714, JP-A-9-272715, etc.).

For example, a vinyl polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group capable of being crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silyl group”). The cured product obtained from the coalescing or its composition has excellent heat resistance or weather resistance, and is used for electric and electronic materials such as sealing materials such as elastic sealing materials for construction, sealing materials for double glazing, and sealing materials on the back of solar cells. Parts materials, electrical insulation materials such as insulation coatings for wires and cables, adhesives, adhesives, elastic adhesives,
Paints, powder paints, coating materials, foams, potting agents for electric and electronic devices, films, gaskets, casting materials, various molding materials, and rust-proof and waterproof seals for netted glass and laminated glass edges (cut sections) It is used for various applications such as anti-stop materials, automobile parts, electric parts, and various mechanical parts.

On the other hand, polyether polymers having at least one crosslinkable silyl group are disclosed, for example, in JP-B-45-36.
No. 319, No. 46-12154, No. 46-30741
No. 49-32673, JP-A-50-156599.
No. 51-73561, No. 54-6096, No. 5
Nos. 5-13767, 55-13768 and 55-8
No. 2123, No. 55-123620, No. 55-125
No. 121, No. 55-131021, No. 55-1310
No. 22, No. 55-135135, No. 55-13712
No. 9, JP-A-3-72527 and JP-A-3-97825, and when cured, a high-elongation cured product is obtained, which is mainly used as an elastic sealing material for buildings and the like. I have. However, these polyethers, especially polyethers having polypropylene oxide as a main chain, have a problem that unless an antioxidant is used, hydrogen atoms bonded to tertiary carbon are easily oxidized and weather resistance is deteriorated. In order to solve this problem, the present inventors have already made Japanese Patent Publication No.
Nos. 42367 and 2-44845, weather resistance is improved by blending an acrylic polymer having at least one crosslinkable silyl group with a polyether polymer having at least one crosslinkable silyl group. A curable composition was proposed. In addition, Japanese Patent Publication No. 4-69667
Discloses a sealant composition prepared by blending an acrylic polymer having an alkoxysilyl group at both molecular ends prepared using a chain transfer agent and a polyether polymer having an alkoxysilyl group at both molecular ends. .

[0010]

A vinyl polymer having at least one crosslinkable functional group blended with a polyether polymer having at least one crosslinkable functional group comprises:
It is usually produced using a radical polymerization initiator having a crosslinkable functional group or a chain transfer agent. For this reason, it is difficult to introduce a crosslinkable functional group at both ends in a high ratio, and there is a problem that the gel content of the cured product is reduced. On the other hand, it is necessary to use a monomer having a crosslinkable functional group in combination in order to obtain a sufficient gel content of the cured product, but in this case, the high elongation characteristic inherent in the polyether polymer is impaired. There was a problem. In this case, particularly, the elongation at break becomes low, so that the use of the composition is greatly limited. Therefore, when used as a sealing material, some physical properties such as an increase in modulus, a decrease in elongation, a deterioration in residual tack, and a decrease in gel content have to be sacrificed in order to improve weather resistance. In addition, since the (meth) acrylic polymer used here is synthesized by free radical polymerization, the molecular weight distribution is wide and the viscosity is high, and the mixture with the polyether polymer also has a high viscosity. There were also problems.

To solve this problem, Japanese Patent Application Laid-Open No. 11-11676 discloses
In 3, the use of a vinyl polymer having a low viscosity and a high proportion of a crosslinkable functional group introduced into the polymer terminal impairs the original high elongation of the polyether polymer having a crosslinkable functional group. It has been proposed that a curable composition having a high gel content and excellent weather resistance can be obtained.
However, in this case, the compatibility of the two polymers may not be sufficient depending on the molecular weight and molecular weight distribution of the vinyl polymer and the polyether polymer, and the blend ratio of the two polymers. In this case, if the blended curable composition is stored for a long period of time, the composition may be separated and storage stability may be deteriorated. In addition, a cured product obtained from a composition having insufficient compatibility may not be able to achieve good mechanical properties due to poor uniformity.

In the present invention, a polymer obtained by polymerizing an organic compound which is not a polymer, a monomer other than a vinyl monomer, or a polymer obtained by polymerizing a single vinyl monomer is used. By adding a selected compatibilizer, a vinyl polymer having at least one crosslinkable functional group and a polyether polymer having at least one crosslinkable functional group are compatible with each other, so that the cured product is a polyether polymer. An object of the present invention is to provide a curable composition having excellent weather resistance and excellent storage stability without impairing high elongation and the like derived from a polymer.

[0013]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned situation, and as a result, have found that the above-mentioned problems can be solved by adding a compatibilizing agent. That is, the present invention provides a vinyl polymer (I) having at least one crosslinkable functional group, which is incompatible with the vinyl polymer, and
Compatibilization for adding a polyether polymer (II) having at least one crosslinkable functional group and a mixture of the vinyl polymer and the polyether polymer to make them compatible with each other At least one phase selected from the group consisting of an organic compound that is not a polymer, a polymer obtained by polymerizing a monomer other than vinyl, and a polymer obtained by polymerizing a single vinyl monomer. The present invention relates to a curable composition containing a solubilizer (III).

In the present invention, the expression that the vinyl polymer (I) and the polyether polymer (II) are "incompatible" means that these two kinds of polymers are sufficiently mixed and then the lid is closed. After standing in a glass bottle at room temperature (15 ° C. to 23 ° C.) for one day, the interface between the vinyl polymer (I) and the polyether polymer (II) is visually confirmed.

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 by mainly polymerizing monomers selected from the group, more preferably a (meth) acrylic monomer, further preferably an acrylic monomer, more preferably an acrylate 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 not limited, but is preferably produced by living radical polymerization, more preferably atom transfer radical polymerization. Further, the atom transfer radical polymerization is not limited, but may be a group 7, 8, 9, 10, or
Alternatively, a complex selected from transition metal complexes having a Group 11 element as a central metal is preferably used as a catalyst, and a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes is more preferable. Particularly preferred.

Further, the vinyl polymer (I) is not particularly limited, but the weight average molecular weight (Mw) and the number average molecular weight (Mw) 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 may be a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, a 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 is preferably at the terminal. In addition, a similar functional group may be provided inside the main chain, but it is preferable to have a functional group only at the terminal when a crosslinked cured product requires rubber elasticity.

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

The compatibilizer is not particularly limited.
Dibutyl phthalate, diheptyl phthalate, di (2-
Phthalates such as ethylhexyl) phthalate and butylbenzyl phthalate; non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate; Aliphatic esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; phosphates such as tricresyl phosphate and tributyl phosphate; trimellitate;
Polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; Polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and derivatives thereof in which hydroxyl groups of these polyether polyols are converted into ester groups, ether groups, etc .; epoxidized soybean oil, benzyl epoxy stearate And other dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid, and ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol. Polyester-based plasticizers obtained from dihydric alcohols such as toluene and dipropylene glycol; vinyl-based polymers obtained by polymerizing a single vinyl-based monomer such as an acrylic plasticizer by various methods; Can be used.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl polymer (I) having at least one crosslinkable functional group and a polyether polymer (II) having at least one crosslinkable functional group.
Characterized in that it is a curable composition comprising the compatibilizer (III), and the cured product has excellent weather resistance without impairing the original high elongation of the polyether polymer having a crosslinkable functional group, Although it relates to a curable composition having good storage stability,
Hereinafter, the curable composition of the present invention will be described in detail. << About the vinyl polymer (I) >><Mainchain> The inventors have hitherto described various vinyl polymers having various crosslinkable functional groups at their terminals, a production method thereof, a curable composition, and applications. (Japanese Patent Application Laid-Open Nos. 11-080249, 11-080250, 11-005815, 11-116617, 11-116606, 11-116606, 11-080571,
JP-A-11-080570, JP-A-11-13093
1, JP-A-11-100433, JP-A-11-1167
63, JP-A-9-272714, JP-A-9-2727
No. 15, etc.). The vinyl polymer (I) of the present invention is not particularly limited, but all the polymers disclosed in the above exemplified invention can be suitably used.

The vinyl monomer constituting the main chain of the vinyl 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,
-Tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) -N-octyl acrylate, 2-ethylhexyl (meth) acrylate,
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) acryl (Meth) acrylic monomers such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth) acrylate and 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 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 monomers such as maleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; acrylonitrile Acrylonitrile monomers such as methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; ethylene; 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 acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. Here, “mainly” means 50% of the monomer units constituting the vinyl polymer.
It means that at least mol%, preferably at least 70%, is the above monomer.

Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and still more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, or further, may be subjected to block copolymerization. In such a case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The molecular weight distribution of the polymer (I) of the present invention, that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is preferably less than 1.8. It is more preferably at most 1.7, further preferably at most 1.6, further preferably at most 1.5, particularly preferably at most 1.4, most preferably at most 1.3.
In the GPC measurement in the present invention, chloroform is usually used as a mobile phase, the measurement is performed using a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

The number average molecular weight of the vinyl polymer (I) of the present invention is not particularly limited, but is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, as measured by gel permeation chromatography. . If the molecular weight is small, high elongation of the cured product may not be easily exhibited. In the same case, 100
It is preferably at most 0000, more preferably at most 100,000, even more preferably at most 50,000. <Synthesis method of main chain> Vinyl polymer (I) in the present invention
Although the synthesis method of is not limited, controlled radical polymerization is preferred, living radical polymerization is more preferred, and atom transfer radical polymerization is particularly preferred. These will be described below. Controlled radical polymerization The 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 using an azo compound, a peroxide, or the like as a polymerization initiator. It can be classified as a "controlled radical polymerization method" in which a specific functional group can be introduced at a controlled position such as a terminal.

The "general radical polymerization method" is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only stochastically. If it is intended to obtain such a monomer, it is necessary to use this monomer in a considerably large amount. Conversely, if the monomer is used in a small amount, there is a problem that the proportion of the polymer into which this specific functional group is not introduced becomes large. In addition, 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" further includes a "chain transfer agent method" in which a vinyl polymer having a terminal functional group is obtained by performing polymerization using a chain transfer agent having a specific functional group. It can be classified as a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing a polymerized growth terminal without causing a termination reaction or the like.

The "chain transfer agent method" is capable of obtaining a polymer having a high degree of functionalization, but requires a considerably large amount of a chain transfer agent having a specific functional group with respect to the initiator, and requires a treatment. There is a problem in the economy, including that. Further, similarly to the above-mentioned "general radical polymerization method", there is also a problem that since the polymerization is a free radical polymerization, only 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 a termination reaction is likely to occur due to coupling between radicals. The reaction hardly occurs 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, the "living radical polymerization method" can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer. Therefore, the method for producing a vinyl polymer having the above specific functional group is more preferable.

In the narrow sense of living polymerization,
This refers to polymerization in which the molecular chain grows with the terminal always having activity. Living polymerization is also included. The definition in the present invention is also the latter.

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

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a vinyl monomer is polymerized with an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned "living radical polymerization method". In addition to the features of the `` radical polymerization method, '' the vinyl-based polymer having a specific functional group has halogens at the terminals that are relatively advantageous for the functional group conversion reaction, and has a high degree of freedom in designing initiators and catalysts. It is more preferable as a method for producing a united product. 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.
Year, Volume 28, p. 7901, Science
e) 1996, 272, 866, WO 96/30
No. 421, WO97 / 18247, WO98
/ 01480, WO98 / 40415, or Sawamoto et al., Macromolecules (M
acromolecules) 1995, volume 28, 1
721 page, JP-A-9-208616, JP-A-8-208
41117 and the like.

In the present invention, any of these living radical polymerization methods is not particularly limited, but an atom transfer radical polymerization method is preferable.

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

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

Hereinafter, living radical polymerization will be described.

First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a 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 radicals and 2,
Preferred are nitroxy free radicals from cyclic hydroxyamines, such as 2,5,5-substituted-1-pyrrolidinyloxy radicals. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,
2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-
1-pyrrolidinyloxy radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical,
N, N-di-t-butylamineoxy radical and the like. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

The above radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator, and the polymerization of the addition-polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of 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 polymerization temperature conditions 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; Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Particularly, benzoyl peroxide is preferred. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of the peroxide.

Macromolecules 199
As reported in US Pat. No. 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]

Embedded image 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 functional group at a terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at a terminal can be obtained.

Polymerization conditions such as a monomer, a solvent, and a polymerization temperature used in the polymerization using a radical scavenger such as a nitroxide compound are not limited, but may be the same as those used for atom transfer radical polymerization described below. . Atom transfer radical polymerization Next, a more preferable 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. For example, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C (H) (X) CH ₃ , C ₆
H ₅ -C (X) (CH ₃ ) ² (where 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 , wherein R ¹ and R ² are a hydrogen atom or an alkyl, aryl, or aralkyl group having 1 to 20 carbon atoms , X is chlorine, bromine or iodine) R ¹ -C at ₆ H ₄ -SO ₂ X (above equations, R ¹ is 1 number of hydrogen atoms or carbon,
To 20 alkyl groups, aryl groups, or aralkyl groups, and X is chlorine, bromine, or iodine).

As the initiator of the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group that initiates the polymerization can be used. In such a case, a vinyl polymer having a functional group at one main chain terminal and a growing 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, and R ⁴ and R ⁵ are hydrogen or carbon A monovalent alkyl group, an aryl group, or an aralkyl of the formulas 1 to 20, or those mutually linked at the other end, R ⁶ is —C (O) O— (ester group), —C (O) — ( Keto group), or o-, m-, p
A phenylene group, R ⁷ is a direct bond, or has 1 to 2 carbon atoms;
0 is a divalent organic group which may contain one or more ether bonds. X is chlorine, bromine, or iodine. Specific examples of the substituents R ⁴ and R ⁵ include hydrogen, methyl, and ethyl. , N-propyl group, isopropyl group, butyl group,
Examples include a pentyl group and a hexyl group. R ⁴ and R ⁵ may be linked at the other end to form a cyclic skeleton.

As specific examples of the organic halide having an alkenyl group represented by the general formula (1), XCH ₂ C (O) O (CH ₂ ) _n CHＣＨCH 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]

Embedded image (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]

Embedded image(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC
(H) (X) -C₆H_Four− (CH_Two)_n-CH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-O- (C
H_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four− (CH_Two)_n-O- (CH_Two)_m-CH =
CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H
_Four− (CH_Two)_n-O- (CH_Two)_mCH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
O- (CH_Two)_n-CH = CH_Two, O, m, p-CH _ThreeCH
_TwoC (H) (X) -C₆H_Four-O- (CH_Two)_n-CH = C
H_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-O-
(CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_n-O- (CH_Two) _m-C
H = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X)-
C₆H_Four-O- (CH _Two)_n-O- (CH_Two)_m-CH = CH
_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Element, n is an integer of 1 to 20, m is an integer of 0 to 20) As an organic halide having an alkenyl group,
A compound represented by the general formula (2) is exemplified. H_TwoC = C (R^Three) -R⁷-C (R^Four) (X) -R⁸-R^Five (2) (where R^Three, 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
R which represents a len group)⁶Is a direct bond or has 1 to 20 carbon atoms
Divalent organic groups (including one or more ether linkages)
Is good, but if it is a direct bond,
A vinyl group is bonded to the bonded carbon, and halogen
Allylic compound. In this case, the adjacent vinyl groups
The carbon-halogen bond is activated,⁸When
It is necessary to have C (O) O group or phenylene group
Alternatively, a direct connection may be used. R⁷Is a direct bond
If not, to activate the carbon-halogen bond,
R⁸Are C (O) O group, C (O) group, phenylene group
Is preferred.

If the compound of the general formula (2) is specifically exemplified, CH ₂ ＣＨCHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH ₂ X, C
H ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (CH ₃ ) C
(H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (CH ₃ ) ₂ ,
CH ₂ ＣＨCHC (H) (X) C ₂ H ₅ , CH ₂ ＣＨCHC
(H) (X) CH (CH ₃ ) ₂ , CH ₂ ＣＨCHC (H)
(X) C ₆ H ₅ , CH ₂ ＣＨCHC (H) (X) CH ₂ C
_{6 H 5, CH 2 = CHCH} 2 C (H) (X) -CO 2 R, C
H ₂ ＣＨCH (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.

Specific examples of the sulfonyl halide compound having an alkenyl group include: o-, m-, p-CH ₂ ＣＨCH— (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).

Organic halogen having crosslinkable silyl group
The compound is not particularly limited, and may be, for example, a compound represented by the general formula (3):
One having a structure shown in FIG. R^FourR^FiveC (X) -R⁶-R⁷-C (H) (R^Three) CH_Two− [Si (R⁹)_2-b(Y)_b O]_m-Si (R^Ten)_3-a(Y)_a (3) (where R^Three, R^Four, R^Five, R⁶, R⁷, X is the same as above,
R⁹, R^TenIs an alkyl group having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ′)_ThreeSiO-
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different
I) represents a triorganosiloxy group represented by⁹Ma
Or R^TenWhen two or more exist, they are the same.
Or may be different. Y is a hydroxyl group or water
A decomposable group, and when two or more Y
They 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. Where a + mb ≧ 1
The compound of the general formula (3)
To give a concrete example, XCH_TwoC (O) O (CH_Two)_nSi (OCH_Three)_Three, CH_Three
C (H) (X) C (O) O (CH_Two)_nSi (OC
H_Three)_Three, (CH_Three)_TwoC (X) C (O) O (CH_Two)_nSi
(OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_nSi (C
H_Three) (OCH_Three)_Two, CH _ThreeC (H) (X) C (O) O
(CH_Two)_nSi (CH_Three) (OCH_Three)_Two, (CH_Three)_TwoC
(X) C (O) O (CH_Two)_nSi (CH_Three) (OCH_Three)
_Two(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 0 to 20, XCH_TwoC (O) O (CH_Two)_nO (CH_Two)_mSi (OC
H_Three)_Three, H_ThreeCC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_mSi (OCH_Three)_Three, (H_ThreeC)_TwoC (X) C
(O) O (CH_Two)_nO (CH_Two)_mSi (OCH_Three)_Three, C
H_ThreeCH_TwoC (H) (X) C (O) O (CH_Two)_nO (CH
_Two)_mSi (OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_n
O (CH_Two)_mSi (CH_Three) (OCH_Three)_Two, H_ThreeCC
(H) (X) C (O) O (CH_Two)_nO (CH_Two)_m-Si
(CH_Three) (OCH_Three)_Two, (H_ThreeC)_TwoC (X) C (O)
O (CH_Two)_nO (CH_Two)_m-Si (CH_Three) (OCH_Three)
_Two, CH_ThreeCH _TwoC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_m-Si (CH_Three) (OCH_Three)_Two(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
(CH_Two)_TwoSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_Two
C (H) (X) -C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_ThreeS
i (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X)-
C₆H_Four− (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, pc
H_ThreeCH_TwoC (H) (X) -C₆H_Four− (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_Two
-O- (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH
_ThreeC (H) (X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)
_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_TwoC (H)
(X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four-O- (C
H_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Three-Si (OCH_Three)_Three, O, m, p-XCH_Two
-C₆H_Four-O- (CH_Two)_Two-O- (CH_Two)_Three-Si (O
CH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four
-O- (CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three(In the above formulas, X represents chlorine, bromine, or iodine.
Element) and the like.

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

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

Embedded image (In each of the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
An aryl group, an aralkyl group, and n is an integer of 1 to 20) To obtain a polymer having two or more terminal structures in one molecule of the present invention, 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]

Embedded image

[0059]

Embedded image And the like.

The vinyl monomer used in this polymerization is not particularly limited, and any of those already exemplified can be suitably used.

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

The 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, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvent, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, alcohol solvents such as tert-butyl alcohol, acetonitrile, propionitrile, nitrile solvents such as benzonitrile, ethyl acetate, ester solvents such as butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, which may be used alone or in combination of two or more. Also, although not limited, polymerization is 0
C. to 200.degree. C., preferably 50.degree.
１５０150 ° C.

The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization refers to a highly oxidized state when a normal atom transfer radical polymerization catalyst generates radicals, for example, Cu (II ′) when Cu (I) is used as a catalyst.
Is reacted with a general radical initiator such as peroxide to produce an equilibrium state similar to that of atom transfer radical polymerization (Macromolecule).
es 1999, 32, 2872). <Functional group> The crosslinkable functional group of the vinyl polymer (I) is not limited, but may be a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, a polymerizable carbon-carbon double bond,
Epoxy groups and the like are preferred.

All of these crosslinkable functional groups can be properly used depending on the use / purpose.

The vinyl polymer (I) has at least one crosslinkable functional group on average. From the viewpoint of curability of the composition, it is preferable to have more than one,
The average is more preferably 1.1 to 4.0 on average, and still more preferably 1.5 to 2.5 on average. Position of crosslinkable functional group When rubber-like properties are particularly required in the cured product of the curable composition of the present invention, the molecular weight between crosslink points that greatly affects rubber elasticity can be increased, so that the crosslinkable functional group Is preferably at the end of the molecular chain. More preferably, it has all crosslinkable functional groups at the molecular chain terminals.

A method for producing a vinyl polymer having at least one crosslinkable functional group at a molecular terminal, in particular, 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 “chain transfer agent method”, the resulting polymer has a relatively high proportion of crosslinkable functional groups at the molecular chain terminals, while Mw / Mn
Has a problem that the value of the molecular weight distribution represented by is generally as large as 2 or more, and 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 high proportion of a crosslinkable functional group at a molecular chain terminal, the above-mentioned "living radical polymerization method" is used. Is preferred.

Hereinafter, these functional groups will be described. The crosslinking silyl group of the crosslinkable silyl group present invention, the general formula (5); - [Si ( R 9) 2-b (Y) b O] m -Si (R 10) 3-a (Y) a (5) In the formula, each of R ⁹ and R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
An aralkyl group, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′
May be the same or different), and R ⁹ or R ¹⁰ is 2
When there are more than one, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. And a group represented by｝.

Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group. It is. Among these, an alkoxy group, an amide group and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 (a + Σ
b) is preferably in the range of 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 a crosslinkable silyl group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number 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 as defined above) is available. Is preferred because it is easy.

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

Further, although not limited, the polymer (I)
Is preferably not activated by a carbonyl group, alkenyl group or aromatic ring conjugated to the carbon-carbon double bond.

The type of bonding between the alkenyl group and the main chain of the polymer is not particularly limited, but 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. The amino group at the amino group present invention, but are not limited to, -NR ¹² ₂ (R ¹² is a hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ¹² are different may be the same with each other even if well, also connected to each other at the other end, but may form a cyclic structure) and the _{^{like, -. (NR 12 3)}} + X - (R 12 is the same .X as above ^- Is a counter anion.), There is no problem.

In the above formula, R ¹² is hydrogen or a group having 1 to 2 carbon atoms.
0 is a monovalent organic group, for example, hydrogen, 1-2 carbon atoms
Examples 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 may be the same or different. Further, they may be connected to each other at the other end to form an annular structure. Polymerizable carbon-carbon double bond The group having a polymerizable carbon-carbon double bond is preferably a compound represented by the following general formula (8): -OC (O) C (R ¹³ ) = CH ₂ (8) In the formula, R ¹³ represents 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 there.

In the general formula (8), specific examples of R ¹³ are not particularly limited, and include, for example, —H, —CH ₃ , —CH ₂
CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , —CH ₂ OH, —CN, and the like, preferably —H, —CH ₃ It is. <Method for Introducing Functional Group> The method for introducing a functional group into the vinyl polymer (I) of the present invention will be described below, but the method is not limited thereto.

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

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a hydrosilane compound having a crosslinkable silyl group in a vinyl polymer having at least one alkenyl group may be used as a hydrosilylation catalyst. (B) at least one hydroxyl group
A method in which 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 is reacted with one vinyl polymer; (C) when synthesizing a vinyl polymer by radical polymerization A method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule; (D) using a chain transfer agent having a crosslinkable silyl group when synthesizing a vinyl polymer by radical polymerization. And (E) a method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a compound having a crosslinkable silyl group and a stable carbanion in one molecule.

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 is not limited thereto.

(Aa) When a vinyl polymer is synthesized by radical polymerization, for example, a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (9) And reacting a compound having the following 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 an o-, m-, p-phenylene group; R ¹⁶ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, including one or more ether bonds. It may be. 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.) 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, when rubbery properties are expected in living radical polymerization, it is preferable to react as a second monomer at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer.

(Ab) When a vinyl-based polymer is synthesized by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 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 an organic tin such as allyltributyltin and allyltrioctyltin may be added to the vinyl polymer having at least one highly reactive carbon-halogen bond. A method in which a halogen is substituted by reacting a metal compound.

(Ad) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (10) to form a halogen. How to replace. ^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10) ( wherein, R ¹⁷ is as defined above, R ^18, R ¹⁹ together carbanion C ^- stable Or one of them is the above-mentioned electron-withdrawing group and the other is hydrogen or a carbon atom having 1 to 10 carbon atoms.
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 groups for R ¹⁸ and R ¹⁹ include —CO ₂ R and —C
Those having the structure of (O) R and -CN are particularly preferred.

(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. An alkenyl group-containing electrophilic compound 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) The vinyl polymer having at least one highly reactive carbon-halogen bond may be, for example, an oxyanion or carboxy having an alkenyl group represented by the general formula (11) or (12). A method in which a halogen is substituted 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
H ₂ C 有機 C (R ¹⁷ ) -R ²² -C (O) O ⁻ M ⁺ (12) wherein R 2 is a divalent organic group which may contain one or more ether bonds. ¹⁷ , M ⁺ is the same as described above, and R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds.

The above-mentioned method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is based on an atom transfer radical using an organic halide as described above as an initiator and a transition metal complex as a catalyst. Examples include, but are not limited to, polymerization methods.

The vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but it is not limited to these. is not.
(Ag) A method in which a base such as sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group to react with an alkenyl group-containing halide such as allyl chloride.

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

(Ai) A method in which an alkenyl group-containing acid halide such as (meth) acrylic acid chloride is reacted 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;

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

When an alkenyl group is introduced by converting a 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 may be used. Halide, 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 terminal
It is preferable to use a vinyl polymer having two or more vinyl polymers. The method (Af) is more preferable because the control is easier.

The hydrosilane compound having a crosslinkable silyl group is not particularly limited, but a typical example is a compound represented by the general formula (13). H- [Si (R ⁹ ) _2-b (Y) _b O] _m -Si (R ¹⁰ ) _3-a (Y) _a (13) wherein R ⁹ and R ¹⁰ each have 1 carbon atom Alkyl group having 20 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms
An aralkyl group, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′
May be the same or different), and R ⁹ or R ¹⁰ is 2
When there are more than one, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied.の Among these hydrosilane compounds, particularly the general formula (1)
4) A compound having a crosslinkable group represented by H-Si (R ¹⁰ ) _3-a (Y) _a (14) (wherein R ¹⁰ , Y and a are the same as above) is preferred from the viewpoint of easy availability. .

When adding the above-mentioned hydrosilane compound having a crosslinkable silyl group to an alkenyl group, a transition metal catalyst is usually used. As the transition metal catalyst, for example, platinum alone, alumina, silica, a dispersion of platinum solids on a carrier such as carbon black, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc.
Platinum-olefin complexes and platinum (0) -divinyltetramethyldisiloxane complexes are mentioned. 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.

The methods for producing the vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) are exemplified by the following methods. It is not limited to.

(Ba) When a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (15) is used. A method of reacting as a second monomer. H ₂ C ＝ C (R ¹⁴ ) —R ¹⁵ —R ¹⁶ —OH (15) (wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above) A polymerizable alkenyl group and a hydroxyl group in one molecule There is no limitation on the timing of reacting the compound having both of the above. Particularly, in the case of living radical polymerization, when a rubber-like property is expected, the reaction is carried out 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, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, for example, an alkenyl such as 10-undecenol, 5-hexenol or allyl alcohol is used. A method of reacting alcohol.

(Bc) For example, JP-A-5-262808
A radical polymerization of a vinyl monomer using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide shown in (1).

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

(Be) For example, Japanese Unexamined Patent Publication No.
A method of radically polymerizing a vinyl monomer by using an excess of alcohols as described in (1).

(Bf) For example, JP-A-4-132706
A method of introducing a hydroxyl group into a 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 by a method such as that described in US Pat.

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

(Bh) An enolate anion is prepared by reacting a vinyl 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 may be added to a hydroxyl group-containing oxyanion or carboxylate represented by the general formula (17) or (18). A method in which halogen is substituted by reacting an anion. ^{HO-R 21 -O - M +} (17) ( wherein, R ²¹ and M ⁺ are the ^{same) HO-R 22 -C (O} ) O - M + (18) ( wherein, R ²² and M ⁽⁺ Is the same as described above). (Bj) When synthesizing a vinyl polymer by living radical polymerization, at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer, a polymerizable compound in one molecule is used as a second monomer. A compound having a low alkenyl group and a hydroxyl group.

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

In the present invention, when a halogen is not directly involved in a method for introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl radical is produced by a living radical polymerization method. Preferably, a polymer is synthesized. The method (Bb) is more preferable because the control is easier.

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

Examples of the compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and the like. γ-isocyanatopropyltriethoxysilane and the like. If necessary, a generally known catalyst for a urethane reaction can be used.

Examples of the compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include, for example, trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. Such a compound represented by the following general formula (20) is exemplified. ^{_{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 Wherein R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ , Y, a, b, and m are the same as those described above, and R ²³ is a direct bond or a divalent organic group having 1 to 20 carbon atoms, and There may be 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 rubbery properties are expected especially in living radical polymerization. In this case, it is preferable to react as the second monomer at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer.

As the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method (D), for example,
And mercaptan having a crosslinkable silyl group, hydrosilane having a crosslinkable silyl group, and the like, which are described in JP-A-14068 and JP-B-4-55444.

In the method for synthesizing the vinyl polymer having at least one highly reactive carbon-halogen bond used in the method (E), the above-mentioned organic halide or the like is used as an initiator, Examples include, but are not limited to, atom transfer radical polymerization using a metal complex as a catalyst. As a compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule, a compound represented by the general formula (21) can be given. ^{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) (wherein, R ⁹ , R ¹⁰ , R ¹⁸ , R ¹⁹ , Y, a, b, and m are the same as those described above. R ²⁴ is a direct bond or a group having 1 to 1 carbon atoms. R ²⁵ may be hydrogen, 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 may contain one or more ether bonds in the divalent organic group of 10.
Represents an aralkyl group. As the electron-withdrawing groups for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferred. 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 reacting a compound having both a reactive functional group and an ethylenically unsaturated group;

Further, in the atom transfer radical polymerization, a method in which an allyl alcohol is reacted at the end of the polymerization, and thereafter, an epoxy cyclization with a hydroxyl group and a halogen group may be mentioned. The method for producing a vinyl polymer having at least one amino group at the terminal of the main chain includes the following steps. (1) A vinyl polymer having at least one halogen group at the terminal of the main chain is produced, and (2) a terminal halogen is converted into a substituent having an amino group using an amino group-containing compound.

Examples of the substituent having an amino group include, but are not particularly limited to, groups represented by the general formula (22). _{^{-O-R 26 -NR 12 2 (}} 22) ( wherein, R ²⁶ represents one or more ether bonds or ester bonds carbon atoms which may contain 1 to 20 divalent organic group .R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ^{12 s} may be the same or different from each other, and are connected to each other at the other end to form a cyclic structure. In the above general formula (22), R26 has 1 or more carbon atoms which may contain one or more ether bonds or ester bonds.
A divalent organic group of 20, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, but like an aralkylene group having 7 to 20 carbon atoms, -C ₆ H ₄ - R ²⁷ − (wherein, C ₆ H ₄ represents a phenylene group, and R ²⁷ represents a divalent organic group having 1 to 14 carbon atoms which may have a direct bond or one or more ether bonds or ester bonds. .) ^{or, -C (O) -R 28 -} ( wherein, R ²⁸ is a direct bond or one or more ether bonds or ester bonds carbon atoms which may contain 1 to 19
Represents a divalent organic group. Is preferred.

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

As specific compounds, 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 be used as a nucleophile. Such a compound is not particularly limited. For example, the compound represented by the general formula (2)
The compound shown in 4) is mentioned. ^{M + O - -R 26 -NR 12} 2 (24) ( wherein, R ²⁶ represents a divalent organic group having one or more ether bonds or carbon atoms, which may contain an ester bond 20 .R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ¹² may be different may be the same each other, 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. Represent. Examples of the alkali metal ion include a lithium ion, a sodium ion, and a potassium ion, and are preferably a sodium ion or a potassium ion. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a trimethylbenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion.

Among the above-mentioned compounds having both an amino group and an oxyanion, the salts of aminophenols represented by the general formula (25) or the general formula ( The salts of the amino acids shown in 26) 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 And the other end may be mutually connected to form a cyclic structure. M ⁺ is the same as described above.) Compounds having oxyanions represented by general formulas (24) to (26) Can be easily obtained by reacting the compound represented by the general formula (23) with a basic compound. That.

Various compounds can be used as the basic compound. For example, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium-tert-butoxide, potassium-tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, hydrogen hydrogen carbonate Sodium, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, ter
t-butyllithium, lithium diisopropylamide,
Lithium hexamethyldisilazide and the like. The amount of the base used is not particularly limited, but is 0.5 to 5 equivalents, preferably 0.8 to 1.2 equivalents, based on the precursor.

Examples of the solvent used for reacting the precursor with the base include: hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; and halogenated solvents such as methylene chloride and chloroform. Hydrocarbon solvents; ketone solvents 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; and sulfoxide solvents such as dimethylsulfoxide. These can be used alone or in combination of two or more.

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

Various solvents may be used for the substitution reaction of the terminal halogen of the polymer. For example, hydrocarbon solvents such as benzene and toluene; diethyl ether;
Ether solvents such as tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents 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, dimethyl Examples 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 can be carried out at a temperature of 0 to 150 ° C. The amount of the amino group-containing compound to be used is not particularly limited, but is 1 to 5 equivalents, preferably 1 to 1.2 equivalents, relative to the terminal halogen of the polymer.

In order to accelerate the nucleophilic substitution reaction, a basic compound may be added to the reaction mixture. Examples of such basic compounds include, in addition to those already exemplified, alkylamines such as trimethylamine, triethylamine and tributylamine; polyamines such as tetramethylethylenediamine and pentamethyldiethylenetriamine; and 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 preferable to protect the amino group-containing compound with an appropriate substituent. Such substituents include a benzyloxycarbonyl group,
Examples thereof include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

Further, there is a method in which the halogen terminal of the vinyl polymer is substituted with an azide anion and then reduced with LAH or the like. Polymerizable carbon-carbon double bond A method for introducing a polymerizable carbon-carbon double bond into the polymer (I) of the present invention is not limited, but includes the following methods. A method for producing a vinyl polymer by substituting a halogen group of a vinyl polymer with a compound having a radically polymerizable carbon-carbon double bond. As a specific example, a method in which a vinyl polymer having a structure represented by the general formula (27) is reacted with a compound represented by the general formula (28). ²⁹ R ³⁰ X (27) (wherein, R ^29, R ³⁰ is a group .X bonded to an ethylenically unsaturated group of a vinyl monomer represents chlorine, bromine, or iodine.) -CR M ^{+ - OC (O) C (R} 13) = CH 2 (2
8) (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 vinyl polymer having a hydroxyl group and a general formula A method by reaction with the compound represented by (29). XC (O) C (R ¹³ ) ＝ CH ₂ (29) (wherein, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.) A diisocyanate compound is allowed to react with a vinyl polymer having
A method by reaction with the compound represented by 0). ^{HO-R 31 -OC (O)} C (R 13) = CH 2 (30) ( wherein, R ¹³ is hydrogen or,, .R ³¹ 2 to 20 carbon atoms represents an organic group having 1 to 20 carbon atoms These methods are described in detail below.

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

The compound represented by the general formula (28) is not particularly limited. 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, preferably —H and —CH ₃ . M ⁺ is a counter cation of the oxyanion, and examples of M ⁺ include an alkali metal ion, specifically, a lithium ion, a sodium ion, a potassium ion, and a quaternary ammonium ion. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a tetrabenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion, and a sodium ion and a potassium ion are preferable. The amount of the oxyanion of the general formula (28) to be used is preferably 1 to 5 equivalents, more preferably 1.0 to 5 equivalents to the halogen group of the general formula (27).
1.2 equivalents. The solvent for carrying out this reaction is not particularly limited, but a polar solvent is preferred because it is a nucleophilic substitution reaction. Triamide, acetonitrile,
Are used. The temperature at which the reaction is carried out is not limited, but is generally from 0 to 150 ° C, preferably from room temperature to 100 ° C in order to maintain the polymerizable terminal group.

The above method will be described. A method in which a vinyl polymer having a hydroxyl group is reacted 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 compound represented by the formula (29) is not particularly limited, but specific examples of R ¹³ include, for example, -H, -CH
_{3, -CH 2 CH 3, -} (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like are exemplified, preferably - H, is a -CH _3.

The vinyl polymer having a hydroxyl group at the terminal, preferably at the terminal, is prepared by a method of polymerizing a vinyl monomer using the above-mentioned organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a method of polymerizing a hydroxyl group. Is produced by a method in which a vinyl monomer is polymerized using a compound having the formula (I) as a chain transfer agent, but the former is preferred. 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 a vinyl polymer is synthesized by living radical polymerization, a compound represented by the following general formula (31) and having both a polymerizable alkenyl group and a hydroxyl group in one molecule is used as a second monomer. As a reaction. ^{_{H 2 C = C (R 32}} ) -R 33 -R 34 -OH (31) ( wherein, R ³² is preferably a hydrogen or a methyl group with an organic group having 1 to 20 carbon atoms, being the same or different R ³³ represents —C (O) O— (ester group) or an o-, m- or p-phenylene group, and R ³⁴ has a direct bond or one or more ether bonds. Represents a divalent organic group having 1 to 20 carbon atoms which may be represented by the formula (1) wherein R ³³ is an ester group, and (R ³³ is a phenylene group, a styrene-based compound). There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, but if rubbery properties are particularly expected, the second reaction may be carried out at the end of the polymerization reaction or after completion of a predetermined monomer reaction. It is preferable to react as a monomer of .

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

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

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

(D) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (27) obtained by atom transfer radical polymerization is added to the general formula (3)
A method in which halogen is substituted by reacting a stabilized carbanion having a hydroxyl group as described in 3). ^{M + C - (R 36)} (R 37) 35 -OH (33) ( wherein -R, electronic and R ³⁵ are the same as those described above .R ³⁶ and R ³⁷ is that together stabilize carbanion C- The attraction group, or one of the above, represents the above-mentioned electron withdrawing group and the other represents 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.
And 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 preferred. (E) General formula (2) obtained by atom transfer radical polymerization
7) a vinyl polymer having at least one carbon-halogen bond is reacted with a simple metal such as zinc or an organometallic compound to prepare an enolate anion, followed by an aldehyde or ketone How to react.

(F) A hydroxyl group-containing oxyanion represented by the following general formula (34) is added to a vinyl polymer having at least one halogen at the terminal of the polymer, preferably a halogen represented by the general formula (27) Alternatively, a method of reacting a hydroxyl group-containing carboxylate anion represented by the following general formula (35) or the like to replace 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 a halogen is not directly involved in a method for introducing a hydroxyl group as in (a) to (b), control is easier. The method (b) is more preferred.

In the case where a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one carbon-halogen bond as shown in (c) to (f), the control is easier. The method f) is more preferred.

The above method will be described. A method comprising reacting a diisocyanate compound with a vinyl polymer having a hydroxyl group and reacting the remaining isocyanate group with a compound represented by the general formula (36). ^{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 the general formula (36) is not particularly limited, and specific examples of R ¹³ include, for example, -H, -CH
_{3, -CH 2 CH 3, -} (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like are exemplified, preferably - H, is a -CH _3. Specific compounds include 2-hydroxypropyl methacrylate.

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

The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, tolylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used.

In order to make better use of weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate. << Polyether Polymer (II) >> The polyether polymer having at least one crosslinkable functional group as the component (II) in the present invention contains a urethane bond or a urea bond in the main chain. And may not be included. The main chain of the polyether polymer is not particularly limited,
For example, polyethylene oxide, polypropylene oxide, polybutylene oxide, polyphenylene oxide and the like can be mentioned. Among them, it is preferably essentially a polyoxyalkylene, more preferably essentially a polypropylene oxide, which may contain ethylene oxide, butylene oxide, phenylene oxide and the like in addition to propylene oxide. Here, “the main chain is essentially polypropylene oxide” means that the propylene oxide unit accounts for 50% or more, preferably 70% or more, more preferably 90% or more of the repeating units constituting the main chain. Say. If the viscosity is lower, the handleability becomes better, so that the molecular weight distribution (Mw / Mn) of the polypropylene oxide polymer is 1.5.
The following are more preferred.

The crosslinkable functional group in the component (II) is not particularly limited, and is preferably a crosslinkable silyl group,
Examples include an alkenyl group, a hydroxyl group, an amino group, a group having a polymerizable carbon-carbon double bond, and an epoxy group. Particularly, a crosslinkable silyl group is preferable. These definitions are the same as those described later. The crosslinkable functional group in the component (II) may be of the same type as the crosslinkable functional group in the component (I), or may be of a different type. And the same type is preferable. Even if they are of the same type, they may have the same structure or different structures. In addition, the number of crosslinkable functional groups contained in the polyether polymer (II) is at least one on average, but it is preferably more than one, and more preferably, from the viewpoint of curability of the composition. Is 1.1 to 4.0 on average, more preferably 1.5 on average
~ 2.5. The crosslinkable functional group is preferably located at the end of the polyether polymer from the viewpoint of rubber elasticity of the cured product. More preferably, the polymer has functional groups at both ends.

The method for producing the polyether polymer as the component (II) is not particularly limited, and may be a conventionally known one.

In the case where the polyether polymer having at least one crosslinkable functional group as the component (II) in the present invention contains a urethane bond or a urea bond in the main chain, it is regarded as a polyether polymer. Any organic polymer containing at least one urethane bond or urea bond in the molecule and having at least one crosslinkable functional group may be obtained by any production method. The crosslinkable functional group particularly limited without various functional groups mentioned are but among them the formula as described above ^{_{(37) -SiY a R 36 3}} -a ··· (37) ( provided that wherein R ³⁶ is C 1 -C To 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or R ′ ₃ SiO— (R ′ is 1 to 20 carbon atoms.
A trivalent hydrocarbon group, and three R's may be the same or different), and when two or more R ³⁶ are present, they are the same. May be present or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present,
They may be the same or different. a
Represents 0, 1, 2, or 3. ) Is preferred. Further, as an industrially easy production method of a polyether polymer, an excessive polyisocyanate compound (E) is reacted with a terminal hydroxyl group of an oxyalkylene polymer (D) having a hydroxyl group at a terminal to form a polyurethane main chain. after the polymer having terminal isocyanate groups of the (F) formula (38) or simultaneously said isocyanate _{^{groups, W-R 37 -SiY a R}} 36 3-a ··· (38) ( in the formula R ³⁶ , Y and a are the same as described above, R ³⁷ is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, W is a hydroxyl group, a carboxyl group, a mercapto group or an amino group (primary or secondary). Selected from the group consisting of active hydrogen-containing compounds) and the oxyalkylene polymer (D) having a hydroxyl group at the terminal. ) ^{= C = N-R 37 -SiY} a R 36 3-a ··· (39) ( provided that wherein ^{R 36, R 37, Y,} a is the same.) Hydrolyzable silicon group-containing represented by Those produced by reacting with the isocyanate compound (H) can be used.

The oxyalkylene polymer (D) includes
Although any of those produced by any production method can be used, those having at least 0.7 hydroxyl groups at the terminal per molecular terminal on the whole molecular average are preferable. Specifically, an initiator such as an oxyalkylene polymer produced using a conventional alkali metal catalyst or a polyhydroxy compound having at least two hydroxyl groups in the presence of a double metal cyanide complex (C) or cesium is used. And an oxyalkylene polymer produced by reacting an alkylene oxide.

Among them, the use of the double metal cyanide complex (C) has a lower degree of unsaturation, a higher molecular weight and a lower unsaturation than that of an oxyalkylene polymer produced using a conventional alkali metal catalyst. Mw / Mn is preferable because it is possible to obtain an oxyalkylene polymer (D) having a narrow Mw, a lower viscosity, and a high acid resistance and a high weather resistance.

As the double metal cyanide complex (C), a complex containing zinc hexacyanocobaltate as a main component is preferable, and an ether and / or alcohol complex thereof is preferable. Its composition can be essentially that described in JP-B-46-27250. As the ether, glymes such as tetrahydrofuran, glyme, and diglyme are preferable. Among them, tetrahydrofuran and glyme are preferable because Mw / Mn is narrower and an oxyalkylene polymer (D) having a low degree of unsaturation can be obtained.
As the alcohol, t-butanol described in JP-A-4-145123 is preferable because an oxyalkylene polymer (D) having a low degree of unsaturation can be obtained.

The number of hydroxyl groups in the oxyalkylene polymer (D) is determined in order to increase the molecular weight by reacting with the polyisocyanate compound (E) and to determine the number of hydroxyl groups in the oxyalkylene polymer (D). In order to increase the introduction rate of the compound, it is preferably at least 1.6 or more, more preferably 1.8 to 4, per molecule on the average of all molecules.
Among them, 1.8 to 3 is preferable in order not to cause gelation during the reaction with the polyisocyanate compound (E). Further, an oxyalkylene polymer having 2 or more hydroxyl groups (D)
Can be produced by substituting a part or all of the bifunctional initiator with a trifunctional or higher functional initiator. The obtained bifunctional or higher functional oxyalkylene polymer and By mixing the alkylene polymer, it is also possible to obtain an oxyalkylene polymer (D) having 1.8 to 3 hydroxyl groups per molecule on the average of all molecules.

Specific examples include polyoxyethylene compounds, polyoxypropylene compounds, polyoxybutylene compounds, polyoxyhexylene compounds, polyoxytetramethylene compounds, and / or copolymers thereof.

Particularly preferred oxyalkylene polymers (D) are polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene tetraol, copolymers of these polymers with ethylene oxide, and mixtures thereof.

In order to facilitate the reaction with the polyisocyanate compound (E) and the hydrolyzable silicon group-containing isocyanate compound (H), an oxyalkylene obtained by copolymerizing ethylene oxide so that the terminal hydroxyl group becomes primary is used. Polymers are preferred.

The number average molecular weight of the oxyalkylene polymer (D) can be 1000 or more. Since the viscosity becomes relatively high, those having 4000 or more are preferable.

In the present invention, the polyurethane-based main chain (F)
Any polyisocyanate compound can be used as the polyisocyanate compound (E) used to obtain the compound.

The number of isocyanate groups contained in the polyisocyanate compound (E) is 2 to 2 per molecule on average.
5 is preferable, and 2-3 is more preferable from availability. Further, 2 is most preferable because gelling does not occur during the reaction with the oxyalkylene polymer (D).

As specific examples, tolylene diisocyanate (TDI), methylene diisocyanate (MD
I), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), tetramethylene diisocyanate (TMDI) and the like. Furthermore, these uretdione derivatives, isocyanurate derivatives, cyanurate derivatives, and carbodiimide derivatives can also be used.

Specific examples of the silicon compound (G) represented by the formula (38) used to introduce the silicon-containing group represented by the formula (37) into the molecule of the polyether polymer include γ -Aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
Amino-substituted alkoxysilanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane, γ -Hydroxypropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane and the like.

Specific examples of the silicon-containing isocyanate compound (H) represented by the formula (39) used to introduce the silicon-containing group represented by the formula (37) into the molecule of the polyether polymer Examples thereof include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, and the like.

A catalyst can be used for the reaction between the hydroxyl group and the isocyanate group of the oxyalkylene polymer (D), and the W group and the isocyanate group of the silicon compound, but the storage stability of the obtained polyether polymer is poor. In such a case, the reaction is preferably performed in the absence of a catalyst. When a catalyst is used, a known catalyst may be used as long as it catalyzes the reaction between a hydroxyl group and an isocyanate group.

In the present invention, among the polyether polymers having at least one crosslinkable functional group as the component (II), the polyether polymers having a urethane bond or a urea bond in the main chain include: Those having a number average molecular weight of 7,500 or more are preferred. Especially number average molecular weight 75
It is more preferred to use from 00 to 25000 organic polymers. The number average molecular weight of the polyether polymer is 750
If it is lower than 0, the cured product is hard and the elongation is low. , The utility becomes low. The number average molecular weight is particularly preferably 8,000 to 20,000 from the viewpoint of viscosity.

The mixing ratio between the vinyl polymer (I) and the polyether polymer (II) was 100% by weight.
/ 1 to 1/100 is preferable, and 100/5 to 5 /
It is more preferably in the range of 100, and 100/10
More preferably, it is in the range of 〜１０100 / 100. If the blend ratio of the vinyl polymer (II) is small, excellent weather resistance, which is one of the effects of the present invention, may not be easily exhibited. << Compatibilizer (III) >> (III) in the present invention
The compatibilizer as a component is a compatibilizer added to improve the compatibility between the vinyl polymer (I) and the polyether polymer (II), and is a non-polymer organic compound or a non-vinyl compound. It is at least one compound selected from the group consisting of a polymer obtained by polymerizing a monomer and a polymer obtained by polymerizing a single vinyl monomer.

As used herein, the term “compatible” means that two or more polymers are sufficiently mixed and mixed at room temperature (15 ° C. to 15 ° C.).
(23 ° C.) for 1 day after standing still for one day.

The compatibilizer for the organic compound which is not a polymer is not particularly limited, and examples thereof include dibutyl phthalate,
Phthalates such as diheptyl phthalate, di (2-ethylhexyl) phthalate and butylbenzyl phthalate; dioctyl adipate, dioctyl sebacate,
Non-aromatic dibasic acid esters such as dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl risilinolate; poly such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester Esters of alkylene glycol; phosphates such as tricresyl phosphate and tributyl phosphate; trimellitic esters and the like.

The compatibilizing agent for the polymer obtained by polymerizing a monomer other than vinyl is not particularly limited. Chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oil And polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and the hydroxyl groups of these polyether polyols are ester groups,
Polyethers such as derivatives converted into ether groups;
Epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid; and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and the like. Examples include polyester plasticizers obtained from dihydric alcohols.

The compatibilizing agent for the polymer obtained by polymerizing a single vinyl monomer is not particularly limited, but polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene,
Butadiene-acrylonitrile, polychloroprene; and vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods.

The above-mentioned acrylic plasticizer is not particularly limited, and examples thereof include those obtained by conventional solution polymerization, and solventless acrylic polymers. The latter acrylic plasticizer uses a high-temperature continuous polymerization method (US Pat. No. 4,414,370, JP-A-59-62) without using a solvent or a chain transfer agent.
07, Tokuhei 5-58005, JP-A-1-313352
2, which is more preferable for the purpose of the present invention. Examples thereof include, but are not particularly limited to, Toagosei product UP series and the like (see October 1999, Industrial Materials).

When a polymer obtained by polymerizing a single vinyl monomer is used as a compatibilizer, the molecular weight is not particularly limited in consideration of compatibility, but is preferably 3,000 or less. The chain is not particularly limited, but is preferably a polyolefin. Further, it is also preferably a polyoxyalkylene, and more preferably a polypropylene oxide. In this case, the number average molecular weight of the polyoxyalkylene or polypropylene oxide is preferably 3000 or less. <Content> The content of the compatibilizer (III) is 100 in total of the vinyl polymer (I) and the polyether polymer (II).
The amount is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, and more preferably 10 to 150 parts by weight with respect to parts by weight.
It is particularly preferred that the amount is from 100 to 100 parts by weight. << Curable Composition >> Some curable compositions of the present invention require a curing catalyst or a curing agent depending on each crosslinkable functional group. Further, various compounding agents may be added according to the desired physical properties. <Curing Catalyst / Curing Agent> In the case of a 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. As the properties of the cured product, a wide range from rubbery to resinous can be prepared according to the molecular weight of the polymer and the main chain skeleton.

Examples of such a condensation catalyst (so-called silanol condensation catalyst) include dibutyltin dilaurate, dibutyltin phthalate, dibutyltin diacetate, and the like.
Dibutyltin bisacetylacetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate,
Dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate,
Dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate, dibutyltin dimethoxide, dibutyltin bisnonylphenoxide,
Tetravalent tin compounds such as dibutenyltin oxide; divalent tin compounds such as tin octylate, tin naphthenate and tin stearate; monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide; Monoalkyltins such as monooctyltin compounds; titanates such as tetrabutyl titanate and tetrapropyltitanate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate Chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, Ethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol , Morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU)
Or a salt of these amine compounds with a carboxylic acid or the like; a reaction product or a mixture of an amine compound and an organotin compound such as a reaction product or a mixture of laurylamine and tin octylate; Low molecular weight polyamide resin obtained from polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; amino such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane Silanol condensation catalysts such as silane coupling agents having groups; and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

These catalysts may be used alone.
Two or more kinds may be used in combination. Silanol condensation catalyst (IV)
Is preferably about 0.1 to 20 parts, more preferably 1 to 10 parts, per 100 parts (parts by weight, the same applies hereinafter) of the vinyl polymer (I) having at least one crosslinkable silyl group. . If the amount of the silanol condensation catalyst falls below this range, the curing rate may be slow, and the curing reaction may not be sufficiently advanced. On the other hand, when the amount of the silanol condensation catalyst exceeds this range, local heat generation and foaming occur during curing, and it becomes difficult to obtain a good cured product, and the pot life becomes too short, which is 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 (40) R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (40) (where R ⁴⁹ and R ⁵⁰ is each independently 1 carbon atom
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.

Examples of the silicon compound include, but are not limited to, those represented by general formula (1) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane. R ⁴⁹ is preferably an aryl group having 6 to 20 carbon atoms, since the effect of accelerating the curing reaction of the composition is large. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because they are low in cost and easily available.

The compounding amount of the silicon compound is determined by the amount of 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
-10 parts is more preferred. If the amount of the silicon compound falls below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease. In the case of an alkenyl group, in the case of crosslinking using an alkenyl group, there is no limitation, but it is preferable that crosslinking is performed by a hydrosilylation reaction using a hydrosilylation catalyst using a hydrosilyl group-containing compound as a curing agent.

Examples of the hydrosilyl group-containing compound include al
Hydrocarbons that can be cured by crosslinking with polymers having kenyl groups
There is no particular limitation as long as it is a silyl group-containing compound.
Can be used. For example, the general formula (41) or
Is a chain polysiloxane represented by (42);⁵¹ _ThreeSiO- [Si (R⁵¹)_TwoO]_a− [Si (H) (R⁵²) O]_b− [Si (R ⁵² ) (R⁵³) O]_c-SiR⁵¹ _Three (41) HR⁵¹ _TwoSiO- [Si (R⁵¹)_TwoO]_a− [Si (H) (R⁵²) O]_b− [Si (R⁵²) (R⁵³) O]_c-SiR⁵¹ _TwoH (42) (wherein, R⁵¹And R⁵²Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁵³Is an alkyl having 1 to 10 carbons
Group or 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) a cyclic siloxane represented by the general formula (43);

[0170]

Embedded image(Where R⁵⁴And R⁵⁵Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁵⁶Is an alkyl having 1 to 10 carbons
Group or 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. ))
it can.

These may be used alone or as a mixture 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 (44) and (45) having a phenyl group, and the general formulas (46) and (45) The cyclic siloxane represented by 47) 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 (44) (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 (45) Wherein R ⁵⁷ represents hydrogen or a methyl group, and g is 2 ≦ g.
≦ 100, h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group. )

[0172]

Embedded image (Wherein, R ⁵⁷ represents hydrogen or a methyl group.
i ≦ 10 and j are integers satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. As the hydrosilyl group-containing compound, a low molecular weight compound having two or more alkenyl groups in the molecule may further include a hydrosilyl group-containing compound represented by any of general formulas (41) to (47) even after the reaction. A compound obtained by performing an addition reaction so that the hydrosilyl group of the above remains can also be used. 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 is slowly added dropwise to the excess amount of the hydrosilyl group-containing compound represented by the above general formulas (41) to (47) in the presence of a hydrosilylation catalyst to convert the compound. Obtainable. Among these compounds, the following compounds are preferred in consideration of the availability of raw materials, the ease of removing excess siloxane, and the compatibility of the component (A) with the polymer.

[0174]

Embedded image 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 more preferably 2.5 to 0.2. It is particularly preferable that the number is 0.4. When the molar ratio is 5 or more, only a cured product with insufficient strength and stickiness is obtained, and when it is less than 0.2, a large amount of active hydrosilyl groups remains in the cured product even after curing. , Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

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

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, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke such as cyclohexane It can be mentioned Lumpur and the like.

The transition metal catalyst is not particularly limited. For example, a platinum solid, a dispersion of platinum solid in a carrier such as alumina, silica, carbon black, etc., chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples include a complex with a ketone, a platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. 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. The amount of the catalyst is not particularly limited, but 1 mol of the alkenyl group of the vinyl polymer (I).
On the other hand, it is good to use in the range of 10 ^-1 to 10 ^-8 mol, and preferably in the range of 10 ^-3 to 10 ^-6 mol. If the amount is less than 10 ^-8 mol, the curing does not proceed sufficiently. Also, since the hydrosilylation catalyst is expensive, it is 10 ^-1.
It is preferable not to use more than mol.

The curing temperature is not particularly limited, but it is generally preferable to cure at 0 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., and more preferably 80 ° C. to 150 ° C. In the case of a 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. As specific examples of the curing agent,
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 etherified product or a low condensed product, a polyfunctional carboxylic acid and its halide, and the like can be mentioned. When preparing a cured product using these curing agents, an appropriate curing catalyst can be used. In the case of an 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 the 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 an alkyl ether or a low condensation product thereof, a polyfunctional carboxylic acid and And halides thereof. When preparing a cured product 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, but examples thereof include aliphatic amines, alicyclic amines, and aromatic amines; acid anhydrides; polyamides; Amine imides; Ureas; Melamines and derivatives thereof; Polyamine salts; Phenolic resins; Polymeric captans, Polysulfides; . In the case of a polymerizable carbon-carbon double bond, a polymer having a polymerizable carbon-carbon double bond can be crosslinked by a polymerization reaction of the polymerizable carbon-carbon double bond.

As a crosslinking method, a method of curing with an active energy ray or a method of curing with heat can be used. 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-based initiator, peroxide, persulfate,
And a redox initiator.

Hereinafter, these crosslinking reactions will be described in detail.

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

Specific examples of the above monomers include (meth) acrylate monomers, cyclic acrylates, N-
Examples include vinylpyrrolidone, styrene-based monomers, acrylonitrile, N-vinylpyrrolidone, acrylamide-based monomers, conjugated diene-based monomers, and vinyl ketone-based monomers. 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 formulas. it can.

[0183]

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[0184]

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[0185]

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[0186]

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[0187]

Embedded image Styrene-based monomers include styrene, α-methylstyrene, etc., acrylamide-based monomers include acrylamide, N, N-dimethylacrylamide, etc., and conjugated diene-based monomers include butadiene and isoprene.
Examples of the vinyl ketone-based monomer include methyl vinyl ketone.

Examples of the polyfunctional monomers include neopentyl glycol polypropoxy diacrylate, trimethylolpropane polyethoxy triacrylate, bisphenol F polyethoxy diacrylate, 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 diethoxy diacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and the like. Examples of the oligomer include an epoxy acrylate resin such as a bisphenol A type epoxy acrylate resin, a phenol novolak type epoxy acrylate resin, a cresol novolak type epoxy acrylate resin, a COOH group-modified epoxy acrylate resin,
Polyols (polytetramethylene glycol, polyester diol of ethylene glycol and adipic acid, ε-
Caprolactone-modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylene) Diisocyanate, etc.) to obtain a hydroxy group-containing (meth) acrylate メ タ hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Urethane acrylate resin obtained by reacting acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc., resin in which a (meth) acryl group is introduced into the above polyol through an ester bond, polyester acrylate resin, etc. Is mentioned.

These monomers and oligomers are selected depending on the initiator and curing conditions used.

The monomer and / or oligomer having an acrylic functional group preferably has a number average molecular weight of 2,000 or less, more preferably 1,000 or less, because of good compatibility.

As a method for crosslinking a polymer having a polymerizable carbon-carbon double bond, it is preferable to use an active energy ray such as UV or an electron beam.

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

The photopolymerization initiator used in the present invention is not particularly limited, but a photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde,
Anthraquinone, triphenylamine, carbazole,
3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophen, 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-chloroxanthone
Chloro-8-nonyl xanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone and the like can be mentioned. These initiators may be used alone or in combination with other compounds. Specifically, a combination with an amine such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combined with an iodonium salt such as diphenyliodonium chloride, and a combination with a dye and an amine such as methylene blue. Can be

Further, as a near-infrared light polymerization initiator, a near-infrared light-absorbing cationic dye may be used. As a near-infrared light-absorbing cationic dye, it is excited by light energy in a range of 650 to 1500 nm, for example, as described in JP-A-3-11.
It is preferable to use a near-infrared light-absorbing cationic dye-borate anion complex or the like disclosed in JP-A No. 1402 or JP-A-5-194609, and it is more preferable to use a boron sensitizer in combination.

The amount of the photopolymerization initiator to be added is not particularly limited since it is only necessary to slightly photofunctionalize the system. Is preferred.

The method for curing the active energy ray-curable composition of the present invention is not particularly limited. Light and electron beam irradiation by a light emitting diode, a semiconductor laser, or the like can be given.

As a method for crosslinking a polymer having a polymerizable carbon-carbon double bond, heat is preferably used.

In the case of crosslinking by 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 (methylisobutyl
G) (V-601) (available from Wako Pure Chemical Industries).

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

[0202] Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.

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

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

Preferred thermal radical initiators are selected from the group consisting of azo initiators and peroxide initiators. More preferred are 2,2'-azobis (methylisobutyrate), t-butylperoxypivalate,
And di (4-tert-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is not limited,
Typically, about 0.01 to 5 parts by weight based on 100 parts by weight of the polymer of the present invention having at least one terminal acrylic functional group and the other monomer and oligomer mixture added. , 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, and the temperature varies depending on the type of the thermal initiator, the polymer (I) and the compound to be added. C. to 250.degree. C. are preferred,
The temperature is more preferably in the range of 70C to 200C. The curing time varies depending on the used polymerization initiator, monomer, solvent, reaction temperature and the like, but is usually in the range of 1 minute to 10 hours. <Adhesiveness-imparting agent> A silane coupling agent or an adhesiveness-imparting agent other than the silane coupling agent can be added to the composition of the present invention. When the adhesion imparting agent is added, the joint width and the like fluctuate due to external force, so that the risk of the sealing material peeling off from the adherend such as a siding board can be further reduced. In some cases, the necessity of using a primer used for improving the adhesiveness is eliminated, and simplification of the construction work is expected. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, 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-
amino group-containing silanes such as γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ- Mercapto group-containing silanes such as mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, Epoxy group-containing silanes such as γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-cal Carboxysilanes such as xylethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyl Vinyl-type unsaturated group-containing silanes such as triethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanurate silanes such as trimethoxysilyl) isocyanurate can be exemplified. Further, derivatives of these modified amino-modified silyl polymer, silylated amino polymer, unsaturated aminosilane complex, phenylamino long-chain alkylsilane, aminosilylated silicone,
Silylated polyesters and the like can also be used as the silane coupling agent.

The silane coupling agent used in the present invention is
Usually, it is used in the range of 0.1 to 20 parts with respect to 100 parts in total of the vinyl polymer (I) and the polyether polymer (II). In particular, it is preferable to use it in the range of 0.5 to 10 parts. If the addition amount is too large, the cured product obtained by curing the curable composition loses rubber elasticity, and may not function as a sealing material. In addition, when adding to the two-component type mentioned below, it is preferable that the total amount added to both of the two components falls within the above range. The effect of the silane coupling agent added to the curable composition of the present invention can be obtained from various adherends, that is, glass, aluminum, stainless steel, zinc, copper, an inorganic substrate such as mortar, PVC, acrylic, polyester, When used for an organic substrate such as polyethylene, polypropylene, and polycarbonate, it exhibits a remarkable effect of improving 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 significant.

Specific examples other than the silane coupling agent are not particularly restricted but include, for example, epoxy resins, phenolic resins, sulfur, alkyl titanates, aromatic polyisocyanates and the like.

The above-mentioned adhesiveness-imparting agents may be used alone or in combination of two or more. The addition of these adhesion-imparting agents can improve the adhesion to the adherend. <Plasticizer> In the curable composition of the present invention, various plasticizers are used as needed. The plasticizer is not particularly limited. For example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate and butyl benzyl phthalate; Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; diethylene glycol dibenzoate;
Esters of polyalkylene glycol such as triethylene glycol dibenzoate and pentaerythritol ester; Phosphates such as tricresyl phosphate and tributyl phosphate; Trimellitic esters; Polystyrenes such as polystyrene and poly-α-methylstyrene Polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene glycol, polypropylene glycol, polytetramethylene glycol Polyether polyols such as polyether polyols and derivatives obtained by converting hydroxyl groups of these polyether polyols into ester groups, ether groups, etc .; Epoxy plasticizers such as petroleum soybean oil and benzyl epoxy stearate; dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid; and 2 such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol. Polyester plasticizers obtained from polyhydric alcohols; vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods, alone or as a mixture of two or more. Can be
It is not necessary. In addition, these plasticizers can be blended at the time of polymer production.

The above-mentioned acrylic plasticizer is not particularly limited, and examples thereof include those obtained by conventional solution polymerization, and solventless acrylic polymers. The latter acrylic plasticizer uses a high-temperature continuous polymerization method (US Pat. No. 4,414,370, JP-A-59-62) without using a solvent or a chain transfer agent.
07, Tokuhei 5-58005, JP-A-1-313352
2, which is more preferable for the purpose of the present invention. Examples thereof include, but are not particularly limited to, Toagosei product UP series and the like (see October 1999, Industrial Materials).

When the plasticizer is used, the amount of the plasticizer is not limited, but is not limited to an amount that does not impair the effect of the compatibilizer, and the total amount of the vinyl polymer (I) and the polyether polymer (II) is 100%.
The amount is 150 parts by weight or less, preferably 120 parts by weight or less, more preferably 100 parts by weight or less based on 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> Various fillers are used as needed in the curable composition of the present invention. Examples of the filler include, but are not particularly limited to, wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, clay, fumed silica, and settled silica. , Crystalline silica, fused silica, dolomite,
Reinforcing fillers such as silicic anhydride, hydrous silicic acid, carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, oxide Fillers such as ferrous iron, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc powder and shirasu balloon; fibrous fillers such as asbestos, glass fiber and filaments. Among these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In particular, when it is desired to obtain a high-strength cured product with these fillers, mainly fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystalline silica, fused silica A filler selected from silica, calcined clay, clay and activated zinc white can be added. When it is desired to obtain a cured product having low strength and large elongation, a filler mainly selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when the specific surface area of calcium carbonate is small, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of a cured product may not be sufficient. As the value of the specific surface area is larger, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product becomes larger. Further, it is more preferable that calcium carbonate has been subjected to surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case where calcium carbonate without the surface treatment is used, and the adhesiveness and weather resistance of the curable composition are improved. 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, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. And salts of the fatty acids such as sodium and potassium, and alkyl esters of the fatty acids. Specific examples of the surfactant include polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, and sulfate-type anionic surfactants such as sodium salts and potassium salts thereof, and alkylbenzenesulfonic acid and alkylnaphthalene. Sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkyl sulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as a sodium salt and a potassium salt thereof, and the like. The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 5% by weight, based on calcium carbonate. If the treatment amount is less than 0.1% by weight, the effect of improving workability, adhesion and weather resistance may not be sufficient, and if it exceeds 20% by weight, the storage stability of the curable composition may be insufficient. May drop. <Addition amount> When a filler is used, the addition amount is a total of 10 for the vinyl polymer (I) and the polyether polymer (II).
The filler is preferably used in a range of 5 to 1000 parts by weight, more preferably in a range of 20 to 500 parts by weight, and more preferably in a range of 40 to 300 parts by weight with respect to 0 parts by weight. Is particularly preferred. If the amount is less than 5 parts by weight, the effect of improving the breaking strength, elongation at break, adhesion and weather resistance of the cured product may not be sufficient. Performance may be reduced. The fillers may be used alone or in combination of two or more. <Physical property adjuster> The curable composition of the present invention may optionally contain a physical property adjuster for adjusting the tensile properties of the resulting cured product.

The physical property modifier is not particularly limited.
For example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldisilane Alkylisopropenoxysilanes such as isopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β
-Aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Alkoxysilanes having a functional group such as mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes. By using the physical property modifier, the hardness of the composition of the present invention when it is cured can be increased, or the hardness can be decreased, and elongation can be obtained. The physical property modifiers may be used alone or in combination of two or more. <Thixotropy-imparting agent (anti-sagging agent)> The curable composition of the present invention may be added with a thixotropy-imparting agent (anti-sagging agent) to prevent sagging and improve workability, if necessary. Is also good.

The anti-sagging agent is not particularly restricted but includes, for example, polyamide waxes; hydrogenated castor oil and derivatives thereof; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. Other Additives Various additives may be added to the curable composition of the present invention as needed for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, flame retardants, curability modifiers, antioxidants, radical inhibitors, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, phosphorus-based additives. Examples thereof include an oxide decomposing agent, a lubricant, a pigment, a foaming agent, a fungicide, a rust preventive, and a photocurable resin. These various additives may be used alone or in combination of two or more.

Specific examples of such additives include, for example,
Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-1088928,
JP-A-63-254149, JP-A-64-22904
It is described in each specification of the issue.

The curable composition of the present invention can also be prepared as a one-component type in which all the components are premixed, sealed and stored, and cured by the moisture in the air after application. Ingredients such as a filler, a plasticizer, and water may be blended in advance, and the blended material and the polymer composition may be mixed before use to prepare a two-component type. When the two-component type is used, a coloring agent can be added at the time of mixing the two components. For example, when providing a sealing material that matches the color of the siding board, it is possible to perform abundant color alignment with limited stock. For example, it becomes possible to easily cope with multi-color demands from the market, and it is more preferable for low-rise buildings and the like.
As the colorant, for example, a pigment and a plasticizer, and in some cases, a mixture of a filler and a paste are used to facilitate the operation. Further, by adding a retarder when mixing the two components, the curing speed can be finely adjusted at the work site. <Use> The curable composition of the present invention is not limited,
Sealing materials such as elastic sealing materials for buildings and sealing materials for double glazing, electric and electronic parts materials such as sealing materials for backside of solar cells, electric insulating materials such as insulating coating materials for electric wires and cables, adhesives, adhesives, Elastic adhesives, paints, powder paints,
Coating materials, foams, potting agents for electrical and electronic equipment,
It can be used for various applications such as films, gaskets, casting materials, various molding materials, and rustproof / waterproof sealing materials for netted glass and laminated glass end faces (cut portions). << Curing Product >> A curable composition containing the vinyl polymer (I), the polyether polymer (II), and the compatibilizer (III) of the present invention is cured without adding a filler or the like. 100
It is preferable that a cured product having a thickness of not more than μm exhibits a weather resistance of not less than 20 hours in a sunshine weather meter test.

The determination of the weather resistance of a cured product having a thickness of 100 μm or less in the present invention is based on visual observation of the surface of the cured product. For example, a weather resistance of 20 hours or more means that the initial good condition is obtained without any change due to waving or disappearance of the surface due to elution of the polymer, cracking, discoloration (in the case of a colored product), whitening (chalking), or the like. This means that a good surface condition is maintained for 20 hours or more.

Further, the weather resistance test in the present invention is as follows.
Refers to the test according to JIS A 1415 WS type.

[0219]

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 between weight average molecular weight and number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, GP
A column filled with a polystyrene crosslinked gel as a C column (shodex GPC K-804; Showa Denko KK)
And GPC solvent was chloroform. (Production Example 1) CuBr (25 g) in acetonitrile (2640 g) was placed in a 50 L reaction vessel equipped with a reflux tower and a stirrer.
(1.82 g, 1.76 mol) was dispersed therein, and the inside of the reactor was sealed with nitrogen and stirred 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 triamine) was added to initiate the reaction. With heating and stirring at 80 ° C., butyl acrylate (24.0 kg) was continuously added dropwise. During the dropping 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 were continued at 80 ° C. for 4 hours. Thereafter, the heating and stirring were temporarily interrupted, and triamine (80.0 mL, 390 mm
ol), and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain a reaction mixture containing the polymer [1] (polymerization reaction mixture [1 ′]). The polymer [1] had a number average molecular weight of 23,600 and a molecular weight distribution of 1.21 by GPC measurement (in terms of polystyrene), and the average number of alkenyl groups introduced per polymer molecule was determined by 1H NMR analysis. However, the number was 2.9.

To the polymer [1] (3.8 kg) were added potassium acetate (87 g) and dimethylacetamide (3.8 L), and the mixture was stirred at 100 ° C. for 8 hours under a nitrogen stream. The mixture was heat-treated under reduced pressure, diluted with toluene, filtered, and the filtrate was concentrated to obtain a polymer [2].

Kyoward 500SH (Kyowa Chemical, 380 g) and Kyoward 7 were added to the polymer [2] (3.8 kg).
00SL (Kyowa Chemical, 190 g) and xylene (76
0 mL), and the mixture was heated and stirred at 100 ° C. for 5 hours and 15 minutes under a nitrogen stream. This was diluted with toluene, filtered, and the filtrate was concentrated to obtain a polymer [3].

In a 2 L pressure-resistant reaction vessel, polymer [3] (1
300 g), and the gas phase was replaced with nitrogen. 100 ℃
Then, dimethyl orthoformate (17 mL, 0.16 mol) and dimethoxymethylhydrosilane (59 mL, 0.47 mol) were added under a nitrogen stream while stirring.
Subsequently, a platinum catalyst (1,1,3,3-tetramethyl-1,0-valent platinum,
3-divinyldisiloxane complex in xylene solution) was added to initiate the reaction. However, the amount of the platinum catalyst used was 30 ppm as platinum. After heating at 100 ° C. for 2 hours, the mixture was cooled and the reaction mixture was discharged. The mixture was concentrated to obtain poly (n-butyl acrylate) having a silyl group at a terminal (polymer [4]). Polymer [4] is GPC
The number average molecular weight was 270 as measured (in terms of polystyrene).
The molecular weight distribution was 1.41, and the number of silyl groups introduced per oligomer-1 molecule was 2.5 according to 1H NMR analysis. (Production Example 2) 10.9 g of copper (I) bromide in a 2 L flask
(76.1 mmol) and 145 mL of acetonitrile were charged and heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. 15.2 g of diethyl 2,5-dibromoadipate (4.
2.3 mmol), 291 mL of butyl acrylate (2.
03 mol), and the mixture was further heated and stirred at 80 ° C. for 40 minutes. 0.53 mL (2.54 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine)
Was added to start the reaction. Furthermore, 1.06 of triamine was added.
mL (5.08 mmol) was added. Heating and stirring were continued at 80 ° C, and 25 minutes after the start of the reaction, 1163 mL (8.11 mol) of butyl acrylate was dropped dropwise over 95 minutes. During this period, 1.06 mL of triamine (5.08
mmol). After 195 minutes from the start of the reaction, the pressure inside the reaction vessel was reduced to remove volatile components. 2 from the start of the reaction
After 60 minutes, 436 mL of acetonitrile, 187 mL (1.27 mol) of 1,7-octadiene, and triamine5.
3 mL (25.4 mmol) was added, and heating and stirring were continued at 80 ° C., and heating was stopped 1130 minutes after the start of the reaction. The reaction solution was heated under reduced pressure to remove volatile components, diluted with toluene, filtered, and the filtrate was concentrated to obtain a polymer [5]. The number average molecular weight of the obtained polymer [5] was measured by GPC (mobile phase: chloroform, converted to polystyrene).
37400, molecular weight distribution 1.25, and 1H-
The number of alkenyl groups per polymer molecule determined by NMR analysis was 2.1.

After subjecting the polymer [5] to heat treatment under reduced pressure, the polymer [5] was diluted with toluene to remove solids. Polymer [5] 100
4 parts of adsorbent per part (Kyoward 500SH 2 parts / Kyoward 700SL 2 parts: Kyowa Chemical Co., Ltd.)
Was added to a xylene solution of the polymer, and the mixture was heated and stirred in an oxygen / nitrogen mixed gas atmosphere. After removing the solid content, the polymer solution was concentrated, and further subjected to a heating and depressurizing treatment while stirring at 180 ° C. for 12 hours (a degree of depressurization of 10 torr or less).

This was diluted with xylene, and adsorbent 6 parts (Kyoward 500SH 3 parts /
KYOWARD 700SL 3 copies: Kyowa Chemical Co., Ltd.
Was added to a xylene solution of the polymer, and the mixture was heated and stirred in an oxygen / nitrogen mixed gas atmosphere. After removing the solid content, the solution was concentrated to obtain a polymer [6].

Polymer [6], dimethoxymethylsilane (3 molar equivalents relative to alkenyl group), methyl orthoformate (1 molar equivalent relative to alkenyl group), platinum catalyst (10 mg of platinum as platinum per kg of polymer) And heated and stirred at 80 ° C. for 1 hour under a nitrogen atmosphere. 1H-NMR confirmed that the alkenyl group had disappeared by the reaction,
The reaction mixture was concentrated to obtain the desired methoxysilyl group-containing polymer [7]. The number average molecular weight was 41,000, and the molecular weight distribution was 1.41. The number of silyl groups introduced per molecule of polymer [7] was 1.9. (Production Example 3) CuBr (22.4 g, 0.1 mL) was placed in a 2 L separable flask equipped with a reflux tube and a stirrer. 156mo
l) was charged, and the inside of the reaction vessel was replaced with nitrogen. Add acetonitrile (112 mL) and place in an oil bath at 70 ° C for 30 minutes.
Stirred for minutes. Add butyl acrylate (0.20k
g), methyl 2-bromopropionate (86.9 g,
0.520 mol), pentamethyldiethylenetriamine (0.19 mL, 0.18 g, 1.04 mmol)
(Hereinafter triamine) was added to initiate the reaction. With heating and stirring at 70 ° C., butyl acrylate (0.80 kg) was continuously added dropwise over 150 minutes.
During the dropping of butyl acrylate, triamine (1.81 m
L, 1.71 g, 9.88 mmol). Subsequently, the mixture was heated and stirred at 70 ° C. for 230 minutes. After diluting the reaction mixture with toluene and passing through an activated alumina column, volatile components were distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [8]). The number average molecular weight of the polymer [8] is 2
600 and the molecular weight distribution was 1.18.

In a 2 L separable flask equipped with a reflux tube, polymer [8] (0.937 kg) and potassium acetate (73.5) were added.
g) and N, N-dimethylacetamide (0.8 L) were charged and heated and stirred at 70 ° C. for 5 hours under a nitrogen stream. After removing N, N-dimethylacetamide under reduced pressure while heating, the mixture was diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatiles in the filtrate were distilled off under reduced pressure to obtain a polymer [9]. (Example 1) Production Example 50 of the vinyl polymer [4] obtained in 1
50 parts of a commercially available polyether-based polymer having a crosslinkable silyl group (S203 manufactured by Kaneka Chemical Industry Co., Ltd.) and 50 parts of a compatibilizer (DIDP (diisodecyl phthalate) manufactured by Kyowa Hakko)
A curable composition in which 0 parts were sufficiently mixed was prepared. (Example 2) 30 of the vinyl polymer [4] obtained in Production Example 1
Parts, 70 parts of a commercially available polyether polymer having a crosslinkable silyl group (S203 manufactured by Kaneka Chemical Industry Co., Ltd.) and 5 parts of a compatibilizer (DIDP (diisodecyl phthalate) manufactured by Kyowa Hakko)
A curable composition in which 0 parts were sufficiently mixed was prepared. Example 3 50 of the vinyl polymer [4] obtained in Production Example 1
Parts, 50 parts of a commercially available polyether polymer having a crosslinkable silyl group (S203 manufactured by Kaneka Chemical Industry Co., Ltd.)
A curable composition in which 0 parts were sufficiently mixed was prepared. Example 4 The vinyl polymer [4] 30 obtained in Production Example 1
Parts, 70 parts of a commercially available polyether polymer having a crosslinkable silyl group (S203 manufactured by Kaneka Chemical Industry Co., Ltd.) and a compatibilizer (acrylic plasticizer (UP-1020) manufactured by Toagosei Co., Ltd.) 5
A curable composition in which 0 parts were sufficiently mixed was prepared. Example 5 Vinyl-based polymer [4] 50 obtained in Production Example 1
Production Example 3 in 50 parts of a commercially available polyether-based polymer having a crosslinkable silyl group (S203 manufactured by Kanegafuchi Chemical Industry Co., Ltd.)
A curable composition was prepared by sufficiently mixing 50 parts of the vinyl polymer [9] obtained in the above. (Example 6) 30 of the vinyl polymer [4] obtained in Production Example 1
Production Example 3 in 70 parts of a commercially available polyether-based polymer having a crosslinkable silyl group (S203, manufactured by Kanegafuchi Chemical Industry Co., Ltd.)
A curable composition was prepared by sufficiently mixing 50 parts of the vinyl polymer [9] obtained in the above. (Example 7) The vinyl polymer [7] 50 obtained in Production Example 2
50 parts of a commercially available polyether-based polymer having a crosslinkable silyl group (S203 manufactured by Kaneka Chemical Industry Co., Ltd.) and 50 parts of a compatibilizer (DIDP (diisodecyl phthalate) manufactured by Kyowa Hakko)
A curable composition in which 0 parts were sufficiently mixed was prepared. Example 8 The vinyl polymer [7] 30 obtained in Production Example 2
Parts, 70 parts of a commercially available polyether polymer having a crosslinkable silyl group (S203 manufactured by Kaneka Chemical Industry Co., Ltd.) and 5 parts of a compatibilizer (DIDP (diisodecyl phthalate) manufactured by Kyowa Hakko)
A curable composition in which 0 parts were sufficiently mixed was prepared. (Comparative Examples 1 and 2) Curable compositions were prepared in the same manner as in Examples 1 and 2, except that the compatibilizer used in Examples 1 and 2 was not added. (Comparative Examples 3 and 4) Curable compositions were prepared in the same manner as in Examples 7 and 8, except that the compatibilizer used in Examples 7 and 8 was not added. (Evaluation 1) The curable compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were put in a glass bottle and sealed, and were cooled at room temperature (15 to 2).
(3 ° C.) for one day, and then their state was visually observed. Although the curable compositions of Examples 1 to 8 were compatible with each other without visually confirming the boundary, the boundaries of the curable compositions of Comparative Examples 1 to 4 were visually confirmed.

[0228]

[Table 1] (Example 9) 100 parts of the curable composition of Example 1 was added with tetravalent S
1 part of n catalyst (dibutyltin diacetylacetonate) was sufficiently mixed and poured into an aluminum mold having a size of about 80 mm x about 60 mm x about 2 mm. A cured product was obtained. (Comparative Example 5) 100 parts of the curable composition of Comparative Example 1 was added to tetravalent S
1 part of n-catalyst (dibutyltin diacetylacetonate) was sufficiently mixed and poured into an aluminum mold having a size of about 80 mm × about 60 mm × about 2 mm. Was obtained. (Evaluation 2) 2 (1/1) of the cured products obtained in Example 9 and Comparative Example 5
3) A No. dumbbell-type test piece (JIS K 7113) was punched out, and the elongation at break (E
b, measurement environment: 23 ° C., tensile speed: 200 mm / mi
n) was measured. Example 9 was higher in elongation than Comparative Example 5.

[0229]

[Table 2] (Example 10) A tetravalent Sn catalyst (dibutyltin diacetylacetonate) was added to 100 parts of the curable composition obtained in Example 1.
The mixture was sufficiently mixed, applied on an aluminum plate of about 100 μm, and allowed to stand at room temperature for 2 days and then at 50 ° C. for 3 days to obtain a cured product. (Comparative Example 6) 100 parts of the curable composition obtained in Comparative Example 1
One part of a divalent Sn catalyst (dibutyltin diacetylacetonate) was sufficiently mixed, applied on an aluminum plate having a thickness of about 100 μm, and allowed to stand at room temperature for 2 days and then at 50 ° C. for 3 days to obtain a cured product. (Evaluation 3) The weather resistance of the cured products obtained in Example 10 and Comparative Example 6 was measured using a sunshine weather meter (WE manufactured by Suga Test Instruments).
L-SUN-DC type, black panel temperature of 63 ° C., irradiation for 2 hours, rainfall of 18 minutes). The surface condition after the weather resistance test was performed for a predetermined time was observed. Example 3 is irradiation test 2 using a sunshine weather meter.
The state after 0 hour and 48 hours was observed.

[0230]

[Table 3] Example 11 A composition was prepared in the same manner as in Examples 1 to 6, except that the vinyl polymer [1] was used instead of the vinyl polymer [4]. And the compatibility was evaluated. As a result, all the compositions were compatible. (Example 12) A composition was prepared in the same manner as in Example 1 except that the vinyl polymer [1] was used instead of the vinyl polymer [4] (this was referred to as composition A). Next, 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was sufficiently mixed with 100 parts of the composition A, and the mixture was mixed with about 80 mm × about 6 mm.
Pour into an aluminum mold of 0mm x about 2mm,
And then left at 50 ° C. for 3 days to obtain a sheet-like cured product. Next, a 2 (1/3) No. dumbbell type test piece (JIS K 7113) was punched from the cured product, and the elongation at break (Eb, measurement environment: 23) was measured using an autograph manufactured by Shimadzu.
(° C., tensile speed: 200 mm / min), it showed a high elongation. Next, the weather resistance of this cured product was measured using a sunshine weather meter (WEL-S manufactured by Suga Test Instruments).
UN-DC type, black panel temperature of 63 ° C., irradiation for 2 hours, rainfall for 18 minutes). No change was observed in the state of the sample after 20 hours and 48 hours of the irradiation test.

[0231]

According to the present invention, at least one crosslinkable functional group is provided.
Curable composition comprising a vinyl polymer (I) having at least one crosslinkable functional group, a polyether polymer (II) having at least one crosslinkable functional group, and a compatibilizer (III), and the cured product is a polyether-based polymer It does not impair the high elongation characteristics inherent to the polymer and is excellent in weather resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 (72) Inventor Yoshiki Nakagawa 5-1-1 Torikai Nishi, Settsu-shi, Osaka Bell Fuchi Chemical Industry Co., Ltd. High Performance Resin Business Development Dept. Laboratory F-term (reference) BG10W BG11W BG13W BH02W BL01W BL02W BQ00W CD16Y CF03Y CF04Y CH02Y CH05X CH05Y EH076 EH096 EH146 EH156 EW046 FD010 FD020 FD140 FD200 GH01 GJ01 GJ02 GQ01 4J015 DA13 A13 A13 A13 A13 A13 A13 A13 A13 A13 A13 A13 A13 A13A13 A13A13A13

Claims (24)

[Claims] 1. The following three components, a vinyl polymer (I) having at least one crosslinkable functional group, and a polyisomer which is incompatible with the vinyl polymer and has at least one crosslinkable functional group An organic compound which is a compatibilizer for adding the ether polymer (II) and a mixture of the vinyl polymer and the polyether polymer to make them compatible with each other, and which is not a polymer. Containing at least one compatibilizer (III) selected from the group consisting of a polymer obtained by polymerizing a monomer other than a vinyl-based monomer and a polymer obtained by polymerizing a single vinyl-based monomer. Characteristic curable composition. 2. The curable composition according to claim 1, wherein the molecular weight distribution of the vinyl polymer (I) is less than 1.8. 3. The main chain of the vinyl polymer (I) is selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. The curable composition according to claim 1, wherein the curable composition is produced by mainly polymerizing a monomer to be produced. 4. The curable composition according to claim 1, wherein the vinyl polymer (I) is a (meth) acrylic polymer. 5. The curable composition according to claim 1, wherein the vinyl polymer (I) is an acrylic polymer. 6. The curable composition according to claim 5, wherein the vinyl polymer (I) is an acrylate 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) is a crosslinkable silyl group.
8. The curable composition according to any one of items 7 to 7. 9. The crosslinkable functional group of the vinyl polymer (I) is an alkenyl group.
The curable composition according to any one of the above. 10. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a hydroxyl group. 11. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an amino group. 12. The method according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a group having a polymerizable carbon-carbon double bond. 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. A catalyst selected from the group consisting of transition metal complexes having a central metal of Group 7, 8, 9, 10 or 11 of the periodic table as a catalyst in the atom transfer radical polymerization. The curable composition according to claim 15, wherein: 17. The metal complex used as a catalyst is copper, nickel,
The curable composition according to claim 16, which is a complex selected from the group consisting of 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 method according to claim 1, wherein when the crosslinkable functional group of the vinyl polymer (I) is a crosslinkable silyl group, the silanol condensation catalyst (IV) is further included as an essential component. The curable composition according to any one of the above. 20. The polyether-based polymer (II) wherein the main chain is essentially a polyoxyalkylene.
10. The curable composition according to any one of 9 above. 21. The main chain of the polyether polymer (II) is essentially polypropylene oxide.
21. The curable composition according to any one of the above items. 22. The compatibilizer (III) having a number average molecular weight of 3
The curable composition according to any one of claims 1 to 21, wherein the composition is a polyoxyalkylene of 000 or less. 23. The compatibilizer (III) having a number average molecular weight of 3
The curable composition according to any one of claims 1 to 22, wherein the curable composition is a polypropylene oxide of 000 or less. 24. The cured product according to claim 1, wherein a cured product having a thickness of 100 μm or less, which is obtained by curing without a filler, has a weather resistance of 20 hours or more in a sunshine weather meter test. The curable composition according to any one of the above.