JP4881330B2 - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problems wherein a curable composition which comprises as a curing component a vinyl polymer which has at least one crosslinkable functional group, has excellent heat-resistance and weatherability, moreover has good painting property in case a coating is applied on it, however, when plasticizers such as a phthalic acid ester conventionally well known having a low molecular weight comparatively are used in order to lower the viscosity of the formulation, the plasticizers flow out with time by heat or rainfall, thereby the cured material becomes difficult to maintain the initial physical properties in the long run, and moreover when a coating called as alkyd paint is applied, the coating becomes to hardly dry and harden. <P>SOLUTION: A curable composition comprising a vinyl polymer (I) which has at least one crosslinkable functional group, and a polymer plasticizer (II) is subjected to curing. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition containing a vinyl polymer having at least one crosslinkable functional group and a polymer plasticizer.

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

If a vinyl polymer having an alkenyl group at the molecular chain terminal can be obtained by a simple method, a cured product having excellent cured product properties can be obtained as compared with those having a crosslinkable group in the side chain. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially. For example, Patent Documents 1 and 2 disclose a method for synthesizing a (meth) acrylic polymer having an alkenyl group at a terminal using an alkenyl group-containing disulfide as a chain transfer agent.

In Patent Document 3, a vinyl polymer having hydroxyl groups at both ends is synthesized using a disulfide having a hydroxyl group, and further, an alkenyl group is provided at the end using the reactivity of the hydroxyl group (meth). A method for synthesizing acrylic polymers is disclosed.

In Patent Document 4, a vinyl polymer having hydroxyl groups at both ends is synthesized using a polysulfide having hydroxyl groups, and further, a hydroxyl group is used to have a silyl group at the terminal (meth). A method for synthesizing acrylic polymers is disclosed.

In these methods, it is difficult to reliably introduce functional groups at both ends, and a cured product having satisfactory characteristics 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 these methods, since ordinary radical polymerization is used, 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.

In contrast to such conventional techniques, the inventors have so far made numerous inventions regarding vinyl polymers having various crosslinkable functional groups at their terminals, their production methods, curable compositions, and applications. (See Patent Documents 5 to 16).

For example, a vinyl polymer having a silicon-containing group (hereinafter also referred to as “crosslinkable silyl group”) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, or The cured product obtained from the composition is excellent in heat resistance or weather resistance, and is used in various applications such as an elastic sealant for construction, a sealing material for double-glazed glass, a paint, a coating material, and a sealing material.

JP-A-1-247403 Japanese Patent Laid-Open No. 5-255415 JP-A-5-262808 Japanese Patent Application Laid-Open No. 5-21922 JP 11-080249 A JP-A-11-080250 JP-A-11-005815 JP-A-11-116617 JP-A-11-116606 JP 11-080571 A JP 11-080570 A JP-A-11-130931 Japanese Patent Laid-Open No. 11-100433 JP 11-116763 A JP-A-9-272714 JP-A-9-272715

A cured product comprising a vinyl polymer having at least one crosslinkable functional group as a curing component has good heat resistance and weather resistance, and also has good paintability when a paint is applied thereon. . However, if a plasticizer having a relatively low molecular weight such as phthalate, which has been well known in the past, is used to lower the viscosity of the compound, the cured product will flow out over time due to heat or rain. This makes it difficult to maintain the initial physical properties for a long time. Moreover, when a coating called an alkyd coating is applied, the coating has a drawback that it is difficult to dry and harden.

In view of the above-mentioned present situation, the present inventors have maintained the heat resistance and weather resistance of a cured product of a vinyl polymer having at least one crosslinkable functional group for a long time by using a polymer plasticizer, It has been found that the paintability of the alkyd paint on the cured product can be improved, and the present invention has been achieved.

That is, the present invention is a curable composition containing the following two components: a vinyl polymer (I) having at least one crosslinkable functional group, and a polymer plasticizer (II). The vinyl polymer (I) is not limited, but is preferably a (meth) acrylic polymer. The crosslinkable functional group of the vinyl polymer (I) is not limited, but a crosslinkable silyl group, alkenyl group, hydroxyl group, amino group, polymerizable carbon-carbon double bond, epoxy group, and the like are preferable.

The position of the crosslinkable functional group of the vinyl polymer (I) is not limited, but the terminal is preferable. In addition, although it may have the same functional group inside the main chain, it is preferable to have a functional group only at the terminal when, for example, rubber elasticity is required for the crosslinked cured product. The number of crosslinkable functional groups of the vinyl polymer (I) is not particularly limited, but in order to obtain a cured product having higher crosslinkability, it is 1 or more on average, preferably 1.2 or more, more Preferably it is 1.5 or more.

The vinyl polymer (I) is not limited, but is preferably produced by living radical polymerization, and more preferably atom transfer radical polymerization. Further, the atom transfer radical polymerization is not limited, but a catalyst selected from a transition metal complex having a central metal of a group 7, 8, 9, 10, or 11 element of the periodic table is used as a catalyst. More preferred is a complex selected from the group consisting of copper, nickel, ruthenium, or iron complexes, and particularly preferred is a copper complex.

Although it does not limit as polymeric plasticizer (II), It is preferable that it is number average molecular weight 800-10000. The polymer plasticizer (II) is not limited, but is preferably a vinyl polymer, and more preferably a (meth) acrylic polymer.

The polymer plasticizer (II) is not limited, but is preferably produced by living radical polymerization, and more preferably atom transfer radical polymerization. Further, the atom transfer radical polymerization is not limited, but a catalyst selected from a transition metal complex having a central metal of a group 7, 8, 9, 10, or 11 element of the periodic table is used as a catalyst. More preferred is a complex selected from the group consisting of copper, nickel, ruthenium, or iron complexes, and particularly preferred is a copper complex.

The present invention comprises the following two components:
(A) A curable composition containing a vinyl polymer (I) having at least one crosslinkable functional group, and (B) a polymer plasticizer (II). The heat resistance and weather resistance of the combined cured product were maintained over a long period of time, and the application of the alkyd paint on the cured product was facilitated.

The curable composition of this invention contains said vinyl polymer (I) and polymer plasticizer (II). Below, the curable composition of this invention is explained in full detail.

<< Vinyl Polymer (I) >> << Main Chain> 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, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 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, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic acid monomers such as hexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and Dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized. Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this 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 represents 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, preferably 1 0.7 or less, more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene. The number average molecular weight of the vinyl polymer of the present invention is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1000 to 100,000.

<Method of synthesizing the main chain>
The method for synthesizing the vinyl polymer (I) of the present invention is not limited, but 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 uses an azo compound, a peroxide or the like as a polymerization initiator to simply copolymerize a monomer having a specific functional group and a vinyl monomer. It can be classified into “polymerization method” and “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 in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. Moreover, since it is free radical polymerization, there is also 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 functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal. 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 without causing a termination reaction.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical scavenger such as a nitroxide compound, and “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / 40415, or Sawamoto et al., Macromolecules. Macromolecules 1995, 28, 1721, JP-A-9-208616, JP-A-8-41117, and the like. In the present invention, there is no particular restriction as to which of these living radical polymerization methods is used, but an atom transfer radical polymerization method is preferred.

The living radical polymerization will be described in detail below, but before that, one of the controlled radical polymerizations that can be used for the production of the polymer (I) described later, polymerization using a chain transfer agent explain. Although it does not specifically limit as radical polymerization using a chain transfer agent (telomer), The following two methods are illustrated as a method of obtaining the vinyl polymer which has the terminal structure suitable for this invention.

JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Below, living radical polymerization is demonstrated. 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 generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical, 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the like. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or 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, Examples include 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 a galvinoxyl free radical may be used.

The 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 radical initiator is appropriate for 1 mol of radical capping agent.

Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis There are peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

As reported in Macromolecules 1995, 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.

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

Polymerization conditions such as a monomer, a solvent, and a polymerization temperature used in polymerization using a radical scavenger such as the above 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, an atom transfer radical polymerization method more preferable 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), or a halogenated compound. A sulfonyl compound or the like is used as an initiator.

If Specific _{examples, C 6 H 5 -CH 2 X} , C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2 ( where upper In which 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 group having 1 to 20 carbon atoms, aryl Group or aralkyl group, X is chlorine, bromine or iodine)
R ¹ —C ₆ H ₄ —SO ₂ X (in the above formulas, R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, X is chlorine, bromine, or iodine), etc. Is mentioned.

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

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

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

(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 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,

(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) _{n -CH = CH 2, o,} m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2, ( in each formula above, X is Chlorine, bromine, or iodine, n is an integer of 0-20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) -C _{6 H 4 - (CH 2)} n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) _{n -O- (CH 2) m CH} = CH 2, ( in each formula above, X is chlorine, bromine or iodine, n represents an integer of 1 to 20, m is 0 to 20 integer,)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- _{(CH 2) n -CH = CH} 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2, ( in the In each formula, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) _{-C 6 H 4 -O- (CH 2} ) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ , wherein X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is 0 to 20 Integer)

The organic halide having an alkenyl group further includes a compound represented by the general formula 2.
_{^{H 2 C = C (R 3}} ) -R 7 -C (R 4) (X) -R 8 -R 5 (2)
(Wherein R ³ , R ⁴ , R ⁵ , R ⁷ and X are the same as above, R ⁸ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or an o-, m-, p-phenylene group)

R ⁶ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, carbon to which a halogen is bonded Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group or a phenylene group as R ⁸ , and a direct bond may be used. When R ⁷ is not a direct bond, R ⁸ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

Specific examples of a compound of general formula _{2, CH 2 = CHCH 2 X} , CH 2 = C (CH 3) CH 2 X, CH 2 = CHC (H) (X) CH 3, CH 2 = C _{(CH 3) C (H)} (X) CH 3, CH 2 = CHC (X) (CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5, CH 2 = CHC (H) ( _{X) CH (CH 3) 2} , CH 2 = CHC (H) (X) C 6 H 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5, CH 2 = CHCH 2 C (H) _{(X) -CO 2 R, CH} 2 = CH (CH 2) 2 C (H) (X) -CO 2 R, CH 2 = CH (CH 2) 3 C (H) (X) -CO 2 R, _{CH 2 = CH (CH 2)} 8 C (H) (X) -CO 2 R, CH 2 = CHCH 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 mentioned above, X May be chlorine, bromine, or iodine, R may be an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group.

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

The organic halide having a crosslinkable silyl group is not particularly limited, and examples thereof include those having a structure represented by the general formula 3.
^{R 4 R 5 C (X)} -R 6 -R 7 -C (H) (R 3) CH 2 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) 3- _a (Y) _a (3)
(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X are the same as above, and R ⁹ and R ¹⁰ are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, 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). Represents an organosiloxy group, and when two or more R ⁹ or R ¹⁰ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, they may be the same or different, a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer from 0 to 19. (Provided that a + mb ≧ 1)

Specific examples of a compound of general formula _{3, XCH 2 C (O)} O (CH 2) n Si (OCH 3) 3, CH 3 C (H) (X) C (O) O (CH 2 ) _N Si (OCH ₃ ) ₃ , (CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ , XCH ₂ C (O) O (CH ₂ ) _n Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₃ C (H) (X) C (O) O (CH ₂ ) _n Si (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₂ C (X) C (O ) O (CH ₂ ) _n Si (CH ₃ ) (OCH ₃ ) ₂ (in the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m Si (OCH ₃ ) ₃ , (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OCH ₃ ) ₃ , CH ₃ CH ₂ C (H) (X _{) C (O) O (CH} 2) n O (CH 2) m Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n O (CH 2) m Si (CH 3) (OCH 3 ) ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m —Si (CH ₃ ) (OCH ₃ ) ₂ , (H ₃ C) ₂ C (X) _{C (O) O (CH 2} ) n O (CH 2) m -Si (CH 3) (OCH 3) 2, CH 3 CH 2 C (H) (X) C (O) O (CH _{2) n O (CH 2)} m -Si (CH 3) (OCH 3) 2, ( in each formula above, X is chlorine, bromine, iodine, n represents 1 to 20 integer, m is from 0 to 20 integer)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2 _{) 2 Si (OCH 3) 3} , o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p- _{XCH 2 -C 6 H 4 - (} CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3 _{) 3, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H _{4 - (CH 2) 2 -O-} (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 2 -O − _{CH 2) 3 Si (OCH 3} ) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH _{3) 3, o, m,} p-XCH 2 -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 _{H 4 -O- (CH 2) 3} Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si ( _{OCH 3) 3, o, m} , p-XCH 2 -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3, o, m, p-CH 3 _{C (H) (X) -C} 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) ( X) _{C 6 H 4 -O- (CH 2} ) 2 -O- (CH 2) 3 Si (OCH 3) 3, ( in each formula above, X is chlorine, bromine or iodine) and the like can be mentioned.

Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula 4.
_{^{(R 10) 3-a (}} Y) a Si- [OSi (R 9) 2-b (Y) b] m - CH 2 -C (H) (R 3) -R 7 -C (R 4) ( X) -R < ⁸ > -R < ⁵ > (4)
(Wherein R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , a, b, m, X, Y are the same as above)

If specifically exemplified such _{compounds, (CH 3 O) 3 SiCH} 2 CH 2 C (H) (X) C 6 H 5, (CH 3 O) 2 (CH 3) SiCH 2 CH 2 C _{(H) (X) C 6} H 5, (CH 3 O) 3 Si (CH 2) 2 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) _{2 C (H) (X)} -CO 2 R, (CH 3 O) 3 Si (CH 2) 3 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH _{2) 3 C (H) (} X) -CO 2 R, (CH 3 O) 3 Si (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 (CH ₃ ) Si (CH ₂ ) ₄ C (H) (X) —C ₆ H ₅ , wherein X is chlorine, bromine, or iodine, R is the number of carbons 1-20 alkyl groups, aryl groups, aralkyl groups) 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) n -OC (} O) C (H) (R) (X)
(In 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)

The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(In 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)

The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

(In 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) In order to obtain a polymer having two or more molecules in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. For example,

Etc. There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated can be used suitably.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. 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, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents. Solvent types 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 ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, and these can be used alone or in admixture of two or more. Moreover, although not limited, superposition | polymerization can be performed in 0 to 200 degreeC, Preferably it is 50 to 150 degreeC.

<Functional group>
The crosslinkable functional group of the vinyl polymer (I) is not limited, but a crosslinkable silyl group, alkenyl group, hydroxyl group, amino group, polymerizable carbon-carbon double bond, epoxy group, and the like are preferable. All of these crosslinkable functional groups can be used properly according to the use / purpose.

Position of the crosslinkable functional group When a rubber property is particularly required for the foamed product obtained by foaming and curing the curable composition of the present invention, the crosslinkable point between the crosslinkable points having a great influence on rubber elasticity is required. In order to increase the molecular weight, it is preferable that at least one of the crosslinkable functional groups is at the end of the molecular chain. More preferably, all the crosslinkable functional groups have at the molecular chain ends.

A method for producing a vinyl polymer having at least one crosslinkable functional group at the molecular end, in particular a (meth) acrylic polymer, is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, No. 6-211922 and the like. 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 ends, while Mw / Mn The value of the molecular weight distribution represented by is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. It is preferable.

These functional groups will be described below.
Crosslinkable silyl group The crosslinkable silyl group of the present invention is represented by the general formula 5;
^{_{- [Si (R 9) 2}} -b (Y) b O] m -Si (R 10) 3-a (Y) a (5)
{In the formula, R ⁹ and R ¹⁰ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ⁹ or When two or more R ¹⁰ are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
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. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) 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 the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula 6
-Si (R ¹⁰ ) _3-a (Y) _a (6)
A crosslinkable silyl group represented by the formula (wherein R ¹⁰ , Y and a are the same as described above) is preferable because it is easily available.

Alkenyl group The alkenyl group in the present invention is not limited, but is preferably one represented by general formula 7.
H ₂ C═C (R ¹¹ ) − (7)
(Wherein R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)

In General Formula 7, R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include the following groups.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 5 (CH 3)} , - C 6 H 5 (CH 3) 2, - (CH 2) n -C 6 H 5, - (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 carbon number of each group is 20 or less)
Among these, a hydrogen atom is preferable.

Further, although not limited, it is preferable that the alkenyl group of the polymer (I) is not activated by a carbonyl group, an alkenyl group or an aromatic ring conjugated with the carbon-carbon double bond. The bonding mode of the alkenyl group and the main chain of the polymer is not particularly limited, but is preferably bonded via a carbon-carbon bond, an ester bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, or the like.

Amino group The amino group in the present invention is not limited, but is -NR ¹² ₂ (R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² are May be the same or different, and may be linked to each other at the other end to form a cyclic structure.)-(NR ¹² ₃ ) ⁺ X ⁻ (R ¹² is as described above) The same, X ⁻ is a counter anion.) Even if it is an ammonium salt shown in FIG.

In the above formula, R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, for example, hydrogen, 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 an aralkyl group. Two R ¹² may be the same as or different from each other. 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 represented by the 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.

In General Formula 8, specific examples of R ¹³ are not particularly limited. 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
Etc. The but is preferably -H, -CH _3.

<Functional group introduction method>
Below, although the functional group introduction | transduction method to the vinyl polymer (I) of this invention is demonstrated, it is not limited to this. First, a method for introducing a crosslinkable silyl group, alkenyl group, and hydroxyl group by terminal functional group conversion will be described. Since these functional groups can be precursors to each other, they are described in the order 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 is added to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. Method of adding (B) Method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule (C) By radical polymerization Method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule when synthesizing a vinyl polymer (D) When synthesizing a vinyl polymer by radical polymerization, (E) A method using a chain transfer agent having a group 1 for a vinyl polymer having at least one highly reactive carbon-halogen bond A method of reacting a compound having a stable carbanion and crosslinkable silyl group in the child; and the like.

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

(Aa) When a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula 9 is used. The method of making it react as a monomer of 2.
_{^{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (9)
(In the formula, R ¹⁴ represents hydrogen or a methyl group, R ¹⁵ represents —C (O) O—, or o-, m-, p-phenylene group, R ¹⁶ represents a direct bond, 20 represents a divalent organic group having 20 and may contain one or more ether bonds, and R ¹⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents -20 aralkyl groups)

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. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.

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

(Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.

(Ad) A method in which halogen is substituted by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in General Formula 10.
^{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 ^- a is an electron withdrawing group stabilizing or one of the other is hydrogen or a 1 to 10 carbon atoms in the electron-withdrawing group 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)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .

(Af) An oxyanion or carboxylate anion having an alkenyl group as represented by the general formula (11) or (12) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of replacing halogen by reaction.
_{^{H 2 C = C (R 17}} ) -R 21 -O - M + (11)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²¹ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
_{^{H 2 C = C (R 17}} ) -R 22 -C (O) O - M + (12)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms, and may contain one or more ether bonds)
Etc.

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

Further, 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 are not limited thereto. A method of reacting a hydroxyl group of a vinyl polymer having at least one hydroxyl group with a base such as (Ag) sodium methoxide and reacting 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 in which an alkenyl group-containing carboxylic acid such as acrylic acid is reacted in the presence of an acid catalyst;

In the present invention, when a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. The method (Ab) is more preferable from the viewpoint of easier control.

When an alkenyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). It is preferable to use coalescence. In view of easier control, the method (Af) is more preferable.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, If a typical thing is shown, the compound shown by General formula 13 will be illustrated.
^{_{H- [Si (R 9) 2}} -b (Y) b O] m -Si (R 10) 3-a (Y) a (13)
{In the formula, R ⁹ and R ¹⁰ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ⁹ or When two or more R ¹⁰ are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }

Among these hydrosilane compounds, in particular, the general formula 14
H-Si (R ¹⁰ ) _3-a (Y) _a (14)
(Wherein R ¹⁰ , Y and a are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like.

Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) include the following methods, but are limited to these methods. It is not something.
(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 reacted as the second monomer. How to make.
_{^{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)

There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second monomer.

(Bb) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to make.

(Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide described in JP-A-5-262808.

(Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.

(Be) A method of radical polymerization of a vinyl monomer by using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.

(Bf) Hydrolysis of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method such as disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.

(Bg) A method of substituting halogen by reacting a vinyl group polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having a hydroxyl group as shown in the general formula 16.
^{M + C - (R 18)} (R 19) -R 20 -OH (16)
(In the formula, R ¹⁸ , R ¹⁹ and R ²⁰ are the same as above)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

(Bh) An enolate anion is prepared by allowing a metal polymer such as zinc or an organometallic compound to act on a vinyl polymer having at least one highly reactive carbon-halogen bond, and then aldehydes. Or a method of reacting ketones.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula 17 or 18, to form a halogen. How to replace.
HO—R ²¹ —O ^— M ⁺ (17)
(Wherein R ²¹ and M ⁺ are the same as above)
HO—R ²² —C (O) O ⁻ M ⁺ (18)
(Wherein R ²² and M ⁺ are the same as above)

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

Although it does not specifically limit as such a compound, The compound etc. which are shown by General formula 19 are mentioned.
_{^{H 2 C = C (R 14}} ) -R 21 -OH (19)
(Wherein R ¹⁴ and R ²¹ are the same as those described above.)

Although it does not specifically limit as a compound shown by the said General formula 19, From an easy acquisition, alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable. Etc.

In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl polymer is obtained by using a living radical polymerization method. It is preferable to synthesize. The method (Bb) is more preferable in terms of easier control.

When introducing a hydroxyl group by converting halogen in a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (Bi) is more preferable from the viewpoint of easier control.

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

As a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C), for example, trimethoxysilylpropyl (meth) acrylate, methyldimethoxysilylpropyl (meth) acrylate, etc., What is shown by the following general formula 20 is mentioned.
_{^{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)
(Wherein R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ , Y, a, b, m are the same as above. R ²³ is a direct bond or a divalent organic group having 1 to 20 carbon atoms. The above ether bond may be included.)

There is no particular limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, the end of the polymerization reaction or a predetermined value is determined. It is preferable to make it react as a 2nd monomer after completion | finish of reaction of this monomer.

Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method of (D) include mercaptans having a crosslinkable silyl group and crosslinkable silyl as shown in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And hydrosilane having a group.

The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (E), uses an organic halide as described above as an initiator, and a transition metal complex. Examples thereof include, but are not limited to, an atom transfer radical polymerization method using a catalyst. Examples of the compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula 21.
^{M + C - (R 18)} (R 19) -R 24 -C (H) (R 25) -CH 2 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) _3-a (Y) _a (21)
(In the formula, R ⁹ , R ¹⁰ , R ¹⁸ , R ¹⁹ , Y, a, b, m are the same as above. R ²⁴ is a direct bond or one divalent organic group having 1 to 10 carbon atoms. R ²⁵ which may contain the above ether bond represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

Epoxy group In the present invention, the vinyl polymer having a reactive functional group at the terminal is not limited, but includes the following steps: (1) A vinyl monomer is obtained by polymerizing a vinyl monomer by a living radical polymerization method. Producing a polymer;
(2) Subsequently, a compound having both a reactive functional group and an ethylenically unsaturated group is reacted. Further, in atom transfer radical polymerization, there is a method in which allyl alcohol is reacted at the end of polymerization and then epoxy cyclized with a hydroxyl group and a halogen group.

Amino group Examples of the method for producing a vinyl polymer having at least one amino group at the main chain terminal include the following steps.
(1) A vinyl polymer having at least one halogen group at the end of the main chain is produced, and (2) the terminal halogen is converted to a substituent having an amino group using an amino group-containing compound.

Although it does not specifically limit as a substituent which has an amino group, The group shown by General formula 22 is illustrated.
—O—R ²⁶ —NR ¹² ₂ (22)
(In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ¹² is hydrogen or monovalent having 1 to 20 carbon atoms. And two R ¹² may be the same or different from each other, and may be connected to each other at the other end to form a cyclic structure.)

In the general formula 22, R ²⁶ is a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds, for example, an alkylene group having 1 to 20 carbon atoms, carbon number Examples thereof include 6-20 arylene groups and C7-20 aralkylene groups.
-C ₆ H ₄ -R ²⁷ -
(In the formula, C ₆ H ₄ represents a phenylene group, and R ²⁷ represents 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.)
Or
—C (O) —R ²⁸ —
(In the formula, R ²⁸ represents a direct bond or a divalent organic group having 1 to 19 carbon atoms which may contain one or more ether bonds or ester bonds.)
Is preferred.

By converting the terminal halogen of the vinyl polymer, an amino group can be introduced at the end of the polymer. Although it does not specifically limit as a substitution method, The nucleophilic substitution reaction which uses an amino group containing compound as a nucleophile from the point that reaction is easy to control is preferable. Examples of such a nucleophile include a compound having both a hydroxyl group and an amino group represented by the general formula 23.
HO-R ²⁶ -NR ¹² ₂ (23)
(In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ¹² is hydrogen or monovalent having 1 to 20 carbon atoms. And two R ¹² may be the same or different from each other, and may be connected to each other at the other end to form a cyclic structure.)

In the above general formula 23, R ²⁶ is a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds, for example, an alkylene group having 1 to 20 carbon atoms, carbon number A 6-20 arylene group, a C7-20 aralkylene group, etc. are mentioned. Among these compounds having both a hydroxyl group and an amino group, R ²⁶ is
-C ₆ H ₄ -R ²⁷ -
(Wherein C ₆ H ₄ represents a phenylene group, and R ²⁷ represents 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). Aminophenols;
—C (O) —R ²⁸ —
(Wherein R ²⁸ represents a direct bond or a divalent organic group having 1 to 19 carbon atoms which may include one or more ether bonds or ester bonds).

Specific examples of the compound include ethanolamine; o, m, p-aminophenol; o, m, p-NH ₂ —C ₆ H ₄ —CO ₂ H; glycine, alanine, aminobutanoic acid, and the like.

A compound having both an amino group and an oxyanion can also be used as a nucleophile. Although it does not specifically limit as such a compound, For example, the compound shown by General formula 24 is mentioned.
M ⁺ O ⁻ —R ²⁶ —NR ¹² ₂ (24)
(In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ¹² is hydrogen or monovalent having 1 to 20 carbon atoms. The two R ¹² groups may be the same or different from each other, and may be linked to each other at the other end to form a cyclic structure, where M ⁺ is an alkali metal ion or 4 Represents a class ammonium ion.)

In the above general formula 24, M ⁺ is a counter cation of an oxyanion and represents an alkali metal ion or a quaternary ammonium ion. Examples of the alkali metal ions include lithium ions, sodium ions, potassium ions, and the like, preferably sodium ions or potassium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like.

Of the compounds having both an amino group and an oxyanion, the salts of aminophenols represented by the general formula 25 or the amino acids represented by the general formula 26 can be easily controlled because of easy control of the substitution reaction. Salts are preferred.
^{_{M + O - -C 6 H 4}} -R 27 -NR 12 2 (25)
M ⁺ O ⁻ —C (O) —R ²⁸ —NR ¹² ₂ (26)
(Wherein C ₆ H ₄ is a phenylene group, R ² 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, R ³ is A direct bond or a divalent organic group having 1 to 19 carbon atoms which may contain one or more ether bonds or ester bonds, and R ¹² 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 may be connected to each other at the other end to form a cyclic structure, and M ⁺ is the same as above.)
Compounds having an oxyanion represented by general formulas 24-26 can be easily obtained by reacting the compound represented by general formula 23 with a basic compound.

Various compounds can be used as the basic compound. For example, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, hydrogen carbonate Sodium, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide and the like can be mentioned. Although the usage-amount of the said base does not have a restriction | limiting in particular, It is 0.5-5 equivalent with respect to the said precursor, Preferably it is 0.8-1.2 equivalent.

Examples of the solvent used in the reaction of the precursor with the base include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon systems such as methylene chloride and chloroform. Solvents; Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, and tert-butyl alcohol; Nitriles such as acetonitrile, propionitrile, and benzonitrile Solvents; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide; Sulfoxide solvents such as Sid the like. These can be used individually or in mixture of 2 or more types.

A compound having an oxyanion in which M ⁺ is a quaternary ammonium ion is obtained by preparing a compound in which M ⁺ is an alkali metal ion and allowing a quaternary ammonium halide to act on the compound. 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 polymer terminal halogen. For example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methanol, Alcohol solvents such as ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate, butyl acetate; ethylene carbonate, propylene Examples thereof include carbonate solvents such as carbonate; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide. These can be used individually or in mixture of 2 or more types.

The reaction temperature can be 0-150 degreeC. Moreover, the usage-amount of an amino group containing compound is although it does not restrict | limit in particular, It is 1-5 equivalent with respect to a polymer terminal halogen, Preferably it is 1-1.2 equivalent.

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 for the nucleophilic substitution reaction affects the nucleophilic substitution reaction, it is preferably protected with an appropriate substituent. Examples of such substituents include benzyloxycarbonyl group, tert-butoxycarbonyl group, 9-fluorenylmethoxycarbonyl group and the like. Further, a method of substituting the halogen terminal of the vinyl polymer with an azide anion and then reducing with LAH or the like can be mentioned.

Polymerizable carbon-carbon double bond The method for introducing a polymerizable carbon-carbon double bond into the polymer (I) of the present invention is not limited, and examples thereof include the following methods. It is done.
(1) A method for producing a vinyl polymer by replacing a halogen group with a compound having a radical polymerizable carbon-carbon double bond. As a specific example, a method of reacting a vinyl polymer having a structure represented by the general formula 27 with a compound represented by the general formula 28.
-CR ²⁹ R ³⁰ X (27)
(In the formula, R ²⁹ and R ³⁰ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ¹³ ) ═CH ₂ (28)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

(2) A method of reacting a vinyl polymer having a hydroxyl group with a compound represented by the general formula 29.
XC (O) C (R ¹³ ) ═CH ₂ (29)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)

(3) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group, and a reaction between a residual isocyanate group and a compound represented by the general formula 30 is performed.
^{HO-R 31} - OC (O) C (R ¹³ ) ═CH ₂ (30)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ³¹ represents a divalent organic group having 2 to 20 carbon atoms.)

Each of these methods will be described in detail below.
The method (1) will be described.
(1) A method of reacting a vinyl polymer having a terminal structure represented by the general formula 27 with a compound represented by the general formula 28.
-CR ²⁹ R ³⁰ X (27)
(In the formula, R ²⁹ and R ³⁰ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ¹³ ) ═CH ₂ (28)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

A vinyl polymer having a terminal structure represented by the general formula 27 is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a halogen compound. The chain transfer agent is used to polymerize vinyl monomers, and the former is preferred.

Examples of the compound represented by the general formula 28 is not particularly ^limited, specific examples of ^{R 13} are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is 2 It represents an integer of _{~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3. M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion. The amount of the oxyanion of the general formula 28 used is preferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalents relative to the halogen group of the general formula 27.

The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile, etc. are used. Although the temperature which performs reaction is not limited, Generally it is 0-150 degreeC, In order to hold | maintain a polymeric terminal group, Preferably it carries out at room temperature-100 degreeC.

The method (2) will be described.
(2) A method of reacting a vinyl polymer having a hydroxyl group with a compound represented by the general formula 29.
XC (O) C (R ¹³ ) ═CH ₂ (29)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)

Examples of the compound represented by the general formula 29 is not particularly ^limited, specific examples of ^{R 13} are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is 2 It represents an integer of _{~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

The vinyl polymer having a hydroxyl group, preferably at the terminal, is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group The chain transfer agent is used to polymerize vinyl monomers, and the former is preferred. Although the method for producing a vinyl polymer having a hydroxyl group by these methods is not limited, the following methods are exemplified.

(A) A method in which a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule represented by the following general formula 31 is reacted as a second monomer when a vinyl polymer is synthesized by living radical polymerization.
_{^{H 2 C = C (R 32}} ) -R 33 -R 34 -OH (31)
(In the formula, R ³² is an organic group having 1 to 20 carbon atoms, preferably hydrogen or methyl group, and may be the same or different from each other. R ³³ is —C (O) O— (ester group), Or represents an o-, m-, or p-phenylene group, and R ³⁴ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds R ³³ There are those of the ester group (meth) acrylate compound, those R ³³ is a phenylene group which is a compound of styrene.)

Although there is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, particularly when a rubber-like property is expected, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer It is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, the second monomer has a low polymerizable alkenyl group and hydroxyl group as the second monomer after the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.

Although it does not specifically limit as such a compound, The compound etc. which are shown by General formula 32 are mentioned.
_{^{H 2 C = C (R 32}} ) -R 35 -OH (32)
(In the formula, R ³² is the same as described above. R ³⁵ represents a C 1-20 divalent organic group which may contain one or more ether bonds.)

Although it does not specifically limit as a compound shown by the said General formula 32, From an easy acquisition, alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable.

(C) A vinyl polymer having 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. A hydroxyl group is introduced into the terminal by hydrolysis or reaction with a hydroxyl group-containing compound.

(D) reacting a vinyl group polymer having at least one carbon-halogen bond represented by the general formula 27 obtained by atom transfer radical polymerization with a stabilized carbanion having a hydroxyl group as shown in the general formula 33 To replace the halogen.
^{M + C - (R 36)} (R 37) -R 35 -OH (33)
(Wherein, R ³⁵ are the same as those described above .R ³⁶ and R ³⁷ together carbanion C ^- an electron-withdrawing group stabilizing or one of the electron-withdrawing several other is hydrogen or a carbon in the group 1 to 10, And an electron withdrawing group of R ³⁶ and R ³⁷ includes —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group) ), - COSR (thioester group), - CN (nitrile group), -. NO ₂ (nitro group), etc. the substituent R is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms An aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group or phenyl group having 1 to 10 carbon atoms, and R ³⁶ and R ³⁷ include —CO ₂ R, —C (O) R and —CN, Especially preferred Yes.)

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula 27 obtained by atom transfer radical polymerization is allowed to react with, for example, a single metal such as zinc or an organometallic compound to produce an enolate anion. And then reacting aldehydes or ketones.

(F) A vinyl-based polymer having at least one halogen represented by the general formula 27, preferably a hydroxyl group-containing oxyanion represented by the following general formula 34 or the following general formula 35 A method of reacting the hydroxyl group-containing carboxylate anion represented 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)
(Wherein R ³⁵ and M ⁺ are the same as those described above.)

In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferable because control is easier. In addition, when a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control of (f) is easier. The method is further preferred.

The method (3) will be described.
(3) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group, and the remaining isocyanate group reacts with a compound represented by the general formula 36.
^{HO-R 31} - OC (O) C (R ¹³ ) ═CH ₂ (36)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ³¹ represents a divalent organic group having 2 to 20 carbon atoms.)

Examples of the compound represented by the general formula 36 is not particularly ^limited, specific examples of ^{R 13} are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is 2 It represents an integer of _{~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3. A specific compound includes 2-hydroxypropyl methacrylate.

The vinyl polymer having a hydroxyl group at the terminal is as described above. The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1 , 5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and the like; and the like. These can be used alone or in combination of two or more. Moreover, you may use block isocyanate.

In order to make better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate as the polyfunctional isocyanate compound (b).

<< About Polymer Plasticizer (II) >>
The polymer plasticizer (II) used in the present invention is a polymer having a number average molecular weight of 500 to 15000. By adding this polymer plasticizer, the viscosity and slump property of the curable composition and the composition are cured. The mechanical properties such as tensile strength and elongation of the cured product can be adjusted, and the initial physical properties are compared with the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. It can be maintained over a long period of time, and the drying properties when the alkyd paint is applied to the cured product can be improved.

The number average molecular weight of the polymer plasticizer is a polymer of 500 to 15000, preferably 800 to 10,000, more preferably 1000 to 8,000. If the molecular weight is too low, the plasticizer flows out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen.

Specific examples of such polymer plasticizers include, for example, vinyl polymers obtained by polymerizing the aforementioned vinyl monomers by various methods; two bases such as sebacic acid, adipic acid, azelaic acid, and phthalic acid. Polyester plasticizers obtained from acids and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and these polyether polyols Polyethers such as derivatives obtained by converting hydroxyl groups of ester groups to ether groups; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylic Nitrile, polychloroprene, although paraffin chloride and the like, but is not limited thereto.

Among these polymer plasticizers, those compatible with the vinyl polymer (I) are preferable. Of these, vinyl polymers are preferred from the viewpoints of compatibility, weather resistance, and heat resistance. Among the vinyl polymers, (meth) acrylic polymers are preferable, and acrylic polymers are more preferable. The polymer synthesis method is preferably a living radical polymerization method, more preferably an atom transfer radical polymerization method, because the molecular weight distribution is narrow and viscosity can be lowered. The said polymeric plasticizer may be used independently and may use 2 or more types together. Moreover, you may use together with a low molecular plasticizer in the range which does not have a bad influence on a physical property if needed.

The polymer plasticizer (II) is used in an amount of 5 to 150 parts by weight, preferably 10 to 120 parts by weight, based on 100 parts by weight of the vinyl polymer (I) having at least one crosslinkable functional group. Preferably it is 20-100 weight part. 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. These plasticizers can also be blended at the time of polymer production.

<< Curable composition >>
In the curable composition of the present invention, a curing catalyst or a curing agent is required depending on each crosslinkable functional group. Moreover, you may add various compounding agents according to the target physical property.

<Curing catalyst and 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. The properties of the cured product can be broadly created from rubbery to resinous depending on the molecular weight and main chain skeleton of the polymer.

Examples of such a condensation catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diester. Isooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate, etc. Tetravalent tin compounds such as: tetrabutyl titanate, tetrapropyl titanate, etc .; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, Organoaluminum compounds such as isopropoxyaluminum ethyl acetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Lead octylate; Butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine , Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo 5,4,0) amine compounds such as undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess A reaction product of a polyamine and an epoxy compound; a silane coupling agent having an amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane; a silanol condensation catalyst such as Examples include other known silanol condensation catalysts such as acidic catalysts and basic catalysts.

These catalysts may be used alone or in combination of two or more. The amount of the condensation catalyst is preferably about 0.1 to 20 parts per 100 parts (parts by weight, the same shall apply hereinafter) of the vinyl polymer (I) having at least one crosslinkable silyl group. Is more preferable. If the amount of the silanol condensation catalyst is less than this range, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, if the blending 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 increase the activity of the condensation catalyst, the general formula 37
R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (37)
(In the formula, R ⁴⁹ and R ⁵⁰ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Furthermore, 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, R ^{49 in} the general formula (1) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane. Is preferably an aryl group having 6 to 20 carbon atoms because it has a large effect of accelerating the curing reaction of the composition. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because of low cost and easy availability.

The compounding amount of the silicon compound is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts with respect to 100 parts of the vinyl polymer (I) having at least one crosslinkable silyl group. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding 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 When crosslinking is performed using an alkenyl group, it is not limited, but it is preferable to crosslink by a hydrosilylation reaction using a hydrosilyl group-containing compound as a curing agent and a hydrosilylation catalyst.

The hydrosilyl group-containing compound is not particularly limited as long as it is a hydrosilyl group-containing compound that can be cured by crosslinking with a polymer having an alkenyl group, and various compounds can be used. For example, a chain polysiloxane represented by the general formula 38 or 39;
^{_{R 51 3 SiO- [Si (R}} 51) 2 O] a - [Si (H) (R 52) O] b - [Si (R 52) (R 53) O] c -SiR 51 3 (38)
HR ⁵¹ ₂ SiO- [Si (R ⁵¹ ) ₂ O] _a- [Si (H) (R ⁵² ) O] _b- [Si (R ⁵² ) (R ⁵³ ) O] _c -SiR ⁵¹ ₂ H (39)
(In the formula, R ⁵¹ and R ⁵² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁵³ represents an alkyl group or aralkyl group having 1 to 10 carbon atoms. A is 0 ≦ a ≦ 100, b Represents an integer satisfying 2 ≦ b ≦ 100 and c represents 0 ≦ c ≦ 100.) Cyclic siloxane represented by the general formula 40;

(In the formula, R ⁵⁴ and R ⁵⁵ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁵⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. D represents 0 ≦ d ≦ 8, e 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and 3 ≦ d + e + f ≦ 10 is satisfied).

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with (meth) acrylic polymers, chain siloxanes represented by the following general formulas 41 and 42 having a phenyl group and cyclic siloxanes represented by the general formulas 43 and 44 Is preferred.
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (41)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (CH 3) {CH 2 C (H) (R 57) C 6 H 5} O] h -Si (CH 3 ₃ (42)
(In the formula, R ⁵⁷ represents hydrogen or a methyl group. G represents an integer of 2 ≦ g ≦ 100 and h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group.)

(In the formula, R ⁵⁷ represents hydrogen or a methyl group. I represents an integer satisfying 2 ≦ i ≦ 10, j represents 0 ≦ j ≦ 8, and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. Is shown.)

Further, as the hydrosilyl group-containing compound, the hydrosilyl group-containing compound represented by the general formulas 38 to 44 with respect to the low-molecular compound having two or more alkenyl groups in the molecule, a part of the hydrosilyl group remains after the reaction. Thus, the compound obtained by carrying out addition reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O Ether compounds such as' -diallyl bisphenol A, 3,3'-diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, carbonates such as diethylene glycol diallyl carbonate System compounds.

The compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst with respect to an excessive amount of the hydrosilyl group-containing compound represented by the general formulas 38 to 44. Of these compounds, the following are preferred in view of the availability of raw materials, the ease of removal of the excessively used siloxane, and the compatibility of the component (A) with the polymer.

The polymer and the curing agent can be mixed at an arbitrary 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 2.5 It is especially preferable that it is -0.4. When the molar ratio is 5 or more, curing is insufficient and only a cured product having low tackiness and a low strength can be obtained. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain 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 advance the reaction more rapidly. Such hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.

The radical initiator is not particularly limited, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, 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, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate such as 1,1 Examples thereof include peroxyketals such as -di (t-butylperoxy) cyclohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

Also, it is not particularly limited as a transition metal catalyst, for example, platinum simple substance, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. Complex, platinum-olefin complex, and platinum (0) -divinyltetramethyldisiloxane complex. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 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. Although there is no restriction | limiting in particular as a catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of alkenyl groups of vinyl-type polymer (I), Preferably 10 ^<-3 > ^-10 <^-6> mol is preferable. It is good to use in the range. If it is less than 10 ⁻⁸ mol, curing does not proceed sufficiently. Moreover, since a hydrosilylation catalyst is expensive, it is preferable not to use ^10-1 mol or more.

Although there is no restriction | limiting in particular about hardening temperature, Generally it is good to make it harden | cure at 0 to 200 degreeC, Preferably it is 30 to 150 degreeC, More preferably, it is 80 to 150 degreeC.

In the case of hydroxyl group The polymer having a hydroxyl group of the present invention is uniformly cured by using a compound having two or more functional groups capable of reacting with a hydroxyl group as a curing agent. Specific examples of the curing agent include, for example, a polyisocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and its alkyl etherified product or low-condensed product, a polyfunctional carboxylic acid, and Examples thereof include halides thereof. In producing 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 polyisocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and its alkyl etherified product or low-condensed product, a polyfunctional carboxylic acid, and Examples thereof include halides thereof. In producing 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, and examples thereof include aliphatic amines, alicyclic amines, aromatic amines; acid anhydrides; polyamides Imidazoles; amine imides; urea; melamine and its derivatives; polyamine salts; phenolic resins; polymercaptans, polysulfides; Etc. are used.

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

Hereinafter, these crosslinking reactions will be described in detail. When cross-linking a polymer having a polymerizable carbon-carbon double bond, a polymerizable monomer and / or oligomer or 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 are preferable. Examples of radical polymerizable groups include acrylic functional groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, vinyl chloride groups, and the like. Is mentioned. Especially, what has the (meth) acryl group similar to the polymer of this invention is 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, a conjugated diene group, and a vinyl ketone group. Among these, those having an acrylic functional group are preferable.

Specific examples of the monomer include (meth) acrylate monomers, cyclic acrylates, N-vinyl pyrrolidone, styrene monomers, acrylonitrile, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, and the like. It is done. Examples of (meth) acrylate monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and compounds of the following formula. it can.

Styrene monomers include styrene and α-methylstyrene, acrylamide monomers include acrylamide, N, N-dimethylacrylamide, conjugated diene monomers include butadiene and isoprene, and vinyl ketone monomers include methyl vinyl ketone. Etc.

Examples of polyfunctional monomers include neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxy) Ethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetra Bromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9 Nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin, polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene diisocyanate (Hydroxylate, xylylene diisocyanate, etc.) Urethane resin obtained from hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Examples thereof include urethane acrylate resins obtained by the above, resins obtained by introducing (meth) acrylic groups into the above polyols through ester bonds, polyester acrylate resins, and the like.

These monomers and oligomers are selected depending on the initiator used and the curing conditions. Further, the number average molecular weight of the monomer and / or oligomer having an acrylic functional group is preferably 2000 or less, and more preferably 1000 or less, from the reason that the compatibility is good.

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

Although there is no restriction | limiting in particular as a photoinitiator used for this invention, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is especially preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophene, 3-bromo Acetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethyl) Minofeniru) ketone, benzyl methoxy ketal, 2-chlorothioxanthone tone, and the like. These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue are included. It is done.

Moreover, you may use a near-infrared light absorptive cationic dye as a near-infrared photoinitiator. As the near-infrared light-absorbing cationic dye, it is excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light absorption disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use a cationic cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

The addition amount of the photopolymerization initiator is not particularly limited since it only needs to slightly functionalize the system, but 0.001 to 10 parts by weight is preferable with respect to 100 parts of the polymer of the composition.

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

Further, it is preferable to use heat as a method for crosslinking the polymer having a polymerizable carbon-carbon double bond. When crosslinking by active energy rays, it is preferable to contain a thermal polymerization initiator.

Although there is no restriction | limiting in particular as a thermal-polymerization initiator used for this invention, An azo initiator, a peroxide, a persulfuric acid, and a redox initiator are contained. Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (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), 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries), etc. I can get lost.

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate. Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; Examples include systems based on 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, pinacol such as tetraphenyl 1,1,2,2-ethanediol. A preferred thermal radical initiator is selected from the group consisting of azo initiators and peroxide initiators. More preferred are 2,2'-azobis (methylisobutylate), t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is typically, but not limited to, a polymer having an acrylic functional group at at least one end of the present invention. When the total amount of the combined monomer and other monomer and oligomer mixture is 100 parts by weight, it is about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight. If a mixture of initiators is used, the total amount of initiator mixture is as if only one initiator was used.

The method for curing the thermosetting composition of the present invention is not particularly limited, but the temperature varies depending on the type of thermal initiator, polymer (I), compound to be added, etc. Within the range of ° C is preferred, and within the range of 70 ° C to 200 ° C is more preferred. The curing time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc. used, but is usually in the range of 1 minute to 10 hours.

<Adhesive agent>
A silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the composition of the present invention. 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-ureido Amino group-containing silanes such as propyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Epoxy group-containing silanes such as lan; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane, etc. Carboxysilanes of vinyl type; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltri Halogen-containing silanes such as methoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate, and the like. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. .

The silane coupling agent used for this invention is normally used in 0.1-20 parts with respect to 100 parts of crosslinkable functional group containing polymers. In particular, it is preferably used in the range of 0.5 to 10 parts. The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.

Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

<Filler>
Various fillers are used in the curable composition of the present invention as needed. Specific examples of the filler include, for example, wood powder, parb, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, fumed silica, sedimentation Reinforcing fillers such as silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, Fillers such as organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust and shirasu balloon; fibrous fillers such as asbestos, glass fiber and filament It is done. Of 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 you want to obtain a cured product with high strength with these fillers, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystalline silica, molten A filler selected from silica, calcined clay, clay and activated zinc white can be added. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. These fillers may be used alone or in combination of two or more. The amount of the filler used is not limited, but is preferably 10 to 1000 parts, more preferably 50 to 300 parts, relative to 100 parts of the vinyl polymer (I).

<Physical property modifier>
You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, the hardness when the composition of the present invention is cured can be increased, the hardness can be decreased, and the elongation can be increased. The said physical property modifier may be used independently and may be used together 2 or more types.

<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging preventing agent is not particularly limited, and examples thereof include polyamide waxes, hydrogenated castor oil derivatives; 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 necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, flame retardants, curability modifiers, anti-aging agents, radical inhibitors, ultraviolet absorbers, metal deactivators, ozone degradation inhibitors, light stabilizers, phosphorous peroxides. Examples include oxide decomposing agents, lubricants, pigments, foaming agents, and photocurable resins. These various additives may be used alone or in combination of two or more. Specific examples of such additives are described in, for example, the specifications of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904. Yes.

The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use.

<Application>
The curable composition of the present invention is not limited, but is a sealing material such as an elastic sealing material for construction and a sealing material for double-glazed glass, and electrical / electronic component materials such as a solar cell back surface sealing material, insulation for electric wires and cables. Electrical insulation materials such as coating materials, adhesives, adhesives, elastic adhesives, paints, powder paints, coating materials, foams, potting agents for electrical and electronic equipment, films, gaskets, casting materials, various molding materials, and It can be used for various purposes such as meshed glass and sealing material for rust prevention and waterproofing of laminated glass end face (cut part).

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. In the following Examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel and chloroform as a GPC solvent were used.

(Production Example 1)
CuBr (42.0 g, 0.293 mol) was charged into a 10 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (559 mL) was added and stirred in an oil bath at 70 ° C. for 45 minutes. To this, butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (176 g, 0.488 mol), pentamethyldiethylenetriamine (4.00 mL, 3.32 g, 19.2 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 190 minutes. Triamine (4.00 mL, 3.32 g, 0.0192 mol) was added during the dropwise addition of butyl acrylate. After 310 minutes from the start of the reaction, 1,7-octadiene (1.44 L, 1.07 kg, 9.75 mol) and triamine (20.5 mL, 17.0 g, 98.1 mol) were added, followed by heating at 70 ° C. for 210 minutes. Stir. The reaction mixture was diluted with hexane, passed through an activated alumina column, and then the volatile component was distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [1]). The number average molecular weight of the polymer [1] was 14,000, and the molecular weight distribution was 1.3.

A 10-liter separable flask equipped with a reflux tube was charged with the polymer [1] (2.7 kg), potassium benzoate (142 g), and N, N-dimethylacetamide (2.7 L), and a nitrogen stream at 70 ° C. for 25 hours. Stir with heating. N, N-dimethylacetamide was removed under heating and reduced pressure, and then diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatile content of the filtrate was distilled off under reduced pressure to obtain a polymer [2].

A 2 L round bottom flask equipped with a reflux tube was charged with polymer [2] (2.7 kg), aluminum silicate (540 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700 PEL), toluene (2.7 L), and 5% at 100 ° C. under a nitrogen stream. Stir with heating for hours. After removing the aluminum silicate by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [3].

In a 1 L pressure-resistant reaction vessel, polymer [3] (760 g), dimethoxymethylhydrosilane (46.3 mL, 0.38 mol), methyl orthoformate (13.7 mL, 0.13 mmol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the platinum catalyst was used in an amount of 10 ⁻³ equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 1 hour. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [4]). The number average molecular weight of the obtained polymer was 15000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis and found to be 2.0.

(Production Example 2)
CuBr (22.4 g, 0.156 mol) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (112 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, butyl acrylate (0.20 kg), methyl 2-bromopropionate (86.9 g, 0.520 mol), pentamethyldiethylenetriamine (0.19 mL, 0.18 g, 1.04 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (0.80 kg) was continuously added dropwise over 150 minutes. Triamine (1.81 mL, 1.71 g, 9.88 mmol) was added during the dropwise addition of butyl acrylate. Subsequently, the mixture was heated and stirred at 70 ° C. for 230 minutes. The reaction mixture was diluted with toluene, passed through an activated alumina column, and then the volatile component was distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [5]). The number average molecular weight of the polymer [5] was 2600, and the molecular weight distribution was 1.18.

A 2 L separable flask equipped with a reflux tube was charged with the polymer [5] (0.937 kg), potassium acetate (73.5 g), and N, N-dimethylacetamide (0.8 L). Stir with heating for hours. N, N-dimethylacetamide was removed under heating and reduced pressure, and then diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatile content of the filtrate was distilled off under reduced pressure to obtain a polymer [6].

Example 1
After mixing 100 parts of the polymer [4] obtained in Production Example 1 with 50 parts of various polymer plasticizers, stirring and mixing with 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate), vacuum degassing Then, a sheet-like cured product having a thickness of 2 mm was produced. The curing curing was allowed to stand indoors for 2 days and then at 50 ° C. for 3 days. A 2 (1/3) type dumbbell test piece was punched from the cured sheet-like cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The results are shown in Table 1.

(Comparative Example 1)
A cured product was produced in the same manner as in Example 1 except that the high-molecular plasticizer in Example 1 was replaced with a low-molecular plasticizer. Similarly, a tensile test was performed. The results are shown in Table 1.

(Example 2)
Several kinds of the sheet-like cured product (dumbbell test piece) obtained in Example 1 were allowed to stand in a dryer at 150 ° C. The sample was taken out after a certain period and a tensile test was conducted in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
Several kinds of cured sheets (dumbbell test pieces) obtained in Comparative Example 1 were allowed to stand in a dryer at 150 ° C. in the same manner as in Example 2. The sample was taken out after a certain period and a tensile test was conducted in the same manner as in Example 2. The results are shown in Table 2.

(Example 3)
About several kinds from the sheet-like hardened material (dumbbell test piece) obtained in Example 1, a sunshine weather meter (WEL-SUN-DC type manufactured by Suga Test Instruments Co., Ltd., black panel temperature of 63 ° C., irradiation for 2 hours, rainfall time) 18 minutes). The sample was taken out after a certain period and a tensile test was conducted in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 3)
About several kinds from the sheet-like hardened material (dumbbell test piece) obtained in Comparative Example 1, a sunshine weather meter (WEL-SUN-DC type manufactured by Suga Test Instruments Co., Ltd., black panel temperature 63 ° C., irradiation time 2 hours, rainfall time) 18 minutes). The sample was taken out after a certain period and a tensile test was conducted in the same manner as in Example 3. The results are shown in Table 3.

Example 4
Various alkyd paints were applied to several kinds of the sheet-like cured product (dumbbell test piece) obtained in Example 1 and allowed to stand indoors. The surface coated after a certain period of time was touched with a finger to determine the degree of curing. The results are shown in Table 4.

(Comparative Example 4)
Various alkyd paints were applied to several kinds of the sheet-like cured product (dumbbell test piece) obtained in Comparative Example 1 and allowed to stand indoors. In the same manner as in Example 4, the painted surface was touched after a certain period of time, and the degree of curing was determined. The results are shown in Table 4.

Claims (13)

Following two components: a vinyl polymer having at least one crosslinkable silyl group (I), and, polymeric plasticizer (II), in electrical and electronic potting agents or coating materials curable composition containing There,
The vinyl polymer (I) is a (meth) acrylic polymer having a molecular weight distribution of less than 1.8,
The curable composition whose polymer plasticizer (II) is a (meth) acrylic polymer having a molecular weight distribution of less than 1.8 . Further, the curable composition according to claim 1 containing a condensation catalyst. The curable composition according to claim 1 or 2 , wherein the vinyl polymer (I) is produced by living radical polymerization. The curable composition according to claim 3 , wherein the living radical polymerization is atom transfer radical polymerization. Atom transfer radical polymerization, the seventh group of the periodic table, Group 8, Group 9, claim 4, characterized in that group 10, or a complex selected from transition metal complexes of Group 11 elements as a central metal as a catalyst The curable composition as described. 6. The curable composition according to claim 5 , wherein the metal complex used as a catalyst is a complex selected from the group consisting of copper, nickel, ruthenium or iron complexes. The curable composition according to claim 6 , wherein the metal complex used as a catalyst is a copper complex. The curable composition according to any one of claims 1 to 7 , wherein the polymer plasticizer (II) has a number average molecular weight of 500 to 15000. The curable composition according to any one of claims 1 to 7 , wherein the polymer plasticizer (II) has a number average molecular weight of 800 to 10,000. The curable composition according to any one of claims 1 to 7 , wherein the polymer plasticizer (II) has a number average molecular weight of 1000 to 8000. The curable composition according to any one of claims 1 to 10 , wherein the production method of the polymer plasticizer (II) is a living radical polymerization method. The curable composition according to any one of claims 1 to 11 , wherein the production method of the polymer plasticizer (II) is an atom transfer radical polymerization method. The amount of the polymeric plasticizer (II) used is 5 to 150 parts by weight based on 100 parts by weight of the vinyl polymer (I) having at least one crosslinkable silyl group. The curable composition according to any one of 12 .