JP2008107511A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for resist excellent in oil, heat and light resistances and flexibility. <P>SOLUTION: The curable composition for resist contains a vinyl polymer (A) having at least one crosslinkable functional group, a compound (B) capable of crosslinking the vinyl polymer and, optionally, a carboxylic acid-containing compound and/or polymer (C). A cured product for resist having good oil, heat and light resistances, good flexibility and compatibility as well as excellent resist performance is provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition for resist and a cured product obtained by curing it. More specifically, the present invention relates to a curable composition for a resist containing a produced vinyl polymer having at least one crosslinkable functional group and a compound capable of crosslinking the vinyl polymer.

  In recent years, there has been a demand for higher performance in resist flexography, resolution enhancement, substrate flexibility, and resist film thinning (Non-patent Document 1). In general, a curable composition for resist is cured by an active energy ray typified by UV, heating, or the like (Non-Patent Document 2), and a multifunctional monomer or multifunctional oligomer is used as a crosslinking reactive component. Is used (Patent Document 1). In addition, adhesion of the resist to the substrate and improvement in etching resistance are also described (Patent Document 2). However, since the resist obtained by crosslinking of these reactive monomers and oligomers is hard and brittle, there are problems such as insufficient substrate following ability and cracking when the resist film pressure changes. is there.

  In order to improve such problems, for example, studies have been made to apply a relatively flexible reactive oligomer such as urethane acrylate. However, since the molecular weight of the reactive oligomer cannot be extremely increased from the viewpoint of workability (viscosity), there is a limit to imparting flexibility in a technique using a flexible reactive oligomer. Even in applications requiring heat resistance and light resistance, such as permanent resists, the technology applying urethane acrylate results in insufficient heat resistance and light resistance performance.

For this reason, a technique for imparting sufficient flexibility without degrading performance such as heat resistance and chemical resistance is desired, but no effective technique has been proposed.
2006 Optical Functional Materials and Product Market Overview (Fuji Keizai Co., Ltd.) UV and EB curable materials (supervised by Yoneho Tabata, edited by Radtech, CMC Co., Ltd., issued on December 28, 1992) JP-A-2005-250111 JP-A-2005-92102

  An object of this invention is to provide the curable composition for resists which can give the hardened | cured material excellent in the base material followability based on a softness | flexibility, maintaining favorable heat resistance and light resistance.

  In addition, the present invention improves the compatibility and curability of the crosslinkable component and the carboxylic acid-containing resin contained in the resist curable composition applied to the application in resist applications exposed to alkali development. The purpose is to do.

    As a result of intensive studies by the present inventors in view of the above circumstances, the present inventors have found that the above problems can be solved by using a vinyl polymer having a specific crosslinkable functional group as a crosslinkable component, and the present invention is completed. It came to.

  That is, the present invention is a resist composition comprising a vinyl polymer (A) having at least one crosslinkable functional group at the molecular end, and a compound (B) capable of crosslinking the vinyl polymer (A). The present invention relates to a curable composition (claim 1).

  The preferable form of this invention is the curable composition for resists of Claim 1 (Claim 2) which contains the prepolymer and / or polymer (C) which have an acidic functional group further.

  A preferred embodiment of the present invention is the resist curable composition (claim 3), wherein the ratio of the vinyl polymer (A) in the curable composition is 1 to 80% by weight.

In a preferred embodiment of the present invention, the crosslinkable functional group in the vinyl polymer (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
It is a curable composition for resists as described in any one of 1-3 which are these (Claim 4).
A compound (B) is an initiator, It is a curable composition for resists as described in any one of Claims 1-4 (Claim 5).

  In a preferred embodiment of the present invention, the compound (B) is at least one selected from the group consisting of a photo radical initiator, a thermal radical initiator, and a redox initiator, according to any one of claims 1 to 5. The resist curable composition (Claim 6).

  The preferable form of this invention is the curable composition for resists (claim 7) according to any one of claims 1 to 6, wherein the molecular weight distribution of the vinyl polymer (A) is less than 1.8. is there.

  In a preferred embodiment of the present invention, the main chain of the vinyl polymer (A) is composed of a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and a silicon-containing vinyl monomer. The curable composition for resists according to any one of claims 1 to 7, which is produced by mainly polymerizing a monomer selected from (8).

  The preferable form of this invention is a curable composition for resists as described in any one of Claims 1-8 in which the principal chain of a vinyl-type polymer (A) has a structure derived from the monomer containing a polar group. Claim 9).

  The preferable form of this invention is the curable composition for resists of Claim 9 (Claim 10) whose monomer which has a polar group has a carboxyl group or an alkyl ether group.

  The preferable form of this invention is the curable composition for resists of Claim 10 (Claim 11) whose monomer which has a polar group is (meth) acrylic-acid alkyl ether ester or (meth) acrylic acid.

  In a preferred embodiment of the present invention, the ratio of the monomer having a polar group is 1 to 100 mol% with respect to the whole monomer constituting the main chain of the vinyl polymer (A). The curable composition according to item (Claim 12).

A preferred embodiment of the present invention is a structure in which the main chain of the vinyl polymer (A) has a carboxyl group, and the functional group of the monomer constituting the main chain is determined by acid and / or heat. It is the curable composition for resists as described in any one of Claims 1-8 (Claim 13) which arises by deprotecting.
The term “deprotection” as used herein refers to t-butyl which is capable of detaching a polar group such as a carboxyl group under specific conditions (acid and / or heat) instead of polymerizing a monomer having a polar group directly on a polymer. A polar group protected by a substituent such as a group or an isobornyl group (hereinafter sometimes referred to as “protecting group”) is introduced into the polymer, and after the polymerization, the protecting group is deprotected, that is, converted into a polar group. Thus, the vinyl polymer (A) is efficiently obtained. According to this method, the vinyl polymer (A) of the present invention can be produced stably and stably regardless of the type of polar group and the polymerization method. Here, “protecting” refers to making a highly reactive functional group (polar group) a functional group inactive to the subsequent reaction, and the functional group is called a protecting group. Further, “deprotection” refers to removing protection by performing an appropriate reaction after a necessary reaction is completed for a protected functional group.

  In this method, first, a monomer containing a protecting group is copolymerized to produce a vinyl polymer having a protecting group introduced.

  Here, the protecting group for the polar group is not particularly limited, and for example, “Protecting Group Chemistry (Oxford Chemistry Primers)” by Jeremy Robertson (Oxford Univ Pr (Sd)) (2000 / 08od) or Th. Greene, Peter G. M.M. Previously known as “Protective Groups in Organic Synthesis” by Wuts (Wiley-Interscience) 3rd edition (1999/05/15), “Organic Synthesis Handbook” (Maruzen) (1990/03/31), etc. You can choose one.

  In a preferred embodiment of the present invention, the monomer having a functional group that is deprotected by acid and / or heat to generate a carboxyl group is tertiary butyl (meth) acrylate or isobornyl acrylate. Composition (claim 14).

  In a preferred embodiment of the present invention, the ratio of the monomer having a functional group that is deprotected by the acid and / or heat to generate a carboxyl group is 0. The curable composition for resists according to claim 13 or 14 (claim 15), which is 5 to 50 mol%.

  The preferable form of this invention is a curable composition for resists as described in any one of Claims 1-15 whose main chain of a vinyl type polymer (A) is a (meth) acrylic-type polymer (Claim). 16).

  The preferable form of this invention is the curable composition for resists as described in any one of Claims 1-16 (Claim 17) whose principal chain of a vinyl polymer (A) is an acrylic polymer. is there.

  A preferred embodiment of the present invention is the resist curable composition according to claim 17 (claim 18), wherein the main chain of the vinyl polymer (A) is an acrylate ester polymer.

  The preferable form of this invention is a curable composition for resists as described in any one of Claims 1-18 whose principal chain of a vinyl type polymer (A) is manufactured by the living radical polymerization method. (Claim 19).

  In a preferred embodiment of the present invention, the main chain of the vinyl polymer (A) is produced by an atom transfer radical polymerization method, and the curable composition for a resist of the curable composition according to claim 19 (claim). 20).

  The preferable form of this invention contains the monomer and / or oligomer which have a radically polymerizable group further, The curable composition for resists as described in any one of Claims 1-20 (Claim 21). It is.

  The preferable form of this invention is a resist composition as described in any one of Claims 1-20 (Claim 22) which contains the monomer and / or oligomer which have an anion polymerizable group further. .

  The preferable form of this invention further contains the monomer and / or oligomer which have a (meth) acryloyl type group, The curable composition for resists as described in any one of Claims 1-22 (Claim 23). ).

  A preferred embodiment of the present invention is the resist curable composition according to claim 22 (claim 24), wherein the number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is 5000 or less.

  In a preferred embodiment of the present invention, the resist application is a permanent resist, a liquid solder resist, a dry film resist, or an electrodeposition resist. Item 25).

  The preferable form of this invention is the hardened | cured material (Claim 26) obtained by hardening the curable composition for resists as described in any one of Claims 1-25.

  According to the curable composition of the present invention, it is possible to give a cured product having good curability, oil resistance, heat resistance and light resistance, and having a substrate follow-up property based on flexibility. In addition, when blended with a (meth) acrylic vinyl polymer and a polymer containing an acidic functional group necessary for alkali developability and cured, flexibility can be imparted, and the substrate followability of the resist can be improved. It is possible to make it up.

The curable composition of the present invention comprises a vinyl polymer (A) having at least one crosslinkable functional group at the molecular end and a compound (B) capable of crosslinking the vinyl polymer (A), if necessary. A polymer (C) having an acidic functional group.
Below, it explains in full detail about each component contained in the curable composition of this invention.
<< About the vinyl polymer (A) >>
<Main chain>
The vinyl monomer constituting the main chain of the component (A) is not particularly limited, and various types can be used. If it illustrates, it will not specifically limit as a (meth) acrylic-type monomer, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylic acid-n- Butyl, (butyl) (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, tolyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic Examples include (meth) acrylic monomers such as 2-aminoethyl acid and ethylene oxide adducts of (meth) acrylic acid. These may be used singly or a plurality thereof may be copolymerized.

  Other preferable monomers include acrylonitrile, aromatic vinyl monomer, fluorine-containing vinyl monomer, silicon-containing vinyl monomer and the like.

  Examples of the acrylonitrile monomer include acrylonitrile, methacrylo and tolyl.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and the like.
Examples of the fluorine-based monomer include trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, perfluoroethyl methyl (meth) acrylate, and 2-perfluoroethyl (meth) acrylate. Ethyl, perfluoroethyl perfluoroethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , Diperfluoromethyl methyl (meth) acrylate, 2,2-diperfluoromethyl ethyl (meth) acrylate, perfluoromethyl perfluoroethyl methyl (meth) acrylate, 2-perfluoromethyl (meth) acrylate 2-perfluoroethylethyl, (me ) 2-perfluorohexylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylmethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic 2-perfluorohexadecylmethyl acid, 2-perfluorohexadecylethyl (meth) acrylate, monofluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, trifluoroethylene, tetrafluoro Examples include ethylene.

  Examples of silicon group-containing vinyl monomers include p-styryltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropyl. Examples include triethoxylane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane, allyloxydimethylvinylsilane, dimethoxymethylvinylsilane, bis (dimethylamino) methylvinylsilane, and triaceoxyvinylsilane. .

  From the viewpoint that physical properties such as low viscosity, light resistance and heat resistance of the blend are required, a butyl acrylate monomer is more preferable. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. According to various uses and required purposes, it is possible to obtain a polymer obtained by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical properties such as heat resistance and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40 to 50/20 to 30/30). To 20).

For the purpose of improving compatibility with the component (C) described later, it is preferable to copolymerize a polar monomer. Although there is no limitation in particular as a polar monomer. Examples thereof include an amide vinyl monomer, a hydroxyl group-containing vinyl monomer, an amine vinyl monomer, a carboxylic acid vinyl monomer, a phosphoric acid vinyl monomer, a sulfonic acid vinyl monomer, and a vinyl monomer having an ether bond. (C) A vinyl having a carboxylic acid-based vinyl monomer, a hydroxy acid-containing vinyl monomer, an amide-based monomer, an amine-based vinyl monomer, and an ether in view of the balance between the alkali developability and the compatibility of the resist curable composition Monomers are preferred.
Specific examples of the carboxylic acid vinyl monomer include (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride and the like.

  Specific examples of the hydroxyl group-containing vinyl monomer include vinyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic. Examples include ε-caprolactone-modified polyester diol ester of acid, (meth) acrylic acid polypropylene glycol ester, and (meth) acrylic acid polyethylene glycol ester.

  Examples of the amide monomer include (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like.

  Examples of the amine monomer include 2-aminoethyl (meth) acrylate, 2-N, N-dimethylaminoethyl (meth) acrylate, 2-N, N-diethylaminoethyl (meth) acrylate, and the like.

  Examples of the monomer having an ether bond include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl acrylate, and 3-methoxybutyl (meth) acrylate. 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate are preferred.

  In addition, as a method for introducing a carboxylic acid into the main chain, in addition to a method of directly (co) polymerizing a monomer containing a carboxyl group such as (meth) acrylic acid as described above, t-butyl (meth) acrylate, A method of (co) polymerizing monomers such as isobornyl (meth) acrylate and benzyl (meth) acrylate and hydrolyzing (deprotecting) the ester moiety by acid and / or heating to produce a carboxylic acid. is there. From the viewpoint of stability and hydrolyzability, tertiary butyl (meth) acrylate and isobornyl (meth) acrylate are preferred.

  Moreover, as a copolymerization ratio of the said polar monomer, it is 1-100 mol%. If it is less than 1 mol%, the compatibility with the later-described component (C) and alkali developability are poor. As a preferable copolymerization ratio, it is 2-90 mol%, More preferably, it is 5-80 mol%.

  The molecular weight distribution of the vinyl polymer of the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography is not particularly limited, but preferably Is less than 1.8, more preferably not more than 1.7, still more preferably not more than 1.6, still more preferably not more than 1.5, particularly preferably not more than 1.4, most preferably Is 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 in the present invention is not particularly limited, but when measured by gel permeation chromatography, a range of 500 to 1,000,000 is preferable, and 1,000 to 100,000 is more preferable. 5,000 to 50,000 are more preferable. The average molecular weight here is measured under the conditions of using chloroform as a solvent for dissolving the sample, column type: Shodex GPC K-804, K-802.5 (shape 8 mmID × 300 mmL), flow rate = 1.0 mL / min. can do.
<Synthesis of main chain>
The method for synthesizing the vinyl polymer in the present invention is controlled radical polymerization and is not limited, but living radical polymerization is preferable, and atom transfer radical polymerization is more preferable. These will be described below.
Controlled radical polymerization The radical polymerization method is a "general radical polymerization method" in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound or peroxide as a polymerization initiator. Can be classified into “controlled radical polymerization methods” 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, It can be classified as “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the terminal without causing a termination reaction or the like.

  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 vinyl polymers described later, the polymerization using a chain transfer agent will be described. To do. 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.

  Macromolecules 1995, 28, P.M. As reported in 2993, instead of using a radical capping agent and a radical generator in combination, an alkoxyamine compound as shown below may be used as an initiator.

アルコキシアミン化合物を開始剤として用いる場合、それが上図で示されているような水酸基等の官能基を有するものを用いると、末端に官能基を有する重合体が得られる。これを本発明の方法に利用すると、末端に官能基を有する重合体が得られる。

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, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

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

  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 (meth) acrylic 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.

It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (1) is illustrated.
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 an aralkyl group, or interconnected at the other end. things, 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 carbon atoms 1 to 20 divalent organic groups which may contain one or more ether bonds, X is chlorine, bromine or iodine. Specific examples of the substituents R ⁴ and R ⁵ include hydrogen, methyl group, Examples include 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 ,

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）
Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（
ＣＨ₂）_mＣＨ＝ＣＨ₂、ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣ
Ｈ＝ＣＨ₂、

(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 C
H = CH ₂ ,

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_mＣＨ＝ＣＨ₂、（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
アルケニル基を有する有機ハロゲン化物としてはさらに一般式（２）で示される化合物が挙げられる。
Ｈ₂Ｃ＝Ｃ（Ｒ³）−Ｒ⁷−Ｃ（Ｒ⁴）（Ｘ）−Ｒ⁸−Ｒ⁵ （２）
（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁷、Ｘは上記に同じ、Ｒ⁸は、直接結合、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）、または、ｏ−，ｍ−，ｐ−フェニレン基を表す） Ｒ⁷は直接結合、または炭素数１〜２０の２価の有機基（１個以上のエーテル結合を含んでいても良い）であるが、直接結合である場合は、ハロゲンの結合している炭素にビニル基が結合しており、ハロゲン化アリル化物である。この場合は、隣接ビニル基によって炭素−ハロゲン結合が活性化されているので、Ｒ⁸としてＣ（Ｏ）Ｏ基やフェニレン基等を有する必要は必ずしもなく、直接結合であってもよい。Ｒ⁷が直接結合でない場合は、炭素−ハロゲン結合を活性化するために、Ｒ⁸としてはＣ（Ｏ）Ｏ基、Ｃ（Ｏ）基、フェニレン基が好ましい。

(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 the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 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 above formulas, 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 ,
(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)
Examples of the organic halide having an alkenyl group further include 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 R ⁷ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). However, in the case of a direct bond, a vinyl group is bonded to carbon to which a halogen is bonded, which is an allyl halide. 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.

If the compound of the general formula (2) is specifically exemplified,
_{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 the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group).

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{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, and n is an integer of 0 to 20)
Etc.

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, what has a structure shown in General formula (3) is illustrated.
^{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)
(Wherein 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)
If the compound of general formula (3) is specifically illustrated,
_{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 the above formulas, X is chlorine, bromine, 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) 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 the above formulas, X is chlorine, bromine, or iodine).

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 such a compound is specifically illustrated,
_{(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, (C _{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,
(In each of the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group).

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 formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
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 formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

（式中、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
生長末端構造を１分子内に２つ以上有する重合体を得るためには、２つ以上の開始点を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物が開始剤として用いるのが好ましい。具体的に例示するならば、

(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
In order to obtain a polymer having two or more growth terminal structures 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,

等が挙げられる。

Etc.

  There is no restriction | limiting in particular as a (meth) acrylic-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 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 preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. 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. Further, 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.

The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, peroxidation with respect to Cu (II ′) when Cu (I) is used as a catalyst. In this method, a general radical initiator such as a compound is allowed to act, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).
<Functional group>
Number of crosslinkable functional groups The vinyl polymer (A) has at least one crosslinkable functional group. From the viewpoint of the curability of the composition and the physical properties of the cured product, it is preferable to have one or more on average per molecule, more preferably 1.1 or more and 4.0 or less, and still more preferably 1.2 or more. 3.5 or less.
Position of the crosslinkable functional group When a rubber-like property is particularly required for a cured product obtained by curing the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be taken. At least one of the crosslinkable functional groups is preferably at the end of the molecular chain. More preferably, it has all crosslinkable functional groups at the molecular chain ends.

  Methods for producing a vinyl polymer having at least one crosslinkable functional group at the molecular end are disclosed in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. ing. 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.

Although it does not necessarily limit as a crosslinkable functional group which a vinyl type polymer (A) has, A polymerizable carbon-carbon double bond, an alkenyl group, a silyl group, or an epoxy group is mentioned.

  These functional groups will be described below.

[Group having a polymerizable carbon-carbon double bond]
The group having a polymerizable carbon-carbon double bond is preferably a general formula (5);
—OC (O) C (R ⁹ ) ═CH ₂ (5)
(In the formula, R ⁹ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms.)
R ⁹ is more preferably hydrogen or a methyl group.

In the general formula (5) is not particularly limited as specific examples of R ^9, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is an integer of 2 to 19 the _{represented), - C 6 H 5,} -CH 2
OH, —CN and the like can be mentioned, and —H and —CH ₃ are preferred.

[Alkenyl group]
Although the alkenyl group in this invention is not limited, It is preferable that it is what is represented by General formula (6).
H ₂ C═C (R ¹⁰ ) − (6)
(Wherein R ¹⁰ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)
In the general formula (6), R ¹⁰ 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 vinyl polymer (A) 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.
(Crosslinkable silyl group)
Although it does not necessarily limit as a crosslinkable silyl group of this invention, General formula (7);
_{^{- [Si (R 11) 2}} -b (Y) b O] m -Si (R 12) 3-a (Y) a (7)
{In the formula, R ¹¹ and R ¹² 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 ¹¹ or When two or more R ¹² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 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. } Is represented.

  Examples of the hydrolyzable group in the above formula include a commonly used group 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. can give. 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. Among the alkoxy groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases in the order of methoxy group> ethoxy group> propoxy group, and can be selected according to the purpose and application.

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 (8);
_{^{-Si (R 12) 3-a}} (Y) a (8)
A crosslinkable silyl group represented by the formula (wherein R ¹² and Y are the same as described above, a is an integer of 1 to 3) is preferable because it is easily available.

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

  Such a (meth) acrylic polymer having a crosslinkable silyl group is often a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom. When extremely fast curing speeds are required, such as when using adhesives or at low temperatures, the curing speed is not sufficient, and when it is desired to provide flexibility after curing, the crosslinking density is reduced. For this reason, the crosslink density is not sufficient, and stickiness (surface tack) may occur. In that case, it is preferable that a is 3 (for example, trimethoxy functional group).

  Further, those having a of 3 (for example, trimethoxy functional group) are faster in curability than those having 2 (for example, dimethoxy functional group), but those having 2 are superior in terms of storage stability and mechanical properties (elongation, etc.). There may be. In order to balance the curability and physical properties, two (for example, dimethoxy functional group) and three (for example, trimethoxy functional group) may be used in combination.

  For example, when Y is the same, the greater the a, the higher the reactivity of Y. Therefore, by variously selecting Y and a, it is possible to control the curability and the mechanical properties of the cured product. It can be selected according to the application.

[Epoxy group]
Preferred examples of the epoxy group include a glycidyl group, a glycidyl ether group, a 3,4-epoxycyclohexyl group, and an oxetane group. In terms of reactivity, a glycidyl group, a glycidyl ether group, and a 3,4-epoxycyclohexyl group are preferable. More preferred.

<Introduction method of crosslinkable functional group>
The method for introducing a crosslinkable functional group into the vinyl polymer (A) will be described below, but the method is not limited to this.

The method for introducing a group having a polymerizable carbon-carbon double bond into the vinyl polymer is not limited, but includes the following methods.
(Ia) A method for producing a vinyl polymer by replacing the halogen group with a compound having a radical polymerizable carbon-carbon double bond. As a specific example, the general formula (9)
The method by reaction with the (meth) acrylic-type polymer which has a structure represented by, and the compound shown by General formula (10).
-CR ¹³ R ¹⁴ X (9)
(In the formula, R ¹³ and R ¹⁴ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ¹¹ ) ═CH ₂ (10)
(In the formula, R ¹¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)
(Ib) A method by a reaction between a (meth) acrylic polymer having a hydroxyl group and the compound represented by the general formula (11).
XC (O) C (R ¹¹ ) ═CH ₂ (11)
(In the formula, R ¹¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)
(Ic) A method of reacting a diisocyanate compound with a (meth) acrylic polymer having a hydroxyl group and reacting the remaining isocyanate group with the compound represented by the general formula (12).
HO—R ¹⁵ —OC (O) C (R ⁹ ) ═CH ₂ (12)
(In the formula, R ¹¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ¹⁵ represents a divalent organic group having 2 to 20 carbon atoms.)
Each of these methods will be described in detail below.

The above method (ia) will be described.
(Ia) The method by reaction of the vinyl polymer which has a terminal structure represented by General formula (7), and the compound shown by General formula (10).
-CR ¹³ R ¹⁴ X (9)
(In the formula, R ¹³ and R ¹⁴ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ¹¹ ) ═CH ₂ (10)
(In the formula, R ¹¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)
The (meth) acrylic polymer having a terminal structure represented by the general formula (9) 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. Alternatively, it is produced by a method in which a vinyl monomer is polymerized using a halogen compound as a chain transfer agent, but the former is preferred.

Formula is not particularly restricted but includes compounds represented by (10), specific examples of R ¹¹ are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

M ⁺ is a counter cation of 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 usage-amount of the oxyanion of General formula (10) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen group of General formula (9), More preferably, it is 1.0-1.2 equivalent. 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 (ib) will be described.
(Ib) A method of reacting a vinyl polymer having a hydroxyl group with a compound represented by the general formula (11).
XC (O) C (R ¹¹ ) ═CH ₂ (11)
(In the formula, R ¹¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)
Formula is not particularly restricted but includes compounds represented by (11), specific examples of R ¹¹ are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN and the like, preferably -H, -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) When a vinyl polymer is synthesized by living radical polymerization, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule represented by the following general formula (13) is reacted as a second monomer. Method.
^{_{H 2 C = C (R 16}} ) -R 17 -R 18 -OH (13)
(In the formula, R ¹⁶ is an organic group having 1 to 20 carbon atoms, preferably hydrogen or methyl group, and may be the same or different. R ¹⁷ is —C (O) O— (ester group), Or represents an o-, m- or p-phenylene group, R ¹⁸ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds R ¹⁵ (A) is an ester group (meth) acrylate compound, and R ¹⁷ is a phenylene group is a styrene compound.)
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 (14) are mentioned.
^{_{H 2 C = C (R 16}} ) -R 19 -OH (14)
(In the formula, R ¹⁶ is the same as described above. R ¹⁹ represents a C 1-20 divalent organic group that may contain one or more ether bonds.)
The compound represented by the general formula (14) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

(C) A vinyl system having at least one carbon-halogen bond represented by the general formula (9) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolyzing or reacting a halogen of a polymer with a hydroxyl group-containing compound.

(D) A hydroxyl group as shown in the general formula (15) in a (meth) acrylic polymer having at least one carbon-halogen bond represented by the general formula (9) obtained by atom transfer radical polymerization. A method in which a halogen is substituted by reacting with a stabilized carbanion having a hydrogen atom.
M ⁺ C ⁻ (R ²⁰ ) (R ²¹ ) —R ¹⁹ —OH (15)
(Wherein, R ¹⁹ are the same as those described above .R ²⁰ and R ²¹ together carbanion C ^- an electron withdrawing group or one of the other from 1 to 10 hydrogen carbon atoms or by the electron-withdrawing group, stabilized And an electron-withdrawing group of R ²⁰ and R ²¹ 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 a phenyl group having 1 to 10 carbon atoms, and as R ²⁰ and R ²¹ , —CO ₂ R, —C (O) R and —CN are Particularly preferred.)
(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (7) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc, for example. A method in which a rate anion is prepared and then an aldehyde or a ketone is reacted.

(F) a hydroxyl group-containing oxyanion represented by the following general formula (16) or the like, or a general polymer represented by the following general formula (16) or the like in a vinyl polymer having at least one halogen represented by the general formula (9): A method of reacting a hydroxyl group-containing carboxylate anion represented by the formula (17) or the like to replace the halogen with a hydroxyl group-containing substituent.
HO—R ¹⁹ —O ⁻ M ⁺ (16)
(In the formula, R ¹⁹ and M ⁺ are the same as those described above.)
HO—R ¹⁹ —C (O) O ⁻ M ⁺ (17)
(In the formula, R ¹⁹ 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 (ic) will be described.
(Ic) A method by reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound and reacting the remaining isocyanate group with the compound represented by the general formula (18).
HO—R ¹⁵ —OC (O) C (R ¹¹ ) ═CH ₂ (18)
(In the formula, R ¹¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ¹⁵ represents a divalent organic group having 2 to 20 carbon atoms.)
As the compound represented by the general formula (18) is not particularly limited, specific examples of R ¹¹ are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3. A specific compound includes 2-hydroxypropyl methacrylate.

  Here, what is obtained by the method similar to the above can be used as a vinyl polymer which has a hydroxyl group.

  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, for example, it is preferable to use a diisocyanate compound having no aromatic ring such as hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate.

  The method for introducing an alkenyl group into the vinyl polymer is not particularly limited, and examples thereof include the following methods.

(Ii-a) When synthesizing a vinyl polymer 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 (19) To react as a second monomer.
^{_{H 2 C = C (R 22}} ) -R 23 -R 24 -C (R 25) = CH 2 (19)
(Wherein R ²² represents hydrogen or a methyl group, R ²³ represents —C (O) O—, or o-, m-, p-phenylene group, R ²⁴ represents a direct bond, or 1 to 20 represents a divalent organic group having 20 and may contain one or more ether bonds, R ²⁵ represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. In addition, although there is no restriction on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule, it has a rubber-like property particularly in living radical polymerization. When expected, it is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer.

  (Ii-b) 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

  (Ii-c) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin are added to a vinyl polymer having at least one carbon-halogen bond having high reactivity. A method of replacing halogen by reaction.

(Ii-d) By reacting a (meth) acrylic polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in the general formula (22), halogen is reacted. How to replace.
^{M + C - (R 26)} (R 27) -R 28 -C (R 25) = CH 2 (22)
(Wherein, R ²⁵ is the same, R ^26, R ²⁷ together carbanion C ^- or 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 ²⁶ 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, As an electron withdrawing group for R ²⁶ and R ²⁷ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (Ii-e) 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 .

(Ii-f) An oxyanion or carboxylate anion having an alkenyl group as represented by the general formula (23) or (24) 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 25}} ) -R 29 -O - M + (23)
(In the formula, R ²⁵ and M ⁺ are the same as above. R ²⁹ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
^{_{H 2 C = C (R 25}} ) -R 30 -C (O) O - M + (24)
(In the formula, R ²⁵ and M ⁺ are the same as above. R ³⁰ 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 above-described method for synthesizing a vinyl polymer having at least one carbon-halogen bond having high reactivity 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.

Moreover, 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. In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ii-g) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride.
(Ii-h) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.
(Ii-i) 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.
(Ii-j) a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst;

  In the present invention, when halogen is not directly involved in the method of introducing an alkenyl group such as (ii-a) and (ii-b), 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 introducing an alkenyl group 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.

  (Iii) The method for producing a vinyl polymer having at least one hydroxyl group used in the methods (ii-g) to (ii-j) is exemplified by the following methods, but is limited to these methods. It is not a thing.

(Iii-a) When synthesizing a vinyl polymer 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 (25) is used as the second monomer. How to react as.
^{_{H 2 C = C (R 22}} ) -R 23 -R 24 -OH (25)
(Wherein R ²² , R ²³ and R ²⁴ are the same as above)
There is no limitation on the timing of reacting a 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.
(Iii-b) 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.
(Iii-c) 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 disclosed in JP-A-5-262808.
(Iii-d) 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.

  (Iii-e) A method in which a vinyl monomer is radically polymerized using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.

  (Iii-f) 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.

(Iii-g) A method of replacing 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 listed in the general formula (26).
M ⁺ C ⁻ (R ²⁶ ) (R ²⁷ ) —R ²⁸ —OH (26)
(Wherein R ²⁶ , R ²⁷ and R ²⁸ are the same as above)
As the electron withdrawing group of R ²⁶ and R ²⁷ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.
(Iii-h) An enolate anion is prepared by allowing a metal-based polymer having at least one carbon-halogen bond having high reactivity to react with, for example, a single metal such as zinc or an organometallic compound, and then aldehydes. Or a method of reacting ketones.
(Iii-i) 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 (27) or (28). To replace the halogen.
HO-R ²⁹ -O ^- M ⁺ (27)
(Wherein R ²⁷ and M ⁺ are the same as above)
HO—R ³⁰ —C (O) O ⁻ M ⁺ (28)
(Wherein R ³⁰ and M ⁺ are the same as above)
(Iii-j) When synthesizing a vinyl polymer by living radical polymerization, as the second monomer, after the completion 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 (29) are mentioned.
^{_{H 2 C = C (R 22}} ) -R 29 -OH (29)
(Wherein R ²² and R ²⁹ are the same as those described above.)
Although it does not specifically limit as a compound shown by the said General formula (29), 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 (iii-a) to (iii-e) and (iii-j), a vinyl polymer is obtained using a living radical polymerization method. It is preferable to synthesize. The method (iii-b) 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 (iii-i) is more preferable because it is easier to control.

  A vinyl polymer having at least one alkenyl group, crosslinkable silyl group, and epoxy group can be synthesized based on, for example, a method described in JP-A-2004-83865.

As mentioned above, any of the crosslinkable functional groups contained in the vinyl polymer may be used, but it is polymerizable carbon-carbon from the viewpoint that it can be instantly cured by liquefaction, active energy rays, and heating. A group having a double bond is preferred. Among them, general formula (1) in terms of reactivity:
—OC (O) C (R ^a ) ═CH ₂ (1)
The crosslinkable functional group represented by is more preferable.
For example, in the case of curing with an electron beam (EB) among the active energy rays, an initiator component described later is not particularly required.
<< Compound (B) capable of crosslinking vinyl polymer (A) >>
The crosslinkable functional group of the vinyl copolymer (A) is not particularly limited, and various compounds that cure the crosslinkable functional group can be used.
Hereinafter, (B) component is described for every crosslinkable functional group of a vinyl polymer (A).
(In the case of polymerizable carbon-carbon double bond)
In the case of a crosslinkable polymerizable carbon-carbon double bond, an initiator can be used. 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 type, the photopolymerization initiator is a photo radical initiator,
Alternatively, it is preferable to use a photoanion initiator. Photo radical initiators are particularly preferred. In the thermosetting type, it is preferable to use a thermal polymerization initiator selected from the group consisting of azo initiators, peroxides, persulfates, and redox initiators. The initiators used may be used singly or as a mixture of two or more, but when used as a mixture, the amount of each initiator used is within the respective ranges described below. It is preferable that it exists in.
Crosslinking system by active energy rays The curable composition for vibration damping materials of the present invention can be crosslinked by active energy rays such as UV and electron beams.

  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.
Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin Ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl- Phenyl - phosphine oxide, and the like. These initiators may be used alone or in combination with other compounds. Specifically, a combination with an amine such as diethanolmethylamine, dimethylethanolamine, triethanolamine, a combination with an iodonium salt such as diphenyliodonium chloride, a combination with a dye and an amine such as methylene blue, and the like. It is done.
In addition, when using the said photoinitiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

  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 amount of the photopolymerization initiator added is not particularly limited since it only needs to slightly functionalize the system, but is preferably 0.001 to 10 parts by weight with respect to 100 parts of the vinyl polymer (A).
The method for curing the curable composition for vibration damping material 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, and a light emitting diode And irradiation with light and an electron beam by a semiconductor laser or the like.

Further, it is preferable to use heat as a method for crosslinking the polymer having a polymerizable carbon-carbon double bond.
Heat-crosslinking system When the curable composition for vibration damping material of the present invention is heat-cured, it preferably contains 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), and 2,2′-azobis (methylisobutylate) (V-601) (available from Wako Pure Chemical Industries, Ltd.) And the like.

  Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl peroxy 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 polymerizable carbon-carbon dioxide at at least one end of the present invention. When the total amount of the (meth) acrylic polymer (I) having a group having a heavy bond and other monomer and oligomer mixture added is 100 parts by weight, 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 curable composition for vibration damping material of the present invention is not particularly limited.
Although it varies depending on the type of the thermal initiator used, the (meth) acrylic polymer (I) and the compound to be added, it is usually preferably in the range of 50 ° C to 250 ° C, more preferably in the range of 70 ° C to 200 ° C. preferable. 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.
As described above, the crosslinkable functional group of the vinyl polymer is preferably a group having a polymerizable carbon-carbon double bond, but in the case of other functional groups, the following curing catalyst and crosslinkage are used as component (B). Agents can be used.
[In the case of an alkenyl group]
In the case of crosslinking 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 using 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 vinyl polymer having an alkenyl group, and various compounds can be used. For example, a chain polysiloxane represented by the general formula (32) or (33);
_{^{R 31 3 SiO- [Si (R}} 31) 2 O] a - [Si (H) (R 32) O] b - [Si (R 32) (R 33) O] c -SiR 31 3 (32)
_{^{HR 31 2 SiO- [Si (R}} 31) 2 O] a - [Si (H) (R 32) O] b - [Si (R 32) (R 33) O] c -SiR 31 2 H (33)
(Wherein R ³¹ and R ³² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ³³ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. A represents 0 ≦ a ≦ 100, b Represents an integer satisfying 2 ≦ b ≦ 100 and c represents 0 ≦ c ≦ 100.)
Cyclic siloxane represented by the general formula (34);

（式中、Ｒ³⁴およびＲ³⁵は炭素数１〜６のアルキル基、または、フェニル基、Ｒ³⁶は炭素数１〜１０のアルキル基またはアラルキル基を示す。ｄは０≦ｄ≦８、ｅは２≦ｅ≦１０、ｆは０≦ｆ≦８の整数を表し、かつ３≦ｄ＋ｅ＋ｆ≦１０を満たす。）
等の化合物を用いることができる。

(In the formula, R ³⁴ and R ³⁵ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ³⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. D represents 0 ≦ d ≦ 8, e Represents an integer of 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and satisfies 3 ≦ d + e + f ≦ 10.)
Etc. can be used.

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with a vinyl polymer, a chain siloxane represented by the following general formulas (35) and (36) having a phenyl group, and general formulas (37) and (38) The cyclic siloxane represented is preferred.
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (35)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (CH 3) {CH 2 C (H) (R 37) C 6 H 5} O] h -Si (CH 3 ₃ (36)
(In the formula, R ³⁷ 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.)

（式中、Ｒ³⁸は水素、またはメチル基を示す。ｉは２≦ｉ≦１０、ｊは０≦ｊ≦８、かつ３≦ｉ＋ｊ≦１０を満たす整数を示す。Ｃ₆Ｈ₅はフェニル基を示す。）
ヒドロシリル基含有化合物としてはさらに、分子中に２個以上のアルケニル基を有する低分子化合物に対し、一般式（３２）から（３８）に表されるヒドロシリル基含有化合物を、反応後にも一部のヒドロシリル基が残るようにして付加反応させて得られる化合物を用いることもできる。分子中に２個以上のアルケニル基を有する化合物としては、各種のものを用いることができる。例示するならば、１，４−ペンタジエン、１，５−ヘキサジエン、１，６−ヘプタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン等の炭化水素系化合物、Ｏ，Ｏ'−ジアリルビスフェノールＡ、３，３'−ジアリルビスフェノールＡ等のエーテル系化合物、ジアリルフタレート、ジアリルイソフタレート、トリアリルトリメリテート、テトラアリルピロメリテート等のエステル系化合物、ジエチレングリコールジアリルカーボネート等のカーボネート系化合物が挙げられる。

(In the formula, R ³⁸ 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 (32) to (38) may be partially converted after the reaction with respect to a low molecular compound having two or more alkenyl groups in the molecule. A compound obtained by addition reaction such that a hydrosilyl group remains can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. Illustratively, 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 the excessive amount of the hydrosilyl group-containing compound represented by the general formulas (32) to (38). it can. Of these compounds, the following are preferable in view of the availability of raw materials, the ease of removing excessive siloxane, and the compatibility with the vinyl polymer (A).

重合体と硬化剤は任意の割合で混合することができるが、硬化性の面から、アルケニル基とヒドロシリル基のモル比が５〜０．２の範囲にあることが好ましく、さらに、２．５〜０．４であることが特に好ましい。モル比が５より大きくなると硬化が不十分でべとつきのある強度の小さい硬化物しか得られず、また、０．２より小さいと、硬化後も硬化物中に活性なヒドロシリル基が大量に残るので、クラック、ボイドが発生し、均一で強度のある硬化物が得られない。

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 greater than 5, only a cured product with insufficient 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 May be mentioned di (t-butylperoxy) cyclohexane, 1,1-di peroxy ketals such as (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like.

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 a vinyl type polymer (A), Preferably it is 10 ^<-3 > ^-10 <^-6> mol. It is good to use in the range. If it is less than 10 ⁻⁸ mol, curing does not proceed sufficiently. Further, since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ⁻¹ mol or more.

  In order to balance storage stability and curability, a curing regulator may be blended. Examples of the curing modifier that can be blended include compounds containing an aliphatic unsaturated bond. For example, acetylene alcohols are exemplified, and examples of acetylene alcohol having a balance between storage stability and curability include 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, 3-methyl-1-hexyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-methyl-3-butyn-2-ol, 3- And methyl-1-pentyn-3-ol.

  Other than acetylene alcohols, compounds containing aliphatic unsaturated bonds that improve storage stability at high temperatures include ene-in compounds, silane compounds, polysiloxane compounds, olefinic compounds, and fats of olefinic alcohols such as vinyl acetate. Examples thereof include carboxylic acid esters, tetravinylsiloxane cyclics, nitriles containing an aliphatic unsaturated bond such as 2-pentenenitrile, alkyl acetylenedicarboxylates, maleic acid esters, diorgano fumarate and the like.

  Although the usage-amount of a sclerosing | hardenable modifier can be chosen arbitrarily, it is preferable to use in the range of 2-10000 molar equivalent with respect to the said hydrosilylation catalyst. A sclerosing | hardenable modifier may be used independently and may use 2 or more types together.

  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 case of hydroxyl group]
When the (meth) acrylic polymer having a hydroxyl group of the present invention is used, it 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 an alkyl etherified product or a low-condensed product thereof, a polyfunctional carboxylic acid, and Examples thereof include halides thereof. When producing a cured product using these curing agents, an appropriate curing catalyst can be used.

[Crosslinkable silyl group]
The (meth) acrylic 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; divalent tin compounds such as tin octylate, tin naphthenate and tin stearate; monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide; Monoalkyltins such as nooctyltin compounds; titanates such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; Bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, nickel carboxylate, carboxylic acid Carboxylic acids such as cobalt, zinc carboxylate, aluminum carboxylate (2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, naphthenic acid, etc.) Metal salts, or reactants and mixtures of these with amine compounds such as laurylamine described below; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; methylamine, ethylamine, propylamine, isopropylamine, Aliphatic primary amines such as butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine , Diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetyla Aliphatic secondary amines such as amine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; aliphatic tertiary amines such as triamylamine, trihexylamine, trioctylamine; triallylamine, oleylamine Aliphatic unsaturated amines such as lauryl aniline, stearyl aniline, triphenylamine and the like; and other amines such as monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, Oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphen Luguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) Amine compounds such as salts of these amine compounds with carboxylic acids, etc .; reactants and mixtures of amine compounds and organotin compounds such as laurylamine and tin octylate reactants or mixtures; excess Low molecular weight polyamide resin obtained from polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane , Γ-aminopropylmethyldimethoxysilane, γ-aminopro Rumethyldiethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminopropyltriethoxysilane, N- (Β-aminoethyl) aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Examples thereof include benzyl-γ-aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane. Silanol condensation such as silane coupling agents having amino groups such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, etc., which are derivatives of these modified Examples of the catalyst include known silanol condensation catalysts such as other 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, more preferably 1 to 10 parts, relative to 100 parts (parts by weight, the same applies hereinafter) of the vinyl polymer having at least one crosslinkable silyl group. .
When the amount of the silanol condensation catalyst is below 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. Although not particularly limited, it is preferable to use a tin-based curing catalyst in order to control curability.
[In case of epoxy group]
Although it does not specifically limit as a hardening | curing agent of the polymer which has an epoxy group of this invention, For example, aliphatic amines, alicyclic amines, aromatic amines; acid anhydride; polyamide; imidazoles; amine imide; Melamine and its derivatives; salt of polyamine; phenol resin; polymercaptan, polysulfide; light / ultraviolet curing agent such as aromatic diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium salt, etc. are used.

Apart from crosslinking with an amine component, the crosslinkable silyl group can be crosslinked by irradiating with active energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays and the like. In that case, acid generators (cationic initiators) such as iodonium salts and sulfonium salts can be used.
<< Prepolymer and / or polymer having acidic functional group >>
When the resist curable composition requires alkali development, a prepolymer and / or polymer having an acidic functional group can be blended. Although there is no limitation in particular as an acidic functional group, a carboxyl group is preferable from the ease of introduction | transduction and alkali developability. The prepolymer and polymer are not particularly limited, but when the resist film is left in an electric circuit, such as a solder resist, a prepolymer or polymer that undergoes a crosslinking reaction by active energy rays, heating, or the like is used. It is preferable to use it. Moreover, when a resist film is not left on a circuit like a dry film resist etc., it is preferable to use a non-reactive polymer. The reactive prepolymer, polymer and non-reactive polymer containing carboxylic acid are described below.

<Carboxylic acid-containing prepolymer, polymer>
As the photosensitive prepolymer,
(1) Esterification reaction (total esterification or partial esterification, preferably total esterification) of an epoxy group of a polyfunctional epoxy compound having at least two epoxy groups in one molecule and a carboxyl group of an unsaturated monocarboxylic acid ), And the resulting hydroxyl group further reacted with a saturated or unsaturated polybasic acid anhydride,
(2) After reacting (meth) acrylic acid with a copolymer composed of alkyl (meth) acrylate and glycidyl (meth) acrylate, further reacting with a saturated or unsaturated polybasic acid anhydride,
(3) After reacting a copolymer of hydroxyalkyl (meth) acrylate, alkyl (meth) acrylate and glycidyl (meth) acrylate with (meth) acrylic acid, a saturated or unsaturated polybasic acid anhydride is further added. The reaction,
(4) A glycidyl (meth) acrylate partially reacted with a copolymer of alkyl (meth) acrylate and (meth) acrylic acid,
(5) A polyfunctional epoxy compound having at least two epoxy groups in one molecule, an unsaturated monocarboxylic acid, at least two hydroxyl groups in one molecule, and one hydroxyl group that reacts with an epoxy group A product obtained by reacting a reaction product (I) with a compound having another reactive group with a saturated or unsaturated polybasic acid anhydride,
(6) Unsaturated groups such as those obtained by reacting a hydroxyalkyl (meth) acrylate with a copolymer of an unsaturated polybasic acid anhydride such as maleic anhydride and an aromatic hydrocarbon having a vinyl group such as styrene. Containing polycarboxylic acid resin,
(7) An unsaturated group-containing polycarboxylic acid urethane resin such as a reaction product of the reaction product (I), a saturated or unsaturated polybasic acid anhydride, and an unsaturated group-containing monoisocyanate can be exemplified.

  Since the photosensitive prepolymer as described above has a number of free carboxyl groups added to the side chain of the backbone / polymer, the composition containing this photosensitive prepolymer can be developed with a dilute aqueous alkali solution. At the same time, a photocured film having a predetermined pattern can be obtained by exposure and development. Moreover, when the thermosetting component (B-2), for example, an epoxy compound is blended together, the epoxy group of the epoxy compound of the thermosetting component and the free carboxyl of the side chain are obtained by post-heating the coating film. An addition reaction occurs with the base, and a solder resist film excellent in various properties such as heat resistance, solvent resistance, acid resistance, adhesion, electroless gold plating resistance, electrical properties, and hardness of the coating film is obtained.

  Moreover, although the suitable range of the acid value of the said photosensitive prepolymer changes with kinds, it needs to exist in the range of 30-200 mgKOH / g generally, and a preferable range is 40-120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated. Conversely, when the acid value is more than 200 mgKOH / g, the resist properties such as alkali resistance and electrical properties of the cured film are lowered. Therefore, neither is preferable.

  The resin (1) is composed of a polyfunctional epoxy compound as described later and an unsaturated monocarboxylic acid (for example, acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyano. Reaction products with cinnamic acid, cinnamic acid, etc., and saturated or unsaturated polybasic acid anhydrides (eg maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride) Dibasic acid anhydrides such as acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and chlorendic anhydride, and aromatic aromatics such as trimellitic anhydride and pyromellitic anhydride Carboxylic acid anhydrides) are reacted. In this case, a resin obtained by reacting 0.15 mol or more of a polybasic acid anhydride per one hydroxyl group of a reaction product of a polyfunctional epoxy compound and an unsaturated monocarboxylic acid is suitable.

On the other hand, the copolymer which is the base polymer of the resins (2) and (3) uses alkyl (meth) acrylate and glycidyl (meth) acrylate, or further hydroxyalkyl (meth) acrylate, as described above. These can be obtained by copolymerization by a known method such as a solution polymerization method.
The alkyl (meth) acrylate is an alkyl ester of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, etc., wherein the alkyl group is an aliphatic hydrocarbon group having 1 to 6 carbon atoms. . The hydroxyalkyl (meth) acrylate is a hydroxyalkyl ester of acrylic acid or methacrylic acid, and the hydroxyalkyl group is preferably a C 1-6 aliphatic hydrocarbon group having a primary hydroxyl group.

  In the resins (2) to (4), the degree of polymerization of the copolymer obtained by copolymerizing each monomer is 10,000 to 70,000, preferably 15,000 to 50, as a weight average molecular weight. A range of 1,000 is desirable. When the weight average molecular weight is less than 10,000, the dryness to touch of the coating film is lowered. On the other hand, when the weight average molecular weight is more than 70,000, the developability tends to be lowered.

  In addition to the above monomers, vinyl compounds such as styrene and methylstyrene can be used as long as the properties are not affected.

The synthetic reaction of the resin of (5) is carried out by using an unsaturated monocarboxylic acid (or at least two hydroxyl groups and one other reactivity other than a hydroxyl group that reacts with an epoxy group) on a polyfunctional epoxy compound. A compound having a group, for example, polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid and dimethylolcaproic acid; dialkanolamines such as diethanolamine and diisopropanolamine) Then, there are a first method of reacting the compound (or unsaturated monocarboxylic acid) and a second method of reacting the polyfunctional epoxy compound, unsaturated monocarboxylic acid and the compound simultaneously. Either method may be used, but the second method is preferable.
The reaction between the reaction product (I) obtained by the above reaction and the polybasic acid anhydride is carried out by adding 0.1 to 10 polybasic acid anhydrides per equivalent of hydroxyl groups with respect to the hydroxyl groups in the reaction product (I). It is preferable to react 0.9 equivalent.

On the other hand, in the synthesis reaction of the unsaturated group-containing polycarboxylic acid urethane resin (7), the reaction product (I) is reacted with a polybasic acid anhydride, and then an unsaturated group-containing monoisocyanate (for example, methacryloyl isocyanate, Reaction of methacryloyloxyethyl isocyanate or organic diisocyanate (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and (meth) acrylates having one hydroxyl group in one molecule at an equimolar ratio. It is preferable to react the reaction product obtained by the reaction.
Other photo-curing resins include HYPERLINK "PNS JP 51-131706" JP 51-131706, HYPERLINK "PNE JP 63-46791" JP 63-46791, HYPERLINK "PNE JP 1- Conventionally known various photosensitive prepolymers such as a photosensitive prepolymer having at least two acryloyl groups or methacryloyl groups in one molecule described in JP-B-1-32868 and the like can be used.

  On the other hand, as the thermosetting resin, conventionally known various thermosetting resins can be used, and the thermosetting resin is not limited to a specific one, but at least 2 in one molecule from the viewpoint of thermosetting characteristics and characteristics of the cured film. A polyfunctional epoxy compound having one epoxy group and / or a polyfunctional oxetane compound having at least two oxetanyl groups in one molecule is preferable. Such a composition containing a thermosetting resin can be used as a solder resist for printed wiring boards, as well as for forming various resin insulation layers, etching resists, marking inks, and the like.

  As a specific example of the polyfunctional epoxy compound having at least two epoxy groups in one molecule, for example, a novolak type epoxy resin (for example, phenol, cresol, alkylphenol, etc., and phenol and formaldehyde are reacted in an acidic catalyst. Obtained by reacting epichlorohydrin and / or methyl epichlorohydrin with the novolaks obtained by the reaction, bisphenol type epoxy resins (for example, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, epichlorohydrin and / or methyl epichlorohydrin). Or the condensate of bisphenol A with diglycidyl ether of bisphenol A and epichlorohydrin and / or methyl epichlorohydrin. Etc.), trisphenol methane type epoxy resins (for example, those obtained by reacting trisphenol methane, triskresol methane, etc. with epichlorohydrin and / or methyl epichlorohydrin), tris (2,3-epoxypropyl) isocyanate Nurate, biphenyl diglycidyl ether, alicyclic, amino group-containing epoxy resin, copolymer type epoxy resin (for example, glycidyl methacrylate / styrene copolymer, glycidyl methacrylate / styrene / methyl methacrylate copolymer, or Copolymers of glycidyl methacrylate and cyclohexylmaleimide, etc.), or other epoxy resins having a special structure, etc., can be used alone or in combination of two or more. Can.

  In addition, polyfunctional oxetane compounds having two or more oxetanyl groups in one molecule include polyfunctional oxetanes such as bisoxetanes, trisoxetanes, novolac oxetanes, calixarene oxetanes, cardo oxetanes, polyhydroxys. Examples thereof include styrene-type oxetane or etherified products of these with a resin having a hydroxyl group such as silicone resins such as silsesquioxane.

Moreover, by using a polyfunctional oxetane compound among the thermosetting resins, it is possible to achieve a one-component solution of the curable resin composition. This is because the reactivity of the polyfunctional oxetane compound is slower than that of the polyfunctional epoxy compound, and the stability over time is excellent. According to the property of excellent stability over time, the curable resin composition can be formed into a dry film.
<< Non-reactive Carboxylic Acid-Containing Polymer >>
Non-reactive carboxylic acid-containing vinyl polymers include vinyl polymers and cellulose. Vinyl polymers are preferred from the standpoint of the balance between resist performance of dry film resist and alkali developability.

There is no limitation in particular as a method of obtaining the vinyl polymer which has carboxylic acid. For example,
(1) A method in which a vinyl monomer having a functional group capable of reacting with a carboxylic acid such as an epoxy group or an amino group is copolymerized and then reacted with a carboxylic acid (in this case, a carboxylic acid anhydride is preferred).
(2) A method of producing a carboxylic acid by copolymerizing a carboxylic acid ester vinyl monomer that is relatively easily hydrolyzed and then hydrolyzing with an acid or a base.
(3) A method of copolymerizing a carboxylic acid vinyl monomer.
The method (3) is preferable in that a carboxylic acid-containing vinyl polymer can be obtained quantitatively and relatively easily. Hereinafter, the method (3) will be described in detail.
At least one monomer selected from α, β-unsaturated carboxylic acid and alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylamide and hydrogen on the nitrogen atom to alkyl group or alkoxy group It is a compound obtained by vinyl copolymerizing at least one second monomer selected from a substituted compound, styrene and derivatives thereof, (meth) acrylonitrile, and glycidyl (meth) acrylate.

  Examples of the first monomer used in the carboxylic acid-containing vinyl copolymer include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid, and half esters thereof. This first monomer may be used alone or in combination of two or more.

The second monomer used in the carboxylic acid-containing vinyl copolymer includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, cyclohexyl (meth) acrylate, and n-butyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene propylene glycol mono (meth) ) Acrylate, (meth) acrylamide, N-methylolacrylamide, N-butoxymethylacrylic, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, (meth) acrylonite Ril, glycidyl (meth) acrylate, and the like. Each may be used alone or in combination of two or more.
The addition amount of the curable component (C) is not particularly limited, and can be appropriately selected according to the intended composition. For example, in the case of constituting a photocurable / thermosetting composition, for example, a curable resist. The proportion of the vinyl polymer (A) in the curable composition for use is preferably from 1 to 80% by weight from the viewpoints of curability, flexibility, and alkali developability. If it is less than 1% by weight, the curability and flexibility of the resist film at the time of exposure are insufficient, and if it exceeds 80% by weight, the alkali developability becomes insufficient. More preferably, it is 5 to 60% by weight.
<Monomer and / or oligomer>
In the present curable composition, a polymerizable monomer and / or oligomer or various additives may be used in combination depending on the purpose. Polymerizable monomers and / or oligomers 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, and chlorides. The thing which has a vinyl group etc. is mentioned. Especially, what has the (meth) acryl group similar to the polymer of this invention is 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. In the following formula, n represents an integer of 0-20.

スチレン系モノマーとしてはスチレン、α−メチルスチレン等が、アクリルアミド系モノマーとしてはアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド等が、共役ジエン系モノマーとしてはブタジエン、イソプレン等が、ビニルケトン系モノマーとしてはメチルビニルケトン等が挙げられる。

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 isocyanates (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. The number average molecular weight of the polymerizable monomer and / or oligomer is 5000 or less. Among these, it is preferable that it is 2000 or less by the reactivity and the viscosity fall at the time of addition, and it is still more preferable that it is 1000 or less from the reason that compatibility is favorable.
<Adhesive agent>
A silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the curable composition of the present invention. When the adhesion-imparting agent is added, the joint width or the like varies due to an external force, thereby further reducing the risk of the sealing material peeling from the adherend such as a siding board. Further, in some cases, it is not necessary to use a primer used for improving adhesion, and simplification of construction work is expected. Specific examples of silane coupling agents include silane coupling agents having functional groups such as amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens, and the like. As γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane and other isocyanate group-containing silanes; γ-aminopropyltrimethoxysilane Γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) amino Propyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ -(2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl -Amino group-containing silanes such as γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy group-containing silanes such as silane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- Carboxysilanes such as (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltrieth Examples thereof include vinyl unsaturated group-containing silanes such as xysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. Further, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, blocked isocyanate silanes, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used.

  The silane coupling agent used for this invention is normally used in 0.1-20 parts with respect to 100 parts of vinyl polymers (A). 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 adhesiveness-imparting agents, the adhesion to the adherend can be improved. Although not particularly limited, 0.1 to 20 parts by weight of a silane coupling agent is used in combination with the above-described adhesion-imparting agent in order to improve adhesion, particularly adhesion to a metal-coated surface such as an oil pan. Is preferred.

The kind and addition amount of the adhesion-imparting agent can control the curability and mechanical properties of the present invention according to the purpose and application. In particular, care must be taken when selecting because it affects curability and elongation.
<Plasticizer>
You may use various plasticizers for the curable composition of this invention as needed. When a plasticizer is used in combination with a filler described later, it becomes more advantageous because the elongation of the cured product can be increased or a large amount of filler can be mixed. However, it does not necessarily have to be added.
Although it does not specifically limit as a plasticizer, Phthalate esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylricinoleate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Esters of polyalkylene glycols such as erythritol esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Polystyrene and poly-α-methylstyrene Polystyrene, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene glycol, polypropylene glycol, poly Polyether polyols such as tetramethylene glycol and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; sebacic acid , Dibasic acids such as adipic acid, azelaic acid, phthalic acid and the like and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc. Examples thereof include polyester plasticizers obtained from coal; (meth) acrylic polymers obtained by polymerizing vinyl monomers including acrylic plasticizers by various methods.

  Among them, the polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000 is added, whereby the viscosity and slump property of the curable composition and the tensile strength of the cured product obtained by curing the composition, Mechanical properties such as elongation can be adjusted, and the initial physical properties can be maintained over a long period of time compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. The drying property (also called paintability) when a paint is applied can be improved. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the polymer plasticizer was described as 500-15000 above, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and moisture, and the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability may not be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen.

Among these polymer plasticizers, those compatible with the vinyl polymer (A) are preferable. Of these, (meth) acrylic polymers are preferred from the viewpoint of compatibility, weather resistance, and heat resistance. Among (meth) acrylic polymers, acrylic polymers are more preferable. Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer is prepared by a high temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-313522, USP 5010166) without using a solvent or a chain transfer agent. More preferred for the purposes of the present invention. Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

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

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.

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

The amount used in the case of using a plasticizer is not limited, but is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (A). is there. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.
<Filler>
You may use various fillers for the curable composition of this invention as needed. Although it varies depending on the type of filler, it is generally useful because it can improve the reduction of the loss factor (damping characteristics) particularly in a high temperature region of 80 ° C. or higher. The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, silica (fumed silica, sedimentation) Silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, Fillers such as clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red pepper, fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, Glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber They include fibrous fillers such as is.

  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 it is desired to obtain a cured product with high strength using 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. Among them, the specific surface area (according to BET adsorption method) of 50 m ² / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface is previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganocyclopolysiloxane, or the like is more preferable.

  More specific examples of silica-based fillers having high reinforcing properties are not particularly limited, but are those of Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Co., Ltd., which is one of precipitated silica. Nipsil and the like.

  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. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product.

  Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the adhesiveness and weather resistance of the curable composition are improved. The improvement effect is considered to be further improved. As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc. And salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids. Specific examples of the surfactants include polyoxyethylene alkyl ether sulfates and long chain alcohol sulfates, sulfate anion surfactants such as sodium salts and potassium salts thereof, alkylbenzene sulfonic acids, and alkylnaphthalenes. Examples thereof include sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkylsulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof. The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability, adhesiveness and weatherability may not be sufficiently improved. When the treatment amount exceeds 20% by weight, the storage stability of the curable composition may be reduced. May decrease.

  Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as thixotropy of the compound, breaking strength of the cured product, elongation at break, adhesion and weather resistance are expected. Is preferred.

  On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, use the following as necessary. be able to.

Heavy calcium carbonate is obtained by mechanically crushing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for the pulverization method, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes a product having various average particle diameters by classification. Although not particularly limited, when the effect of improving the breaking strength, elongation at break, adhesion and weather resistance of the cured product is expected, the specific surface area value is 1.5 m ² / g or more and 50 m ² / g or less. , more preferably from 2m ² / g or more 50 m ² / g or less, more preferably 2.4 m ² / g or more ^{50m 2 / g, 3m 2 /} g or more 50 m ² / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply lowered or when the purpose is to increase the viscosity only.

  In addition, the value of the specific surface area means a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

These fillers may be used alone or in combination of two or more according to the purpose and necessity. Although there is no particular limitation, for example, if a combination of heavy calcium carbonate and colloidal calcium carbonate having a specific surface area value of 1.5 m ² / g or more as necessary, the increase in the viscosity of the compound is moderately suppressed, and the cured product The effect of improving the breaking strength, breaking elongation, adhesiveness and weathering adhesion can be greatly expected.

When the filler is used, it is preferable to use the filler in the range of 5 to 1000 parts by weight, preferably in the range of 20 to 500 parts by weight, with respect to 100 parts by weight of the vinyl polymer (A). It is more preferable to use in the range of 40 to 300 parts by weight. If the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts by weight, the work of the curable composition May decrease. A filler may be used independently and may be used together 2 or more types.
<Micro hollow particles>
Furthermore, for the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles may be used in combination with these reinforcing fillers.

Such fine hollow particles (hereinafter referred to as “balloons”) are not particularly limited, but as described in “the latest technology of functional filler” (CMC), the diameter is 1 mm or less, preferably 500 μm or less, and more preferably Is a hollow body made of an inorganic or organic material of 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and it is more preferable to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

  Examples of the inorganic balloon include silicate balloons and non-silicate balloons. Silicate balloons include shirasu balloons, perlite, glass balloons, silica balloons, fly ash balloons, etc., and non-silicate balloons include alumina. Examples include balloons, zirconia balloons, and carbon balloons. Specific examples of these inorganic balloons include Shirasu balloons manufactured by Idichi Kasei Co., Ltd., Sankilite manufactured by Sanki Kogyo Co., Ltd., Nippon Glass Co., Ltd., Caloon made by Sumitomo 3M, Cellstar Z-28 made by Sumitomo 3M, and MICRO made by EMERSON & CUMING. BALLON, PELTSBURGE CORNING's CELAMIC GLASSMMODULES, 3M's GLASS BUBBLES, Asahi Glass's Q-CEL, Taiheiyo Cement's E-SPHERES, Fly Ash Balloon's, PERAMARKET's CEROSPHERES S. FILLITE manufactured by A, BW manufactured by Showa Denko as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA as a zirconia balloon, clecas sphere manufactured by Kureha Chemical, and CARBOS sphere manufactured by GENERAL TECHNOLOGIES as a carbon balloon are commercially available.

  Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon. The thermosetting balloon includes a phenol balloon, an epoxy balloon, and a urea balloon. The thermoplastic balloon includes a saran balloon, a polystyrene balloon, Examples thereof include polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons. A crosslinked thermoplastic balloon can also be used. The balloon here may be a balloon after foaming, or a balloon containing a foaming agent may be foamed after blending.

  Specific examples of these organic balloons include UCAR and PHENOLIC MICROBALLONONS made by Union Carbide as phenolic balloons, ECCOSPHERES made by EMERSON & CUMING as epoxy balloons, ECCOSPHERES VF-O made by EMERSON & CUMING, and DOWEMIC PHALS made by Saran Balloon by Saran Balloon. EXPANSEL made by Nippon Filament, Matsumoto Microsphere made by Matsumoto Yushi Seiyaku, DYLITE EXPANDABLE POLYSTYRENE made by ARCO POLYMERS as polystyrene balloon, EXPANDABLE POLYSTYREN BEADS made by BASF WYANDOTE, SX863 (P) made by Nippon Synthetic Rubber is commercially available for the cross-linked styrene-acrylic acid balloon.

  The balloons may be used alone or in combination of two or more. In order to improve the dispersibility and the workability of the compound by using fatty acid, fatty acid ester, rosin, rosin lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. on the surface of these balloons. The processed one can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

  Although content of a balloon is not specifically limited, Preferably it is 0.1-50 parts with respect to 100 weight part of vinyl-type polymer (A), More preferably, it can use in 0.1-30 parts. If this amount is less than 0.1 part, the effect of weight reduction is small, and if it is 50 parts or more, a decrease in tensile strength may be observed among the mechanical properties when this compound is cured. When the specific gravity of the balloon is 0.1 or more, 3 to 50 parts, more preferably 5 to 30 parts are preferred.

  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 modifier, 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.
<Silanol-containing compound>
You may add a silanol containing compound to the curable composition of this invention as needed, such as changing the physical property of hardened | cured material. The silanol-containing compound refers to a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting with moisture. Only one of these may be used, or both compounds may be used simultaneously.

The compound having one silanol group in the molecule which is one of the silanol-containing compounds is not particularly limited, and the compounds shown below,
(CH ₃ ) ₃ SiOH, (CH ₃ CH ₂ ) ₃ SiOH, (CH ₃ CH ₂ CH ₂ ) ₃ SiOH, (n-Bu) ₃ SiOH, (sec-Bu) ₃ SiOH, (t-Bu) ₃ SiOH , (T-Bu) Si (CH ₃ ) ₂ OH, (C ₅ H ₁₁ ) ₃ SiOH, (C ₆ H ₁₃ ) ₃ SiOH, (C ₆ H ₅ ) ₃ SiOH, (C ₆ H ₅ ) ₂ Si ( CH ₃ ) OH, (C ₆ H ₅ ) Si (CH ₃ ) ₂ OH, (C ₆ H ₅ ) ₂ Si (C ₂ H ₅ ) OH, C ₆ H ₅ Si (C ₂ H ₅ ) ₂ OH, C ₆ H ₅ CH ₂ Si (C ₂ H ₅ ) ₂ OH, C ₁₀ H ₇ Si (CH ₃ ) ₂ OH
(In the above formula, C ₆ H ₅ represents a phenyl group, and C ₁₀ H ₇ represents a naphthyl group.)
A compound that can be represented by (R ″) ₃ SiOH, where R ″ is the same or different substituted or unsubstituted alkyl or aryl group,

等のようなシラノール基を含有する環状ポリシロキサン化合物、

Cyclic polysiloxane compounds containing silanol groups such as

等のようなシラノール基を含有する鎖状ポリシロキサン化合物、なお、上式のおいてｎは１〜２０の整数を示す。

A chain polysiloxane compound containing a silanol group such as n, etc. In the above formula, n represents an integer of 1 to 20.

等のような主鎖が珪素、炭素からなるポリマー末端にシラノール基が結合した化合物、なお、上式のおいてｎは１〜２０の整数を示す。

A compound in which the main chain is composed of silicon, carbon and the like, and a silanol group is bonded to the polymer terminal. In the above formula, n represents an integer of 1 to 20.

等のようなポリシラン主鎖末端にシラノール基が結合した化合物、なお、上式のおいてｎは１〜２０の整数を示す。

A compound in which a silanol group is bonded to the polysilane main chain terminal, such as in the above formula, where n represents an integer of 1 to 20.

等のような主鎖が珪素、炭素、酸素からなるポリマー末端にシラノール基が結合した化合物等が例示できる。なお、上式のおいてｍは１〜２０の整数、ｎは１〜２０の整数を示す。このうち下記一般式（３９）で表される化合物が好ましい。
（Ｒ³⁹）₃ＳｉＯＨ （３９）
（式中、Ｒ³⁹は炭素数１〜２０の１価の炭化水素基を示す。複数のＲ³⁹は同一であっても
よく又は異なっていてもよい。）
Ｒ³⁹は、メチル基、エチル基、ビニル基、ｔ−ブチル基、フェニル基が好ましく、さらにメチル基が好ましい。

Examples thereof include compounds in which a main chain is composed of silicon, carbon, oxygen, and a silanol group bonded to a polymer terminal. In the above formula, m represents an integer of 1 to 20, and n represents an integer of 1 to 20. Among these, the compound represented by the following general formula (39) is preferable.
(R ³⁹ ) ₃ SiOH (39)
(In the formula, R ³⁹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ³⁹ may be the same or different.)
R ³⁹ is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group, or a phenyl group, and more preferably a methyl group.

Among them, (CH ₃ ) ₃ SiOH having a small molecular weight is preferable because it is easily available and effective.

When the compound having one silanol group in the molecule is used as an adhesion imparting agent based on silane, the silane coupling agent reacts with a siloxane bond formed by silyl group or crosslinking. It is presumed that the crosslinked cured product is given flexibility by suppressing excessive crosslinking.
The compound capable of producing a compound having one silanol group in the molecule by reacting with moisture is not particularly limited, but a compound having one silanol group in the molecule produced by reacting with moisture (hydrolysis) The product is preferably a compound represented by the general formula (39). For example, although not particularly limited, the following compounds may be mentioned in addition to the compound represented by the general formula (40) as described later.

N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N -Methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) Imidazole, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl phenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris of glycerol Chirushiriru) iodide, tris (trimethylsilyl) ated trimethylolpropane, tris (trimethylsilyl) ated pentaerythritol, pentaerythritol tetra (trimethylsilyl) ated _{product, (CH 3) 3 SiNHSi (} CH 3) 3, (CH 3) 3 SiNSi (CH ₃ ) ₂ ,

等が好適に使用できるが加水分解生成物の含有シラノール基の量からは（ＣＨ₃）₃ＳｉＮＨＳｉ（ＣＨ₃）₃が特に好ましい。

However, (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is particularly preferred from the amount of silanol groups contained in the hydrolysis product.

Although the compound which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting with a water | moisture content is not specifically limited, The compound represented by following General formula (29) other than the said compound is preferable.
((R ³⁹ ) ₃ SiO) _n R ⁴⁰ (40)
(In the formula, R ³⁹ is the same as described above. N represents a positive number, and R ⁴⁰ represents a group obtained by removing some or all of the active hydrogen from the active hydrogen-containing compound.)
R ⁴⁰ is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group, or a phenyl group, and more preferably a methyl group.
The (R ³⁹ ) ₃ Si group is particularly preferably a trimethylsilyl group in which all three R ³⁹ are methyl groups. N is preferably 1 to 5.

The active hydrogen-containing compound from which R ⁴⁰ is derived is not particularly limited. For example, methanol, ethanol, n-butanol, i-butanol, t-butanol, n-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol , Alcohols such as diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, tetramethylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol; phenol, cresol, bisphenol A, hydroquinone, etc. Phenols; formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, behenic acid, acrylic acid, methacrylic acid Carboxylic acids such as oleic acid, linoleic acid, linolenic acid, sorbic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid; ammonia; methylamine, dimethyl Amines such as amine, ethylamine, diethylamine, n-butylamine and imidazole; acid amides such as acetamide and benzamide; ureas such as urea and N, N′-diphenylurea; acetone, acetylacetone and 2,4-heptadione Examples include ketones.

The compound capable of generating a compound having one silanol group in the molecule by reacting with the water represented by the general formula (40) is, for example, trimethylsilyl chloride or dimethyl (t It can be obtained by reacting a compound having a group capable of reacting with an active hydrogen such as a halogen group together with a (R ³³ ) ₃ Si group, which is also called a silylating agent such as -butyl) chloride, but is not limited thereto. (However, R ³³ is the same as described above.)

  Specific examples of the compound represented by the general formula (40) include allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- Methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, Hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyl trifluoromethanesulfonate, trimethylsilylphenoxide, n-octanol trimethyl Silylated, 2-ethylhexanol trimethylsilylated, glycerol tris (trimethylsilyl), trimethylolpropane tris (trimethylsilyl), pentaerythritol tris (trimethylsilyl), pentaerythritol tetra (trimethylsilyl) However, it is not limited to these. These may be used alone or in combination of two or more.

In addition, a compound represented by the general formula (((R ⁴¹ ) ₃ SiO) (R ⁴² O) _s ) _t Z, CH ₃ O (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ , CH ₂ = CHCH ₂ (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ , (CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ , ( CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₇ Si (CH ₃ ) ₃
(Wherein R ⁴¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom, R ⁴² is a divalent hydrocarbon group having 1 to 8 carbon atoms, and s and t are positive integers. , S is 1-6, s × t is 5 or more, Z is a 1-6 valent organic group)
Etc. can also be used suitably. These may be used alone or in combination of two or more.

  Among the compounds that can generate a compound having one silanol group in the molecule by reacting with moisture, the active hydrogen-containing compound generated after hydrolysis in that it does not adversely affect storage stability, weather resistance, etc. Phenols, acid amides, and alcohols are preferable, and phenols and alcohols in which the active hydrogen-containing compound is a hydroxyl group are more preferable.

  Among the above compounds, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, A tris (trimethylsilyl) product of trimethylolpropane, a tris (trimethylsilyl) product of pentaerythritol, a tetra (trimethylsilyl) product of pentaerythritol and the like are preferable.

  A compound that can generate a compound having one silanol group in the molecule by reacting with moisture has one silanol group in the molecule by reacting with moisture during storage, curing or after curing. A compound is produced. The compound having one silanol group in the molecule thus produced reacts with a crosslinkable silyl group or a siloxane bond formed by crosslinking when a silane coupling agent is used as an adhesiveness imparting agent as described above. By doing so, it is presumed that excessive condensation reaction is suppressed and the cured product is given flexibility.

  The addition amount of the silanol-containing compound can be appropriately adjusted according to the expected physical properties of the cured product. The silanol-containing compound can be added in an amount of 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer (A). If the amount is less than 0.1 parts by weight, the effect of addition does not appear. If the amount exceeds 50 parts by weight, the crosslinking becomes insufficient, and the strength and gel fraction of the cured product are too low.

Further, the timing of adding the silanol-containing compound to the vinyl polymer (A) is not particularly limited, and it may be added at the time of producing the vinyl polymer (A), or may be added at the time of producing the curable composition. Good.
<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.

Further, the sagging preventing agent is not particularly limited, and examples thereof include 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.
<Photo-curing substance>
You may add a photocurable substance to the curable composition of this invention as needed. The photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a short time due to the action of light, resulting in a change in physical properties such as curing. By adding this photocurable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. This photo-curing substance is a substance that can be cured by exposure to light, but a typical photo-curing substance should be allowed to stand at room temperature for one day, for example, in a room where the sun is exposed (near the window). It is a substance that can be cured by. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and the type thereof is not particularly limited. For example, unsaturated acrylic compounds, polycinnamic acid Examples thereof include vinyls and azido resins.

The unsaturated acrylic compound is a monomer, oligomer or mixture thereof having an unsaturated group represented by the following general formula (41).
^{_{CH 2 = CHR 37 CO (O}} ) - (41)
In the formula, R ³⁷ 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.

  Specific examples of unsaturated acrylic compounds include (meth) acrylic esters of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and neopentyl alcohol; bisphenol A, isocyanuric acid, and the like. (Meth) acrylic acid esters of alcohols obtained by modifying acids or the above low molecular weight alcohols with ethylene oxide or propylene oxide; polyether polyols having a main chain as a polyether and having a hydroxyl group at the terminal, in a polyol having a main chain as a polyether A polymer polyol obtained by radical polymerization of a vinyl monomer, a polyester polyol having a main chain of polyester and a hydroxyl group at the terminal, a main chain of a vinyl or (meth) acrylic polymer, and a hydroxyl group in the main chain (Meth) acrylic acid esters such as polyols having epoxy; epoxy acrylate oligomers obtained by reacting bisphenol A type or novolak type epoxy resins with (meth) acrylic acid; containing polyols, polyisocyanates and hydroxyl groups ( Examples thereof include urethane acrylate oligomers having a urethane bond and a (meth) acryl group in a molecular chain obtained by reacting meth) acrylate or the like.

  Polyvinyl cinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group, and includes many polyvinyl cinnamate derivatives other than those obtained by esterifying polyvinyl alcohol with cinnamic acid.

  Azide resin is known as a photosensitive resin having an azide group as a photosensitive group. In general, in addition to a rubber photosensitive solution in which an azide compound is added as a photosensitive agent, “photosensitive resin” (published March 17, 1972). , Published by the Printing Society Press, page 93 to page 106 to page 117), these are detailed examples, and these can be used alone or in combination, and a sensitizer can be added if necessary.

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

The photocurable material is preferably added in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer (A). If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.
<Air oxidation curable substance>
If necessary, an air oxidation curable material may be added to the curable composition of the present invention. The air oxidation curable substance is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By adding this air oxidation curable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. The air oxidation curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of curing by reacting with oxygen in the air. A typical air oxidative curable substance can be cured by, for example, standing in air indoors for 1 day.

  Examples of the air oxidative curable substance include drying oils such as paulownia oil and linseed oil; various alkyd resins obtained by modifying these drying oils; acrylic polymers, epoxy resins and silicone resins modified with drying oils; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers and copolymers, and various modified products of the polymers and copolymers (maleinized modified products, boiled oil modified products, etc.) A specific example is given. Of these, paulownia oil, diene polymer liquid (liquid diene polymer) and modified products thereof are particularly preferred.

  Specific examples of the liquid diene polymer include a liquid polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and copolymerizable with these diene compounds. Polymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene having a main component with a diene compound, and various modified products thereof (maleinized modified products, boiled oils) Modified products, etc.). These may be used alone or in combination of two or more. Of these liquid diene compounds, liquid polybutadiene is preferred.

  The air oxidation curable substance may be used alone or in combination of two or more. In addition, the effect may be enhanced if a catalyst that promotes the oxidative curing reaction or a metal dryer is used together with the air oxidative curable substance. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, amine compounds, and the like.

The air oxidation curable substance is preferably added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the vinyl polymer (A). If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected.
<Antioxidant>
You may add antioxidant to the curable composition of this invention as needed. Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.

  For example, phosphorus antioxidants such as thioethers such as MARK PEP-36 and MARK AO-23 (all of which are manufactured by Adeka Gas Chemical), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all of which are manufactured by Ciba Geigy Japan) Etc. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following.
2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4 ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4 ' -Thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3-t- Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5- -T-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine , Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4 -Hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2, , 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, Tris- (3,5 -Di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy -3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzoto Riazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzo Triazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, methyl-3- [3- t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4- Perijiru), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

  In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Manufactured by Ouchi Shinsei Chemical Industry), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Adeka Argus Chemical), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGA NOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of which are manufactured by Ciba Geigy, Japan), Sumizer GM, Sumilizer GA-80 (all of which are manufactured by Sumitomo Chemical), etc. However, it is not limited to these.

  Antioxidants may be used in combination with the light stabilizer described later, and are particularly preferred because they can further exert their effects and particularly improve the weather resistance. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which an antioxidant and a light stabilizer are mixed in advance may be used.

It is preferable that the usage-amount of antioxidant is the range of 0.1-10 weight part with respect to 100 weight part of vinyl-type polymer (A). If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.
<Light stabilizer>
You may add a light stabilizer to the curable composition of this invention as needed. Various types of light stabilizers are known, and are described in, for example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.

  Although not particularly limited, among the light stabilizers, an ultraviolet absorber is preferable. Specifically, TINUVIN P, TINUVIN 234, TINUVIN 320, TINUVIN 326, TINUVIN 327, TINUVIN 329, TINUVIN 213 (all of which are manufactured by Ciba Geigy Japan) Benzotriazole compounds such as TINUVIN 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as TINUVIN 120 (manufactured by Ciba Geigy Japan).

  Hindered amine compounds are also preferred, and such compounds are described below. Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3aminopropyl) ethylenediamine- 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) ester and the like.

  In terms of product names, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL, Irgafos 168 (all of which are manufactured by Ciba Geigy Japan), MARK LA-52, MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-67 63, MARK LA-68, MARK LA-82, MARK LA-87 (all manufactured by Adeka Gas Chemical), Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS -1114, Sanol LS-744, Sanol LS-440 (all of which are manufactured by Sankyo) and the like, but are not limited thereto.

  Furthermore, since the combination of the ultraviolet absorber and the hindered amine compound may exhibit more effect, it is not particularly limited but may be used in combination, and it is preferable to use in combination.

  The light stabilizer may be used in combination with the above-described antioxidant, and it is particularly preferable because the effect is further exhibited and the weather resistance may be improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which a light stabilizer and an antioxidant are mixed in advance may be used.

The amount of the light stabilizer used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer (A). If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.
<< cured product >>
The curable composition of the present invention has excellent curability at normal temperature (23 ° C. × 55 RH) and a cured product obtained by curing the curable composition has mechanical properties, oil resistance, heat resistance, Excellent weather resistance. In addition, since this curable composition uses an amine component as a crosslinking agent, it can be blended and co-crosslinked with an epoxy resin, and the flexibility of the cured epoxy resin is not reduced. It is possible to improve or increase the strength of the cured vinyl polymer.
<Application>
Although the curable composition of this invention will not be limited if it is a resist use, A semiconductor resist, a liquid solder resist, an electrodeposition resist, a dry film resist, the photoresist for liquid crystals, etc. are mentioned. Semiconductor resists include UV resists, Deep UV resists, and EB resists depending on the form of curing. It is roughly divided into electrodeposition resist and dry film resist. In addition, a permanent resist application that does not require etching, such as an insulating coating, can be cited as one of the resist applications.
The curable composition for resist can be applied to the electronics field around home appliances and automobiles. More specifically, it is used for circuit pattern formation, heat-resistant coating during soldering on a printed circuit board, and the like. For use in semiconductor resist for semiconductor resist, printed wiring board for liquid solder resist, printed circuit board, build-up board, three-dimensional circuit board for electrodeposition resist, and single-sided / double-sided / multi-layered circuit board for dry film resist The photoresist for liquid crystal can be used for TFT wiring, color filters, and the like.
<Printed wiring board manufacturing process>
Among the above resist applications, an example of a printed circuit board manufacturing process using a liquid solder resist and a dry film resist described in Examples will be shown.
[Liquid solder resist]
(1) Coating process The process of apply | coating the curable composition for soldering resists to the printed wiring board by which the circuit was formed by methods, such as a screen printing method, a curtain coat method, and a spray coat method.
(2) Exposure process The process of selectively exposing with an active energy ray through a photomask.
(3) Development process The process which develops a non-exposed part with alkaline aqueous solution, and forms a resist pattern.
(4) Curing step A step of forming a resist film having excellent heat resistance, adhesion, plating resistance, and electrical characteristics by curing the resist pattern by heating or the like.
[Dry film resist]
(1) Lamination process The process of making it adhere on a copper-clad laminated board and a flexible substrate, making the curable composition for dry film resist peel from a protective sheet.
(2) Exposure process The process which makes the mask film which has a specific wiring pattern closely_contact | adhere on a dry film, and is hardened with an active energy ray light source.
(3) Development process The process which removes a masking film, melt | dissolves or disperses the uncured part of the photosensitive curable composition layer, and forms a resist pattern on a substrate.
(4) Etching process or plating process A copper or solder nickel plating process is performed on a copper surface not covered with a resist pattern or a process of etching a copper surface not covered with a resist pattern from the formed resist pattern Process.
(5) Stripping step A step of removing the resist pattern from the substrate using an alkaline stripping solution.

  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, “part” and “%” are “part by weight” and “% by weight”, respectively.
". In this example, “triamine” refers to pentamethyldiethylenetriamine.

  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 (shodex GPC K-804; manufactured by Showa Denko) and chloroform as a GPC solvent were used.

(Production Example 1)
(Method for producing n-butyl acrylate polymer having acryloyl group at terminal)
A 1 L flask was charged with 3.36 g (23.5 mmol) of copper (I) bromide and 89.4 mL of acetonitrile, and the mixture was heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. To this, 14.0 g (38.9 mmol) of diethyl 2,5-dibromoadipate and 894 mL (6.24 mol) of butyl acrylate were added, and the mixture was further heated and stirred at 80 ° C. for 20 minutes. Triamine 0.16 mL (0.77 mmol) was added to initiate the reaction. Further, triamine was added as appropriate and stirring was continued at 80 ° C., and the polymerization was terminated when the polymerization reaction rate exceeded 95%.

  400 g of this polymer is dissolved in N, N-dimethylacetamide (400 mL), 7.4 g of potassium acrylate is added, and the mixture is heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere to give an acryloyl group-terminated n-butyl acrylate polymer. A mixture of ([1]) was obtained. After N, N-dimethylacetamide in this mixture was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [1]. The number average molecular weight of the polymer [1] after purification was 22500, the molecular weight distribution was 1.25, and the average number of terminal acryloyl groups was 1.9.

(Production Example 2)
(Synthesis of poly (acryloyl group) terminal poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
A 0.5 L flask was charged with 1.4 g (9.7 mmol) of copper (I) bromide and 30.9 mL of acetonitrile, and heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. To this, 7.8 g (21.6 mmol) of diethyl 2,5-dibromoadipate, 7.4 ml (51.9 mmol) of n-butyl acrylate, 134.9 ml (1.24 mol) of ethyl acrylate, 2-methoxyethyl acrylate 166.7 ml (1.30 mol) was further heated and stirred at 80 ° C. for 20 minutes. Triamine 0.14 mL (0.6 mmol) was added to start the reaction. Further, triamine was added as appropriate and stirring was continued at 80 ° C., and the polymerization was terminated when the polymerization reaction rate exceeded 95%. 300 g of this polymer was dissolved in N, N-dimethylacetamide (300 mL), 8.5 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere, and acryloyl group-terminated poly (n-butyl acrylate) was added. / Ethyl acrylate / 2-methoxyethyl acrylate) (polymer [2]) was obtained. After N, N-dimethylacetamide in this mixture was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [2]. The purified polymer [2] had a number average molecular weight of 15,200, a molecular weight distribution of 1.08, and an average number of terminal acryloyl groups of 1.7.

(Production Example 3)
(Synthesis of poly (acryloyl group) terminal poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
A 0.5 L flask was charged with 1.2 g (8.7 mmol) of copper (I) bromide and 30.6 mL of acetonitrile, and heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. To this, 6.9 g (19.4 mmol) of diethyl 2,5-dibromoadipate and 76.6 m of n-butyl acrylate
1 (0.53 mol), ethyl acrylate 5.0 ml (46.5 mmol), 2-methoxyethyl acrylate 224.1 ml (1.74 mol), and further heated and stirred at 80 ° C. for 20 minutes. The reaction was initiated by adding 0.12 mL (0.6 mmol) of triamine. Further, triamine was added as appropriate and stirring was continued at 80 ° C., and the polymerization was terminated when the polymerization reaction rate exceeded 95%. 300 g of this polymer was dissolved in N, N-dimethylacetamide (300 mL), 7.4 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours under a nitrogen atmosphere, and acryloyl group-terminated poly (n-butyl acrylate) was added. / Ethyl acrylate / 2-methoxyethyl acrylate) (polymer [3]) was obtained. After N, N-dimethylacetamide in this mixture was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [3]. The purified polymer [3] had a number average molecular weight of 17,200, a molecular weight distribution of 1.09, and an average number of terminal acryloyl groups of 1.8.

(Production Example 4)
(Synthesis of acryloyl group both terminal poly (n-butyl acrylate / acrylic acid))
A 3 L flask was charged with 5.9 g (41.0 mmol) of copper (I) bromide and 123.3 mL of acetonitrile, and heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. To this, 49.2 g (0.14 mol) of diethyl 2,5-dibromoadipate, 1409.4 ml (9.83 mol) of n-butyl acrylate, 160.0 ml (1.09 mol) of t-butyl acrylate, and 20 at 80 ° C. Stir with heating for a minute. The reaction was initiated by adding 0.57 mL (2.7 mmol) of triamine. Further, triamine was added as appropriate and stirring was continued at 80 ° C., and the polymerization was terminated when the polymerization reaction rate exceeded 95%. 629 g of this polymer was dissolved in N, N-dimethylacetamide (629 g), 10.6 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours under a nitrogen atmosphere, and acryloyl group-terminated poly (butyl acrylate / t -Butyl acrylate) mixture was obtained. After N, N-dimethylacetamide in this mixture was distilled off under reduced pressure, 550 g of toluene was added to 550 g of the residue, and the insoluble matter was removed by filtration. 5.5 g of p-toluenesulfonic acid was added to toluene in the filtrate, and the mixture was stirred at 100 ° C. for 3 hours. Unnecessary substances were filtered, and then toluene in the filtrate was distilled off under reduced pressure to purify the polymer [4]. The purified polymer [4] had a number average molecular weight of 22,000, a molecular weight distribution of 1.09, and an average number of terminal acryloyl groups of 1.8.

It was confirmed by ¹³ C-NMR that the methyl group signal (28 ppm) of the t-butyl group, which was present in the polymer before addition of p-toluenesulfonic acid, disappeared in the polymer [4]. Further, the presence of a carboxyl group in the polymer [4] was confirmed as follows.
The polymer [4] was dissolved in chloroform, and separately generated diazomethane was added and stirred. After removing the volatile matter by reducing the pressure, this was dissolved in deuterated chloroform and analyzed by ¹ H-NMR. As a result, a signal derived from —COOCH ₃ group was observed at 3.6 ppm. In this system, since diazomethane selectively reacts only with —COOH groups (carboxyl groups) to generate —COOCH ₃ groups, it was shown that carboxyl groups exist in the polymer [2]. Further, the amount of carboxyl groups of the polymer [4] calculated from the integrated value of —COOCH ₃ groups was 10 mol% in the total acrylic unit, which is the acrylic used for polymer synthesis before the addition of p-toluenesulfonic acid. It was consistent with the amount of t-butyl acid.

From the above, it was shown that in the polymer [4], the —COOC (CH ₃ ) ₃ group of the polymer before addition of p-toluenesulfonic acid was quantitatively converted to a carboxyl group.

(Production Example 5)
(Synthesis of non-reactive carboxylic acid-containing vinyl polymer)
To a place where 60 g of methyl ethyl ketone was charged in a 1 L flask and heated and stirred at 70 ° C., 130 g of methyl methacrylate, 50 g of methacrylic acid, 20 g of butyl acrylate, 2,2-azobis (2-methylbutyronitrile) (trade name; V-59 , Manufactured by Wako Pure Chemical Industries, Ltd.) 1.0 g and methyl ethyl ketone 120 g were dropped into the flask over 4 hours. Subsequently, a solution of 0.15 g of 2,2-azobis (2-methylbutyronitrile) in 180 g of methyl ethyl ketone was added to the flask over 1 hour and held at 70 ° C. for 1 hour to obtain a polymer [5]. . The number average molecular weight of the polymer [5] was 43800, the molecular weight distribution was 3.06, 105 ° C., and the non-volatile component when dried for 60 minutes was 35.1%.

(Production Example 6)
The polymer [5] obtained in Production Example 5 is heated to 90 ° C., a polymerization inhibitor, 0.05 g of methoquinone and 0.5 g of triphenylphosphine are added, and 50 g of glycidyl methacrylate is gradually added dropwise to react for 18 hours. , A polymer [6] having both a (meth) acryloyl group and a carboxyl group was obtained.

Example 1
Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane as a phenolic antioxidant was added to 100 parts of the polymer [1] obtained in Production Example 1. IRGANOX 1010 (manufactured by Ciba Specialty Chemicals) 1 part of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCURE 1173; manufactured by Ciba Specialty Chemicals) as a photo radical initiator, bis (2, 4 , 6-Trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819; manufactured by Ciba Specialty Chemicals), dissolved and mixed well, defoamed at 60 ° C for 1 hour, and cured for resist. A composition was prepared.
Using the obtained resist curable composition, a resist film was produced by the following method. Further, the obtained curable composition for resist is poured into a mold to produce a 2 mm-thick cured product sheet in the same manner as the exposure conditions described below, and the 2 mm-thick cured product sheet is used for the permanent measurement by the following measurement method. Resist performance (moisture permeability, volume resistivity and dielectric properties) was evaluated. Table 1 shows the composition and evaluation results of the resist curable composition.
<Preparation of resist film>
As a permanent resist such as an insulating coating, a resist film was produced only by an exposure process.
(exposure)
Using a UV irradiator (model: LH-6, manufactured by Fusion UV Systems Japan Co., Ltd.), a photosensitive curable composition for resist having a thickness of 50 μm applied or laminated on a substrate, lamp energy = 184 W / cm, The exposure was performed at a conveyor speed of 1 m / min and an integrated light amount of 3030 mJ / cm ² .
<Moisture permeability>
Based on the method described in JIS Z 0208, moisture permeability for 24 hours was measured for a cured sheet having a thickness of 2 mm under temperature conditions = 40 ± 0.5 ° C. and humidity conditions = 90 ± 2%.
<Volume specific resistance>
Using a resistivity measuring device (model: R8340 ULTRA HIGH RESISTANCE METER / RESIST CHAMBER R12702A, manufactured by Advantest Co., Ltd.) for a cured sheet having a thickness of 2 mm, an applied voltage of 500 V, temperature and humidity = 23 ° C. × 55 RH% It was measured.
<Dielectric properties>
About 2 mm thick cured sheet, Q meter (model MQ-161, MEGURO
ELECTRONIC Co., Ltd.), frequency = 1 MHz, Q range = 250 C, temperature and humidity = 23 ° C. × 55 RH%.

Example 2
40 parts of the polymer [2] obtained in Production Example 2, 171 parts of the polymer [5] obtained in Production Example 5, 1 part of IR, GANOX 1010, 0.08 part of DAROCURE11173 as a photoradical initiator, IRGACURE819 04 parts were added and sufficiently dissolved and mixed, and then heated and degassed at 60 ° C. for 1 hour to prepare a curable composition for resist. The obtained resist curable composition was applied to a copper-clad plate to a thickness of 50 μm and exposed in the same manner as in Example 1 above. The resulting photosensitive resist film was further subjected to alkali development, etching, resist Peeling was performed as described below to prepare a resist film for a dry film, and the resist performance was evaluated as described below. Table 1 shows the composition and evaluation results of the resist curable composition.
<Alkali development>
The exposed photosensitive resist film is immersed in a 1 wt% Na ₂ CO ₃ aqueous solution at 25 ° C. for a predetermined time to dissolve and remove the unexposed portion, and the unexposed portion of the photosensitive resin layer is completely dissolved. The minimum time required for this was defined as the minimum development time.
<Etching>
A portion of the copper foil that is not covered with the resist pattern on the substrate by applying a mixed aqueous solution of cupric chloride concentration of 250 g / L and hydrochloric acid concentration of 3 mol / L at 50 ° C. to the substrate on which the resist pattern is formed by the above development Was removed.
<Resist stripping>
A resist film cured by applying a 3 wt% aqueous sodium hydroxide solution heated to 50 ° C. to the substrate after the etching step was peeled off to produce a printed wiring board.

<Resist performance evaluation method>
The evaluation items common to dry film applications and solder resist applications are shown below.
(Compatibility)
The compatibility between the vinyl polymer (A) having at least one crosslinkable functional group at the molecular terminal and the polymer (C) having an acidic functional group was evaluated by applying the curable composition of Example to a glass plate. .

  ○: The film is transparent.

  Δ: Some turbidity and opaque.

X: The film becomes cloudy.
(Sensitivity (curability during exposure))
The resist film after the UV irradiation was evaluated according to the following criteria.

  ○: After exposure, the resist film has no tack and is cured.

X: After exposure, tack remains on the resist film and is in an uncured state.
(Developability)
Development was performed under the above experimental conditions, and the determination was made according to the following criteria.

○: Minimum development time within 30 seconds Δ; Minimum development time over 30 seconds and 60 seconds or less ×; Minimum development time over 60 seconds (resist pattern peelability)
The resist was coated on the printed circuit board with a film thickness of 50 μm, which was the same as the above conditions, exposed, and developed in a time twice as long as the minimum development time of each level. The time until the resist of the obtained pattern was completely removed was measured. The evaluation criteria are as follows.

○: Peeling time is 30 seconds or less. Δ; Peeling time is more than 30 seconds and 60 seconds or less.

X: The peeling time exceeded 60 seconds.
(Resist flexibility)
The resist curable composition was cured by 2 mm alone, the film was bent 90 °, and it was visually confirmed whether the film had any abnormality.

  ○: No change.

  ×: There are cracks and cracks.

Example 3
Except for changing the polymer [2] of Example 2 to the polymer [3] obtained in Production Example 3, production of a curable composition for resist, production of a resist film under the same conditions as in Example 2, And evaluated. Table 1 shows the composition and evaluation results of the resist curable composition.

Example 4
Except for changing the polymer [2] in Example 2 to the polymer [4] obtained in Production Example 4, preparation of a curable composition for resist under the same conditions as in Example 2, preparation of a resist film, And evaluated. Table 1 shows the composition and evaluation results of the resist curable composition.

Example 5
After adding 191 parts of polymer [6] obtained in Production Example 6 to 33 parts of polymer [2], adding 1 part of IRGANOX 1010, 0.2 part of DAROCURE 1173, and 0.1 part of IRGACURE 819, sufficiently dissolving and mixing, 85 parts 85 parts of isopropyl alcohol was added and completely dissolved to prepare a resist curable composition. The obtained resist curable composition was applied to a copper-clad plate to a thickness of 50 μm, and exposed according to the same conditions as in Example 1 to produce a resist film. The obtained resist film was subjected to alkali development in the same manner as in Example 2, and then subjected to the following heat curing to produce a resist film for solder resist. The obtained resist film for solder resist was evaluated in the same manner as in Example 2, and a solder heat resistance test was performed according to the following method. The composition and evaluation results of the resist curable composition are shown in Table 2.
(Heat curing)
A solder resist substrate was prepared by heating and curing at 150 ° C. for 60 minutes.
(Solder heat resistance test)
The evaluation substrate produced by the heat curing was immersed in a solder bath maintained at 250 ° C. for 30 seconds and washed with isopropyl alcohol, and then the resist was swollen, peeled off, and discolored.

○: No change at all.
X: The resist layer is swollen or peeled off.

Comparative Example 1
Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as a phenolic antioxidant in 100 parts of urethane acrylate (EBECRYL230; manufactured by Daicel Cytec) as a photocurable resin Methane (trade name IRGANOX1010: manufactured by Ciba Specialty Chemicals) As a photoradical initiator, 0.5 part of 2,2 diethoxyacetophenone was added, and after sufficient dissolution and mixing, heating and defoaming was performed at 60 ° C. for 1 hour. A resist curable composition was prepared. A resist film was produced from the obtained resist curable composition in the same manner as in Example 1, and the permanent resist performance (moisture permeability, volume resistivity and dielectric properties) was evaluated. Table 1 shows the composition and evaluation results of the resist curable composition.

Comparative Example 2
Preparation of curable composition for resist and evaluation of resist performance in the same manner as in Example 5 except that trimethylolpropane triacrylate (TMPTA) was used instead of the polymer [2] in Example 5. Went. Table 1 shows the composition and evaluation results of the resist curable composition.

本発明のレジスト用硬化性組成物によれば、耐油性、耐熱性、耐光性、柔軟性に優れたレジスト用硬化物が得られる。具体的には、表１よりリビングラジカル重合法によって製造されたビニル系重合体（Ａ）用いることで硬化させて得られたレジスト用硬化性組成物は、良好な湿分バリアー性、絶縁性、静電特性を示しており、優れた永久レジスト性能有することが分かる。また（Ａ）成分ではメトキシエチルアクリレートの共重合量をアップさせた重合体またはカルボン酸を導入した重合体を用いることで、アルカリ現像性に必要なカルボン酸含有アクリル重合体（Ｃ）との相溶性の良好で、柔軟性に優れると共に、優れたドライフィルムレジスト特性、ソルダーレジスト特性を有することが分かる。

According to the resist curable composition of the present invention, a resist cured product excellent in oil resistance, heat resistance, light resistance and flexibility can be obtained. Specifically, the curable composition for a resist obtained by curing using a vinyl polymer (A) produced by the living radical polymerization method from Table 1, has good moisture barrier properties, insulating properties, It can be seen that it exhibits electrostatic properties and has excellent permanent resist performance. In addition, as the component (A), a polymer having an increased copolymerization amount of methoxyethyl acrylate or a polymer into which a carboxylic acid is introduced is used, so that a phase with the carboxylic acid-containing acrylic polymer (C) necessary for alkali developability is used. It can be seen that it has good solubility, excellent flexibility, and excellent dry film resist characteristics and solder resist characteristics.

Claims (26)

A vinyl polymer (A) having at least one crosslinkable functional group at the molecular end, and
A curable composition for a resist, comprising a compound (B) capable of crosslinking the vinyl polymer (A). Furthermore, the curable composition for resists of Claim 1 containing the prepolymer and / or polymer (C) which have an acidic functional group.   The curable composition for resists according to claim 2, wherein the ratio of the vinyl polymer (A) in the curable composition is 1 to 80% by weight. The crosslinkable functional group in the vinyl polymer (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The curable composition for resists as described in any one of 1-3 which are these. Compound (B) is an initiator, The curable composition for resists as described in any one of Claims 1-4. The curable composition for resists according to any one of claims 1 to 5, wherein the compound (B) is at least one selected from the group consisting of a photo radical initiator, a thermal radical initiator, and a redox initiator. .   The curable composition for resists according to any one of claims 1 to 6, wherein the molecular weight distribution of the vinyl polymer (A) is less than 1.8.   The main chain of the vinyl polymer (A) is mainly a monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. The curable composition for resists according to any one of claims 1 to 7, wherein the curable composition for a resist is produced.   The curable composition for resists according to claim 1, wherein the main chain of the vinyl polymer (A) has a structure derived from a monomer containing a polar group.   The curable composition for a resist according to claim 9, wherein the monomer having a polar group has a carboxyl group or an alkyl ether group.   The curable composition for resists according to claim 10, wherein the monomer having a polar group is (meth) acrylic acid alkyl ether ester or (meth) acrylic acid.   The ratio of the monomer which has a polar group is 1-100 mol% with respect to the whole monomer which comprises the principal chain of a vinyl polymer (A), The curable composition as described in any one of Claims 9-11 object.   The main chain of the vinyl polymer (A) has a carboxyl group, and the carboxyl group is generated by deprotecting the functional group of the monomer constituting the main chain with acid and / or heat. The curable composition for resists as described in any one of Claims 1-8 which is a thing.   The curable composition for resists according to claim 13, wherein the monomer having a functional group that is deprotected by acid and / or heat to generate a carboxyl group is tertiary butyl (meth) acrylate or isobornyl acrylate.   The ratio of the monomer having a functional group that is deprotected by the acid and / or heat to generate a carboxyl group is 0.5 to 50 mol% with respect to the whole monomer constituting the main chain of the vinyl polymer (A). The curable composition for resists of Claim 13 or 14.   The curable composition for resists according to any one of claims 1 to 15, wherein the main chain of the vinyl polymer (A) is a (meth) acrylic polymer.   The curable composition for resists as described in any one of Claims 1-16 whose main chain of a vinyl polymer (A) is an acrylic polymer.   The curable composition for a resist according to claim 17, wherein the main chain of the vinyl polymer (A) is an acrylate ester polymer.   The curable composition for resists according to any one of claims 1 to 18, wherein the main chain of the vinyl polymer (A) is produced by a living radical polymerization method.   The curable composition for a resist of a curable composition according to claim 19, wherein the main chain of the vinyl polymer (A) is produced by an atom transfer radical polymerization method. Furthermore, the curable composition for resists as described in any one of Claims 1-20 containing the monomer and / or oligomer which have radically polymerizable group. Furthermore, the composition for resists as described in any one of Claims 1-20 containing the monomer and / or oligomer which have an anion polymerizable group. Furthermore, the curable composition for resists as described in any one of Claims 1-22 containing the monomer and / or oligomer which have a (meth) acryloyl type group. The curable composition for resists according to claim 22, wherein the number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is 5000 or less. The resist curable composition according to any one of claims 1 to 24, wherein the resist application is a permanent resist, a liquid solder resist, a dry film resist, or an electrodeposition resist.   Hardened | cured material obtained by hardening the curable composition for resists as described in any one of Claims 1-25.