JP2007077182A - Active energy ray curable composition and cured product obtained by curing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active ray curable composition excellent in curability which can provide membranes excellent in heat resistance, weatherability, oil resistance, curability, compression set and the like for the above each application. <P>SOLUTION: This curable composition comprises (A) a vinyl polymer having at least two (meth)acryloyl groups in the molecule and at the molecular terminal, (B) a vinyl monomer having a ring structure, and (C) an initiator as essential components, and the compound has a low viscosity and can improve the elongation of a cured product. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an active energy curable composition and a cured product produced using the composition. More specifically, the present invention relates to a composition comprising a vinyl polymer having a (meth) acryloyl group at the molecular terminal as an essential component, and a cured product produced using the composition.

  Acrylic resins are used in a wide range of applications such as building seals, functional parts around automobile engines, security parts, adhesives, adhesives, etc. due to their heat resistance and oil resistance characteristics.

  However, taking acrylic rubber as an example, it can be obtained by kneading a compounding agent such as a filler and a vulcanizing agent in unvulcanized rubber and then vulcanizing it. It is hard to be smooth when adhering, sheeting, or non-flowable during molding, slow vulcanization speed, or long curing time required. There is a problem. There are also problems such as the reliability of the seal and the necessity of precision machining of the flange surface.

  Although the thing which improved workability and curability is reported (patent document 1), photocuring in which quick hardening is possible is possible and productivity cannot be improved.

  In addition, as a sealing material, a silicone material or a urethane (meth) acrylate resin as a main component is used. When a silicone material is used, SJ grade engine oil, which is a recent high-performance engine oil, Incorporates basic zinc carbonate that is highly damaged when using part of transmission oil and gear oil for automatic vehicles, and the content of iminoxysilane and zinc hydroxide is 5 to 50% by weight (hereinafter referred to as%) The conventional technology such as the method (Patent Document 2) cannot solve the problem.

  On the other hand, when the main component is a urethane (meth) acrylate resin, some have excellent oil resistance (Patent Document 3), but since the main chain has an ether bond or an ester bond, it has long-term heat resistance. There is a problem.

The present inventors have so far reported on a polymer having a main chain as an acrylic polymer obtained by living radical polymerization and having a (meth) acryloyl group at its terminal (Patent Documents 4 and 5). In parts where oil resistance and oil resistance are required, the mechanical properties (especially elongation) of the cured products obtained from the above polymers are insufficient, and depending on the application, the elongation decreases during long-term use and the sealing properties and adhesion over time There was concern about the decline in sex.
JP 2000-154370 A Japanese Patent Laid-Open No. 3-203960 JP-A 64-112 JP 2000-72816 A JP 2000-95826 A

  The present invention is a sealing material excellent in heat resistance, weather resistance, oil resistance, compression set, mechanical properties, etc., electrical / electronic component materials, electrical insulation materials, adhesives, adhesives, potting agents, heat dissipation materials, waterproofing materials To provide an active energy curable composition having excellent curability for use in vibration-proof / vibration / vibration-isolating materials, films, marine deck coking, casting materials, various molding materials, and various materials using the cured products. With the goal.

The present invention relates to an active energy curable composition having the following constitution and the above-mentioned various materials for use produced using the composition.
(1) The following three components;
(A) 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)
And two or more groups represented by the general formula (1)
A curable composition comprising, as an essential component, a vinyl-based polymer (B) having a cyclic structure and a vinyl-based monomer (C) having at least one group represented by the following formula:
(2)
The curable composition according to (1), further comprising (D) a vinyl polymer having one group per molecule represented by the general formula (1) at the molecular end.
(3)
The curable composition according to (1) or (2), wherein the vinyl polymer as the component (A) and / or (D) is a (meth) acrylic polymer.
(4)
The curable composition according to any one of (1) to (3), wherein the main chain of the component (A) and / or the component (D) is produced by living radical polymerization of a vinyl monomer.
(5)
The curable composition according to (4), wherein the living radical polymerization is atom transfer radical polymerization.
(6)
The curable composition according to any one of (1) to (3), wherein the main chain of the component (A) and / or the component (D) is produced by polymerization of a vinyl monomer using a chain transfer agent.
(7)
The curable composition according to any one of (1) to (6), wherein the vinyl polymer as the component (A) and / or (D) has a number average molecular weight of 3000 or more.
(8)
The vinyl polymer as the component (A) and / or (D) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of less than 1.8 (1) to (7 ) The curable composition in any one of.
(9)
(E) The curable composition according to any one of (1) to (8), which contains a monomer and / or an oligomer (excluding the component (B)) having a radical polymerizable group.
(10)
(E) The curable composition according to any one of (1) to 8 containing a monomer and / or an oligomer (excluding the component (B)) having an anionically polymerizable group.
(11)
The curable composition according to any one of (9) to (10), wherein the component (E) is a monomer and / or oligomer having a (meth) acryloyl group.
(12)
The curable composition according to (11), wherein the monomer and / or oligomer having the (meth) acryloyl group has a number average molecular weight of 5000 or less.
(13)
The curable composition according to any one of (1) to (12), wherein the cyclic structure of the component (B) is an aromatic ring and / or an alicyclic structure.
(14)
The curable composition according to (13), wherein the cyclic structure of the component (B) is at least one selected from the group consisting of a benzene ring, a cyclohexyl ring and an isoboronyl ring.
(15)
(B) Component is a (meth) acrylic-acid type monomer and / or a styrene-type monomer, The curable composition in any one of (13), (14) characterized by the above-mentioned.
(16)
(C) The curable composition in any one of (1)-(15) whose component is a radical initiator.
(17)
(C) The curable composition in any one of (1)-(15) whose component is an anionic initiator.
(18)
(C) The curable composition in any one of (1)-(15) whose component is a redox-type initiator.
(19)
A cured product obtained by curing the curable composition according to any one of (1) to (18).
(20)
Hardened | cured material obtained by irradiating an active energy ray to the curable composition of (1)-(17).
(21)
Hardened | cured material obtained by heat-hardening the curable composition of (1)-(17).
(22)
Hardened | cured material obtained by hardening the curable composition of (17)-(18) by normal temperature 2 liquid system.
(23)
Sealing materials, electrical / electronic component materials, electrical insulation materials, adhesives, adhesives, potting agents, heat dissipation materials, waterproofing materials, anti-vibration / vibration / vibration isolation materials, films, marine deck caulking, casting materials, or molding The curable composition in any one of (1)-(18) used for material.

  By using the active energy curable composition of the present invention, it is possible to provide a curable composition for various applications that is excellent in curability and excellent in heat resistance, weather resistance, oil resistance, compression set, and the like. it can.

The active energy curable composition of the present invention is described below.
<(A) component>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra represents ^a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a vinyl polymer having 2 or more groups per molecule ((meth) acryloyl group) per molecule.

  The number of (meth) acryloyl groups in the component (A) is 2 or more per molecule from the viewpoint of crosslinking.

  The (meth) acryloyl group is present at the molecular terminal of the vinyl polymer from the viewpoint of obtaining rubber elasticity by making the molecular weight between cross-linking points uniform and large, preferably 500 to 100,000.

^Ra in the (meth) acryloyl group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a nitrile group, and the like. And the like.

  Examples of the alkyl group having 1 to 20 carbon atoms include aryl groups having 6 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. Examples of the aralkyl group having 7 to 20 carbon atoms such as phenyl group and naphthyl group include benzyl group and phenylethyl group.

Specific examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , —CH ₂ OH, —CN and the like are mentioned, and preferably —H, —CH ₃ .

  (A) There is no limitation in particular in the vinyl-type monomer which comprises the principal chain of a component, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluoroethylethyl, 2- (perfluoroethyl) 2- (perfluoroethyl) (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, di (meth) acrylate Perfluoromethyl methyl, 2-meth (meth) acrylic acid Such as fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, ) Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and di Kill esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; containing nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or in combination. Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and more preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Furthermore, from the viewpoint of oil resistance of the obtained cured product, it is particularly preferable that the vinyl monomer constituting the main chain contains at least two selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate.

  In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more.

  The molecular weight distribution of component (A) (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)) is not particularly limited, but is preferably less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.

  In the GPC measurement in the present invention, a polystyrene gel column is usually used with chloroform or tetrahydrofuran as a mobile phase, and the molecular weight value is obtained in terms of polystyrene.

The lower limit of the number average molecular weight of the component (A) is preferably 500, more preferably 3000, and the upper limit is preferably 100,000, more preferably 40000. When the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and when it exceeds 100,000, handling tends to be difficult.
<(D) component>
The component (D) is a vinyl polymer having one group per molecule ((meth) acryloyl group) represented by the general formula (1) and one (meth) acryloyl group. It is preferable that the group is present at the molecular end from the viewpoint of rubber elasticity after curing.

  (D) There is no limitation in particular in the vinyl-type monomer which comprises the principal chain of a component, A various thing can be used. As a specific example, the same vinyl monomer that constitutes the main chain of the component (A) can be used, and the vinyl monomer that constitutes the main chain of the component (A) can also be used and preferred vinyl monomers and the like. The same.

  The molecular weight distribution of component (D) (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)) is not particularly limited, but is preferably less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.

  The lower limit of the number average molecular weight of component (D) is preferably 500, more preferably 2000, and the upper limit is preferably 100,000, more preferably 40000. When the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and when it exceeds 100,000, handling tends to be difficult.

  In addition, since (D) component has the objective of reducing the viscosity of a composition, it is preferable that the viscosity in 23 degreeC is 100 Pa.s or less.

Although there is no limitation in particular in the usage-amount of (D) component, it is preferable that it is 5-200 parts with respect to 100 parts of (A) component (a weight part, the following similarly), and it is further more preferable that it is 10-100 parts. . When the amount is less than 5 parts, the effect of reducing the viscosity of the composition is small, and when it exceeds 200 parts, the curability tends to be low.
<(A) component, manufacturing method of (D) component>
There is no limitation in particular about the manufacturing method of (A) component and (D) component.

  The vinyl polymer is generally produced by anionic polymerization or radical polymerization, and radical polymerization is preferred because of the versatility of the monomer or ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, and the former is particularly preferable.

  The radical polymerization method used for the production of the component (A) and the component (D) uses an azo compound, a peroxide or the like as a polymerization initiator, and simply combines a monomer having a specific functional group and a vinyl monomer. It can be classified into “general radical polymerization method” for polymerization and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

  The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount, and conversely, in the case of using 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 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.

  Therefore, 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 production method of 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. Pseudo-living polymerization in which is grown while in equilibrium. 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 Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, macromolecules. “Atom transfer radical polymerization” using radical scavengers such as nitroxide compounds as shown in Macromolecules, 1994, 27, 7228, organic halides as initiators and transition metal complexes as catalysts. (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 “living radical polymerization method” described above. In addition to the characteristics of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the terminal, and has a large degree of freedom in designing initiators and catalysts, so it can produce vinyl polymers with specific functional groups. The method is more preferable.

  Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules. 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421 pamphlet, WO97 / 18247 pamphlet or Sawamoto et al., Macromolecules 1995, 28, And the method described on page 1721.

  In the present invention, there is no particular restriction as to which of these methods is used, but basically, a controlled radical polymerization method is used, and a living radical polymerization method is preferred from the standpoint of ease of control. The transfer radical polymerization method is preferred.

  First, one of the controlled radical polymerization methods, a polymerization method using a chain transfer agent will be described.

  The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.

  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 of 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.

  Next, the living radical polymerization method will be described.

  First, a method using a radical scavenger (capping agent) such as a nitroxide compound will be described.

  In this polymerization method, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such compounds are not particularly limited, but are cyclic such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from 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 examples of the nitroxy free radical compound include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl- 1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, Examples thereof include 1,1,3,3-tetramethyl-2-isoindolinyloxy radical and N, N-di-t-butylamineoxy radical.

  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.

  Although there is no limitation in the usage ratio of both, 0.1-10 mol of radical initiators are suitable with respect to 1 mol of radical capping agents.

  As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under the polymerization temperature condition is preferable.

  The peroxide is not particularly limited, but diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, Examples thereof include peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctoate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable.

  Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

  As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, the following alkoxyamine compound may be used as an initiator. I do not care.

アルコキシアミン化合物を開始剤として用いる場合、それが前記のような水酸基など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, a polymer having a functional group at the terminal can be obtained by using an alkoxyamine compound having a functional group such as a hydroxyl group as described above. When this is used in the present invention, a polymer having a functional group at the terminal can be obtained.

  There are no particular limitations on the polymerization conditions such as the monomer, solvent and polymerization temperature used in the polymerization using a radical scavenger such as the nitroxide compound, but it may be the same as that used for the atom transfer radical polymerization described below.

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

  In this atom transfer radical polymerization method, 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 halogen Sulfonyl compounds and the like are used as initiators.

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
(Wherein C ₆ H ₅ is a phenyl group, X is a chlorine atom, a bromine atom or an iodine atom)
^{R 3 -C (H) (X} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 R ³ —C (CH ₃ ) (X) —C (O) R ⁴ ,
Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom )
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom)
Etc.

  As an initiator of the atom transfer radical polymerization method, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (1) at the end of one main chain and the functional group at the other main chain end is produced.

  Examples of the functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having the alkenyl group is not particularly limited. For example, the general formula (6):
R ⁶ R ⁷ C (X) —R ⁸ —R ⁹ —C (R ⁵ ) ═CH ₂ (6)
(Wherein R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or the like. Connected to each other at the ends, R ⁸ is —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group, R ⁹ is directly A divalent organic group having 1 to 20 carbon atoms which may contain a bond or one or more ether bonds, X is a chlorine atom, a bromine atom or an iodine atom)
What is shown by is illustrated.

Specific examples of the substituents R ⁶ and R ⁷ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

Examples of the divalent organic group having 1 to 20 carbon atoms that may contain one or more ether bonds of R ⁹ include, for example, 1 to 20 carbon atoms that may contain one or more ether bonds. Examples thereof include an alkylene group.

Specific examples of the organic halide having an alkenyl group represented by the general formula (6) 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

（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、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）_mＣＨ＝ＣＨ₂

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

（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、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
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、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
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、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
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、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
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、ｎは１〜２０の整数、ｍは０〜２０の整数）
前記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（７）：
Ｈ₂Ｃ＝Ｃ（Ｒ⁵）−Ｒ⁹−Ｃ（Ｒ⁶）（Ｘ）−Ｒ¹⁰−Ｒ⁷ （７）
（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁹、Ｘは前記に同じ、Ｒ¹⁰は、直接結合、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）またはｏ−，ｍ−，ｐ−フェニレン基を表わす）
で示される化合物があげられる。

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, 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 formula, X is a chlorine atom, bromine atom or iodine atom, 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 the above formula, X is a chlorine atom, bromine atom or iodine atom, 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 -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 formula, X is a chlorine atom, bromine atom or iodine atom, 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 the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 20)
The organic halide having an alkenyl group is further represented by the general formula (7):
^{_{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (7)
Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group ) Or o-, m-, p-phenylene group)
The compound shown by these is mention | raise | lifted.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), but in the case of a direct bond, a halogen atom is bonded. A vinyl group is bonded to carbon, 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 ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ 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 represented by the general formula (7) 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 formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

Specific examples of the sulfonyl halide compound having the alkenyl group include
_{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 formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, the general formula (8):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (8)
(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and X are the same as described above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups, or C 1-20. (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 ¹¹ or R ¹² 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 is 0, 1, 2 or 3, b is 0, 1 or 2, m is an integer from 0 to 19, provided that a + mb ≧ 1 Satisfied to be)
The following are exemplified.

If the compound represented by the general formula (8) is specifically exemplified,
_{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 formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 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 formula, X is a chlorine atom, bromine atom or iodine atom, 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 formula, X is a chlorine atom, a bromine atom or an iodine atom)
Etc.

The organic halide having a crosslinkable silyl group is further represented by the general formula (9):
^{_{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (9)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, X and Y are the same as above, m is an integer of 0 to 19)
What is shown by is illustrated.

If the compound represented by the general formula (9) is specifically exemplified,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C (H) (X) C ₆ H ₅ ,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ C (H) (X) C ₆ H ₅ ,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said hydroxyl group, The following are illustrated.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, 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)
There is no limitation in particular in the organic halide or sulfonyl halide compound which has the said amino group, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, 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)
There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said epoxy group, The following are illustrated.

（式中、Ｘは塩素原子、臭素原子またはヨウ素原子、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）
一般式（１）で表わされる基を１分子あたり２個以上、分子末端に有するビニル系重合体を得るためには、２個以上の開始点を有する有機ハロゲン化物またはハロゲン化スルホニル化合物を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、

(Wherein X is a chlorine atom, bromine atom or iodine atom, 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 vinyl polymer having two or more groups represented by the general formula (1) per molecule at the molecular end, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator. It is preferable to use as. For example,

などがあげられる。

Etc.

  There is no restriction | limiting in particular in the vinyl-type monomer used in the said superposition | polymerization, and all already illustrated can be used suitably.

  Further, the transition metal complex used as a polymerization catalyst is not particularly limited, but preferably a metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element as a central metal, such as copper, It is a complex of nickel, ruthenium and iron. Further preferred are 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 the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. Can be given.

  In the case of using a copper compound, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. to increase the catalytic activity A ligand such as a polyamine can be added.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.

  When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator.

Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine 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. These may be used alone or in combination of two or more.

Moreover, superposition | polymerization can be performed in room temperature-200 degreeC, Preferably it is 50-150 degreeC.
<Functional group introduction method>
There are no particular limitations on the method for producing the component (A) and the component (D). For example, a vinyl polymer having a reactive functional group is produced by the method described above, and the reactive functional group is converted to a (meth) acryloyl group. It can manufacture by converting into the substituent which has.

  Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.
(Introduction Method 1) Vinyl-based polymer having a halogen group at the terminal, and general formula (2):
M ⁺ -OC (O) C (R ^a ) = CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The method by reaction with the compound shown by these.

As a vinyl polymer having a halogen group at the terminal, the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
Those having a terminal group represented by are preferred.
(Introduction method 2) A vinyl polymer having a hydroxyl group at the terminal, and the general formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The method by reaction with the compound shown by these.
(Introduction method 3) A vinyl polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and the general formula (5):
HO-R'- OC (O) C (R ^a ) = CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The method by reaction with the compound shown by these.

Below, each said method is demonstrated in detail.
[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).

  Although there is no limitation in particular in the vinyl polymer which has a halogen group at the terminal, What has a terminal group shown in General formula (3) is preferable.

  A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (3), is prepared by using the above-described organic halide or sulfonyl halide compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

  There is no limitation in particular in the compound represented by General formula (2).

Examples of the organic group having 1 to 20 carbon atoms in ^Ra in the general formula (2) are the same as those described above, and specific examples thereof are also the same as those described above.

M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples thereof include alkali metal ions and quaternary ammonium ions.

  Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, and tetrabutyl. Examples thereof include ammonium ion and dimethylpiperidinium ion. Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

  The usage-amount of the compound shown by General formula (2) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (3), More preferably, it is 1.0-1.2 equivalent.

  The solvent for carrying out the 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 trimethyl. Amides, acetonitrile and the like are preferably used.

Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.
[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).

  There is no limitation in particular in the compound represented by General formula (4).

Examples of the organic group having 1 to 20 carbon atoms in ^Ra in General Formula (4) are the same as those described above, and specific examples thereof are also the same as those described above.

  The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Although it is produced by a method of polymerizing a vinyl monomer, the former is preferred.

  The method for producing the vinyl polymer having a hydroxyl group at the terminal is not particularly limited, but examples thereof include the following methods.

(A) When synthesizing a vinyl polymer by living radical polymerization, the general formula (10):
^{_{H 2 C = C (R 13}} ) -R 14 -R 15 -OH (10)
Wherein R ¹³ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹⁴ is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹⁵ is a direct bond. Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds)
A method of reacting a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

R ¹³ is preferably a hydrogen atom or a methyl group. Further, when R ¹⁴ is an ester group, it is a (meth) acrylate compound, and when R ¹⁴ is a phenylene group, it is a styrene compound.

  There is no restriction on the timing for reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, 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 there is no limitation in particular in such a compound, For example, General formula (11):
^{_{H 2 C = C (R 13}} ) -R 16 -OH (11)
(In the formula, R ¹³ is the same as above, and R ¹⁶ represents a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds.)
And the like.

  The compound represented by the general formula (11) 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 polymer having at least one carbon-halogen bond represented by the general formula (3) 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 atom with a hydroxyl group-containing compound.

(D) To a vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization, the general formula (12):
M ⁺ C ⁻ (R ¹⁷ ) (R ¹⁸ ) —R ¹⁶ —OH (12)
(In the formula, R ¹⁶ and M ⁺ are the same as above, and R ¹⁷ and R ¹⁸ are both an electron-withdrawing group for stabilizing carbanion C ⁻ or one is the electron-withdrawing group, the other is a hydrogen atom, Represents an alkyl group or a phenyl group of
A method of replacing halogen by reacting a stabilized carbanion having a hydroxyl group represented by

As the electron-withdrawing group, -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) and the like, —CO ₂ R, —C (O) R, —CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

  (E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization is allowed to react with a metal alone or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl polymer having at least one halogen atom represented by the general formula (3), preferably a halogen atom at the end of the polymer, represented by the general formula (13):
HO-R ¹⁶ -O ^- M ⁺ (13)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A hydroxyl group-containing compound represented by
General formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A method in which the halogen atom is substituted with a hydroxyl group-containing substituent by reacting the hydroxyl group-containing compound represented by formula (1).

  In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.

  In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

  The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.

  The solvent for carrying out the 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 trimethyl. Amides, acetonitrile and the like are preferably used.

Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.
[Introduction method 3]
In the introduction method 3, a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
It is the method by reaction with the compound shown by.

Examples of the organic group having 1 to 20 carbon atoms in ^Ra in General Formula (5) are the same as those described above, and specific examples thereof are also the same as those described above.

  Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And alkylene groups having 7 to 20 carbon atoms.

  Although there is no limitation in particular in the compound shown by General formula (5), As a particularly preferable compound, 2-hydroxypropyl methacrylate etc. are mention | raise | lifted.

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

  There is no particular limitation on the diisocyanate compound, and any conventionally known one can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Examples thereof include xylylene diisocyanate and isophorone diisocyanate. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining superior weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

  The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the terminal hydroxyl group of the vinyl polymer.

  The reaction solvent is not particularly limited, but an aprotic solvent is preferred.

  Although there is no limitation in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.
<(B) component>
The component (B) is a vinyl monomer having a cyclic structure. The component (B) is not particularly limited as long as it is a vinyl monomer having a cyclic structure, and specific examples include aromatic rings such as benzene ring, naphthalene ring, pyrene ring, cyclopentadiene ring, N atom. A pyridine ring, an imidazole ring, a triazine ring, a thiazole ring having an S atom, an oxirane ring having an oxygen atom, a furan ring, an oxazoline ring having an oxygen-nitrogen atom, a cyclopentyl ring hydrogenated with an unsaturated bond, a cyclohexyl ring, There are heterocyclic structures in which different ring structures are combined, spiro ring structures, cube structures, etc., but the present invention is not limited to these. In the present invention, among these, an aromatic ring and an alicyclic structure are preferable, and among them, a benzene ring, a cyclohexyl ring, and an isobornyl ring are particularly preferable. The component (B) vinyl monomer can contain a plurality of cyclic structures, and the above-mentioned cyclic structures may have one kind or two or more kinds.
As the vinyl monomer having a cyclic structure as the component (B), a monomer having a radical polymerizable or anion polymerizable group is preferable in view of reactivity.

  Examples of radical polymerizable groups include (meth) acryloyl groups such as (meth) acryl groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, And vinyl chloride group. Especially, what has the (meth) acryloyl group similar to the polymer used for this invention is preferable.

  Examples of the anionic polymerizable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, and vinyl ketone groups. Especially, what has the (meth) acryloyl type group similar to the polymer used for this invention is preferable.

  Specific examples of vinyl monomers having a cyclic structure as component (B) include (meth) acrylate monomers, cyclic acrylates, N-vinyl pyrrolidone, styrene monomers, acrylonitrile monomers, N-vinyl pyrrolidone, acrylamide monomers. Conjugated diene monomers, vinyl ketone monomers and the like.

  Specific examples of the component (B) include the following.

  Examples of the styrenic monomer include styrene and α-methylstyrene. Examples of acrylamide monomers include acrylamide and N, N-dimethylacrylamide. Examples of the conjugated diene monomer include butadiene and isoprene. Examples of the vinyl ketone monomer include methyl vinyl ketone.

(Meth) acrylate monomers include cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid Tetrafurfuryl, glycidyl (meth) acrylate, isobornyl (meth) acrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecanedi Methylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4 And 4 dimercapto diphenyl monkey phi mistakes methacrylate.
Specific examples of the other component (B) include compounds represented by the following formulas. In the following formula, n represents an integer of 0-20.

硬化物の伸び向上の点から、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボロニルが好ましく、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボロニルが特に好ましい。

From the point of improving the elongation of the cured product, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid Isobornyl is preferred, and benzyl (meth) acrylate and isobornyl (meth) acrylate are particularly preferred.

  The vinyl monomer having the cyclic structure of the component (B) may be used alone or in combination of two or more.

(B) As addition amount of the vinyl-type monomer which has the cyclic structure of component, 1-300 parts are preferable with respect to a total of 100 parts of (A) component or (A) component + (D) component, 200 parts are more preferred, and 3 to 100 parts are even more preferred.
<(C) component>
Although there is no restriction | limiting in particular in the initiator of (C) component, a photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is especially preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4 -Methoxyacetophene, 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, benzoyl, benzoin methyl ether, benzoin Tyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxyketal, 2-chlorothioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Examples include 2,4,4-trimethylpentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue, etc. can give.

The content of the component (C) is only required to be slightly functionalized, and is not particularly limited, but is 0.001 to 10 parts with respect to a total of 100 parts of the component (A) + component (D). Is preferred.
<(E) component>
As the curable composition of the present invention, in addition to the component (B), as the component (E), a polymerizable monomer / or oligomer, that is, a monomer and / or oligomer having a radical polymerizable group, or From the viewpoint of reactivity, it is preferable to use a monomer and / or an oligomer having an anion polymerizable group.

  Examples of radical polymerizable groups include (meth) acryloyl groups such as (meth) acryl groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, and vinyl chloride. Group. Especially, what has the (meth) acryl group similar to the polymer used for this invention is preferable.

  Examples of the anionic polymerizable group include (meth) acryloyl group such as (meth) acryl group, styrene group, acrylonitrile group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group and the like. Especially, what has the (meth) acryloyl type group similar to the polymer used for this invention is preferable.

  Specific examples of the component (B) monomer include (meth) acrylate monomers, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, and polyfunctional monomers.

  (Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth ) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , 2-methoxyethyl (meth) acrylate, 3-methoxybutyrate (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, ( Ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2- (meth) acrylic acid 2- Perfluoromethyl-2-perfluoroethylethyl, (me T) 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, and the like. Moreover, the compound etc. which are shown by the following Formula can also be mention | raise | lifted. In the following formula, n represents an integer of 0-20.

（Ｅ）成分のモノマーとしては、多官能モノマーも使用することができ、トリメチロールプロパントリアクリレート、ネオペンチルグリコールポリプロポキシジアクリレート、トリメチロールプロパンポリエトキシトリアクリレート、ジペンタエリスリトールポリヘキサノリドヘキサクリレート、ポリテトラエチレングリコールジアクリレート、１，９−ノナンジオールジアクリレート、ジトリメチロールプロパンテトラアクリレートなどがあげられる。

(E) As a monomer of a component, a polyfunctional monomer can also be used, such as trimethylol propane triacrylate, neopentyl glycol polypropoxy diacrylate, trimethylol propane polyethoxy triacrylate, dipentaerythritol polyhexanolide hexacry. Rate, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and the like.

  (E) Component oligomers include bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, cresol novolac type epoxy acrylate resins, and other epoxy acrylate resins, COOH group-modified epoxy acrylate resins, polyols (polytetramethylene glycol) Polyester diol of ethylene glycol and adipic acid, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate) , Isophorone diisocyanate, diphenylmethane diisocyanate, hexa Urethane resin obtained from tylene diisocyanate, xylylene diisocyanate, etc.) is hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} And urethane acrylate resins obtained by reacting with the above, resins obtained by introducing (meth) acrylic groups into the polyols via ester bonds, polyester acrylate resins, and the like.

  The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is preferably 5000 or less. Further, in the case of using a monomer for improving the surface curability and reducing the viscosity for improving workability, it is more preferable that the molecular weight is 1000 or less because of good compatibility.

It is preferable that content of (E) component is 1-200 parts with respect to a total of 100 parts of (A) component + (D) component, Furthermore, 5-100 parts.
<Active energy curable composition>
The active energy curable composition of the present invention contains the components (A), (B), and (C) as essential components, and in particular, by blending the component (B), the mechanical properties of the cured product (particularly, Elongation) can be improved, and the durability of the cured product in applications requiring heat resistance and oil resistance can be improved.

  Furthermore, addition of reinforcing silica is useful for the active energy curable composition of the present invention from the viewpoint of improving the strength of the cured product.

Examples of the reinforcing silica include fumed silica and precipitated silica. Among these, those having a particle diameter of 50 μm or less and a specific surface area of 80 m ² / g or more are preferable from the viewpoint of reinforcing effect.

  Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it is easy to exhibit fluidity suitable for molding.

  More specific examples of the reinforcing silica system are not particularly limited. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Industry Co., Ltd., which is one of precipitated silicas. Nipsil and the like.

  The reinforcing silica may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the addition amount of a reinforcing silica, 0.1-100 parts with respect to a total of 100 parts of said (A) component and (D) component, Preferably 0.5-80 parts, Especially 1 It is preferable to use ~ 50 parts. When the amount is less than 0.1 part, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts, the workability of the composition may be deteriorated.

  In addition to the reinforcing silica, various fillers may be used in the composition of the present invention as necessary.

  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, dolomite, silicic acid anhydride, Hydrous silicic acid), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide , Filler, aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate and shirasu balloon, etc .; asbestos, glass fiber and glass filament, carbon fiber, kevlar fiber, polyethylene fiber, etc. Examples of such fibrous fillers. Of these fillers, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. 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, etc. may be added. it can.

  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. Moreover, 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.

  Examples of the surface treatment agent include 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. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. And sodium salts and potassium salts of these fatty acids and alkyl esters of these fatty acids. Specific examples of surfactants include sulfuric acid ester type anionic surfactants such as sodium salts and potassium salts such as polyoxyethylene alkyl ether sulfates and long chain alcohol sulfates, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, paraffins. Examples thereof include sulfonic acid type anionic surfactants such as sodium salts and potassium salts such as sulfonic acid, α-olefin sulfonic acid and alkylsulfosuccinic acid.

  The treatment amount of the surface treatment agent is preferably treated in the range of 0.1 to 20%, more preferably in the range of 1 to 5% with respect to calcium carbonate. When the treatment amount is less than 0.1%, the workability, adhesiveness and weatherability may not be improved sufficiently, and when it exceeds 20%, the storage stability of the composition may be lowered. is there.

  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 adhesion 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 pulverizing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for pulverization methods, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the composition of the present invention. Heavy calcium carbonate becomes products having various average particle sizes by classification. There is no particular limitation, but when the effect of improving the breaking strength, breaking elongation, 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 preferable. 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 reduced or when the purpose is only to increase the viscosity.

  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 heavy calcium carbonate and colloidal calcium carbonate having a specific surface area of 1.5 m ² / g or more are combined as necessary, the increase in viscosity of the compound is moderately suppressed, and a cured product is obtained. The effect of improving the breaking strength, breaking elongation, adhesiveness and weathering adhesion can be greatly expected.

  When the filler is used, the addition amount is preferably in the range of 5 to 1000 parts, preferably in the range of 20 to 500 parts with respect to 100 parts in total of the components (A) and (D). It is more preferable to use it, and it is particularly preferable to use it in the range of 40 to 300 parts. If the blending amount is less than 5 parts, the effect of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts, the workability of the composition is lowered. Sometimes. A filler may be used independently and may be used together 2 or more types.

  The active energy curable composition of the present invention is preferably composed mainly of a (meth) acrylic polymer, so that it is not always necessary to add an adhesion-imparting resin. Can be used. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.

  In the active energy curable composition of the present invention, various additives such as an anti-aging material, a plasticizer, a physical property modifier, a solvent and the like may be blended in order to adjust physical properties.

  The acrylic polymer is originally a polymer excellent in heat resistance, weather resistance, and durability, and therefore, an anti-aging agent is not necessarily required, but conventionally known antioxidants and light stabilizers can be appropriately used. . The anti-aging agent can also be used for polymerization control during polymerization, and can control physical properties. 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) published by CM Chemical Co., Ltd. Although various things are mention | raise | lifted, it is not necessarily limited to these. For example, thioethers such as MARK PEP-36 and MARK AO-23 (all manufactured by Adeka Gas Chemical Co., Ltd.), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Ciba Geigy Japan) And phosphorus-based antioxidants. 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-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1, 3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-tert-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-trime Til-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxypheny L) Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 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-pen) Methyl-4-piperidyl), e.g., 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 Also manufactured by Ouchi Shinsei Chemical Co., Ltd.), 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 Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX- 10 4, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of these are manufactured by Ciba Geigy Japan), Sumitizer GA-80 (all of which are Sumitomo Chemical) However, it is not limited to these. Furthermore, monoacrylate phenolic antioxidants having both acrylate groups and phenol groups, nitroxide compounds and the like can be mentioned. Examples of the monoacrylate phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilizer GM), 2, Examples include 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name: Sumilizer GS). Nitroxide compounds include, but are not limited to, cyclic hydroxyamines such as 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals. The nitroxy free radicals from are illustrated. 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. Antioxidants may be used in combination with light stabilizers, and are particularly preferred because they can further exert their effects and in particular improve the heat resistance. Tinuvin C353, tinuvin B75 (all of which are manufactured by Nippon Ciba Geigy Co., Ltd.) or the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

  As plasticizers, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; non-dioctyl adipate, dioctyl sebacate, etc. Aromatic dibasic acid esters; Polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Chlorinated paraffins; Alkyl diphenyl and partially hydrogenated Hydrocarbon oils such as terphenyl can be used alone or in admixture of two or more, but this is not always necessary. These plasticizers can also be blended at the time of polymer production.

  Solvents that may be used in the production of the polymer include, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl. Examples thereof include ketone solvents such as ketones.

  Moreover, you may add various adhesive improvement agents to the active energy curable composition of this invention in order to improve the adhesiveness with respect to various support bodies (plastic film etc.). Illustrative examples include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxy Alkylisopropenoxysilane such as propylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltri Methoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane γ-mercaptopropyltrimethoxysila , Alkoxysilanes having a functional group such as γ- mercaptopropyl methyldimethoxysilane; silicone varnishes; polysiloxanes and the like.

  An organic solvent can be added to the curable composition of the present invention for the purpose of reducing the viscosity of the formulation and improving workability.

As the organic solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane. These solvents may be used alone or in combination of two or more.
<Curing method>
The active energy curable composition of the present invention is cured by an active energy ray such as UV or electron beam or an active energy such as heat. In order to obtain good curability and compression set, curing with an active energy ray such as UV or electron beam is particularly preferable.
<Active energy ray curing>
In the case of curing by active energy rays, it is preferable to contain the photopolymerization initiator of the component (C) as an initiator.

  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, near-infrared light which is excited by light energy in the region of 650 to 1500 nm, for example, disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer in combination.

  The addition amount of the photopolymerization initiator is not particularly limited since it is only necessary to slightly functionalize the system, but 0.001 to 10 parts with respect to 100 parts in total of the components (A) and (D). Is preferred.

There is no particular limitation on the source of active energy rays, but depending on the nature of the photopolymerization initiator, for example, high-pressure mercury lamp, low-pressure mercury lamp, electron beam irradiation device, halogen lamp, light-emitting diode, semiconductor laser, etc. Irradiation.
<Active energy curable composition>
The cured product obtained by curing the curable composition of the present invention on site with active energy ensures the durability during use of each application, so that the elongation in the tensile test specified in JIS K 6251 is 100%. It is preferable that In order to sufficiently satisfy the required heat resistance and sealing properties, the cured product was subjected to compression set as defined in JIS K 6262 (measured after compression for 25 hours at 150 ° C. for 70 hours and 25% compression). It is preferable that the ratio that is not present is expressed as a compression amount of 100%) is 30% or less. The cured product is suitably used as a seal for parts that require oil resistance or oil resistance and heat resistance, a seal around an automobile engine, a seal on an oil pan joint surface of an automobile, and the like.
<Application>
The curable composition of the present invention includes an elastic sealant for buildings, a sealant for siding boards, a sealant for multi-layer glass, a sealant for vehicles, such as an architectural and industrial sealant, and a solar cell back surface sealant. Electrical and electronic parts materials, electrical insulation materials such as insulation coatings for electric wires and cables, adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, paints, powder paints , Coating materials, foams, sealing materials such as can lids, heat dissipation sheets, potting agents for electrical and electronic use, films, marine deck caulking, casting materials, various molding materials, artificial marble, and meshed glass and laminated glass end faces ( Anti-rust / water-proof sealing material for cutting parts), vibration-proof / vibration-proof / sound-proof / isolation materials used in automobiles, ships, home appliances, etc., automotive parts, electrical parts, various machines Liquid sealing agent used in such goods, are available in a variety of applications such as waterproofing agents.

  Furthermore, the molded object which shows the rubber elasticity obtained from the curable composition of this invention can be widely used centering on a sealing material. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, and an anti-vibration material for vehicle body parts. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker seals, speaker edges, turntable systems for audio equipment such as diaphragm valves and air pipes Door, belts, pulleys, and the like. In the construction field, it can be used for structural sealing materials, air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

  Among them, the curable composition of the present invention is useful as an adhesive / adhesive composition, particularly useful as a sealant, an adhesive, a pressure-sensitive adhesive, a potting agent, and a coating agent, and particularly requires weather resistance and heat resistance. It is also useful for applications where transparency is required. Moreover, since the curable composition of this invention is excellent in a weather resistance and adhesiveness, it can be used for the construction method of an outer wall tile adhesion | attachment without joint filling. Furthermore, it can be used for adhesion of materials with different linear expansion coefficients, application of elastic adhesives for adhesion of members that are repeatedly displaced by heat cycle, and coating agents for applications where the base can be seen by taking advantage of transparency. It is also useful for applications such as adhesives used for bonding transparent materials such as glass, polycarbonate and methacrylic resin.

  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, the number average molecular weight and the 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). A GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

In the following examples, the average number of terminal (meth) acryloyl groups is the number of (meth) acryloyl groups introduced per molecule of polymer, and is calculated based on the number average molecular weight determined by ¹ H NMR analysis and GPC. did.
Production Example 1 (acryloyl group both terminal poly (synthesis of acrylic acid n-butyl acrylate))
Using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, and diethyl-2,5-dibromoadipate as an initiator, n-butyl acrylate is polymerized, and has a number average molecular weight of 22300 and a molecular weight distribution of 1.11. Bromine-based poly (n-butyl acrylate) was obtained.

  400 g of this polymer was dissolved in N, N-dimethylacetamide (400 mL), 7.2 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. Butyl) (hereinafter referred to as polymer [1]) was obtained. After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. Toluene in the filtrate was distilled off under reduced pressure to purify the polymer [1].

The number average molecular weight of the purified acryloyl group-terminated polymer [1] is 22600, the molecular weight distribution is 1.14, and the average terminal acryloyl group number is 1.74 (that is, the introduction rate of acryloyl group at the terminal is 87%). there were.
Production Example 2 (Synthesis of n-butyl polyacrylate with one end of acryloyl group)
Polymerization of n-butyl acrylate using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, and ethyl 2-bromobutyrate as an initiator, and a one-terminal bromine group having a number average molecular weight of 11600 and a molecular weight distribution of 1.08 Poly (n-butyl acrylate) was obtained.

  510 g of this polymer was dissolved in N, N-dimethylacetamide (510 g), 8.8 g of potassium acrylate was added, the mixture was heated and stirred at 70 ° C. for 4 hours under a nitrogen atmosphere, and acryloyl group one-end poly (acrylic acid n- A mixture of butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [2]) was obtained. After N, N-dimethylacetamide in the mixed solution 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 number average molecular weight of the purified acryloyl group single terminal polymer [2] is 11700, the molecular weight distribution is 1.10, and the average terminal acryloyl group number is 1.0 (that is, the introduction rate of acryloyl group at the terminal is almost 100%). Met.
Example 1
100 parts of the polymer [1] obtained in Production Example 1 is 10 parts of isobornyl acrylate, 1.0 part of IRGACURE 184 (manufactured by Ciba Specialty Chemicals), 0.5 part of IRGACURE 819 (manufactured by Ciba Specialty Chemicals) Part and Irganox 1010 (manufactured by Ciba Specialty Chemicals) were added and mixed well to obtain a curable composition. The viscosity of this composition at room temperature (23 ° C.) was 17 Pa · s.

  Subsequently, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .

Moreover, based on JISK6251, the mechanical property after hardening curing of a hardened | cured material and the gel fraction were measured. The results are shown in Table 1.
The hardness of the obtained cured product, oil resistance (weight increment / ASTM No. 1 oil, 150 ° C. × 70 hours) was measured according to JIS K 6301, and the results are shown in Table 2.
Furthermore, the compression set (25% compression / 150 ° C. × 70 hours) after curing and curing of the cured product was measured according to JIS K 6262, and the results are shown in Table 3.
Example 2
100 parts of the polymer [1] obtained in Production Example 1 is 20 parts of isobornyl acrylate, 1.0 part of IRGACURE 184 (manufactured by Ciba Specialty Chemicals), 0.5 part of IRGACURE 819 (manufactured by Ciba Specialty Chemicals) Part and Irganox 1010 (manufactured by Ciba Specialty Chemicals) were added and mixed well to obtain a curable composition. The viscosity of this composition at room temperature (23 ° C.) was 13 Pa · s.

Next, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .
Further, the mechanical properties and gel fraction after curing curing of the cured product were measured in the same manner as in Example 1. The results are shown in Table 1.
The hardness and oil resistance (weight increment / ASTM No. 1 oil, 150 ° C. × 70 hours) of the obtained cured product were measured in the same manner as in Example 1, and the results are shown in Table 2.
Further, the compression set (25% compression / 150 ° C. × 70 hours) after curing and curing of the cured product was measured in the same manner as in Example 1, and the results are shown in Table 3.
Example 3
100 parts of the polymer [1] obtained in Production Example 1 30 parts of isobornyl acrylate, 1.0 part of IRGACURE 184 (manufactured by Ciba Specialty Chemicals), 0.5 part of IRGACURE 819 (manufactured by Ciba Specialty Chemicals) Part and Irganox 1010 (manufactured by Ciba Specialty Chemicals) were added and mixed well to obtain a curable composition. The viscosity of this composition at room temperature (23 ° C.) was 6 Pa · s.

  Subsequently, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .

Further, the mechanical properties and gel fraction after curing curing of the cured product were measured in the same manner as in Example 1. The results are shown in Table 1.
The hardness and oil resistance (weight increment / ASTM No. 1 oil, 150 ° C. × 70 hours) of the obtained cured product were measured in the same manner as in Example 1, and the results are shown in Table 2.
Further, the compression set (25% compression / 150 ° C. × 70 hours) after curing and curing of the cured product was measured in the same manner as in Example 1, and the results are shown in Table 3.
Example 4
100 parts of the polymer [1] obtained in Production Example 1 20 parts of benzyl acrylate, 1.0 part of IRGACURE 184 (manufactured by Ciba Specialty Chemicals), 0.5 part of IRGACURE 819 (manufactured by Ciba Specialty Chemicals), 1 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added and mixed well to obtain a curable composition. The viscosity of this composition at room temperature (23 ° C.) was 7 Pa · s.

  Subsequently, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .

Further, the mechanical properties and gel fraction after curing curing of the cured product were measured in the same manner as in Example 1. The results are shown in Table 1.
The hardness and oil resistance (weight increment / ASTM No. 1 oil, 150 ° C. × 70 hours) of the obtained cured product were measured in the same manner as in Example 1, and the results are shown in Table 2.
Further, the compression set (25% compression / 150 ° C. × 70 hours) after curing and curing of the cured product was measured in the same manner as in Example 1, and the results are shown in Table 3.
Example 5
100 parts of the polymer [1] obtained in Production Example 1, 10 parts of the polymer [2] obtained in Production Example 2, 10 parts of isobornyl acrylate, IRGACURE 184 (manufactured by Ciba Specialty Chemicals) 1.1 Part, IRGACURE819 (manufactured by Ciba Specialty Chemicals) 0.55 part, and Irganox 1010 (manufactured by Ciba Specialty Chemicals) 1.1 parts were mixed well to obtain a curable composition. The viscosity of this composition at room temperature (23 ° C.) was 25 Pa · s.

Next, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .
Further, the mechanical properties and gel fraction after curing curing of the cured product were measured in the same manner as in Example 1. The results are shown in Table 1.
The hardness and oil resistance (weight increment / ASTM No. 1 oil, 150 ° C. × 70 hours) of the obtained cured product were measured in the same manner as in Example 1, and the results are shown in Table 2.
Further, the compression set (25% compression / 150 ° C. × 70 hours) after curing and curing of the cured product was measured in the same manner as in Example 1, and the results are shown in Table 3.
Comparative Example 1
100 parts of the polymer [1] obtained in Production Example 1 is 1.0 part of IRGACURE 184 (manufactured by Ciba Specialty Chemicals), 0.5 part of IRGACURE 819 (manufactured by Ciba Specialty Chemicals), Irganox 1010 (Ciba Specialty Chemicals) 1 part) was added and mixed well to obtain a curable composition. The viscosity of this composition at room temperature (23 ° C.) was 160 Pa · s.

Next, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .
Further, the mechanical properties and gel fraction after curing curing of the cured product were measured in the same manner as in Example 1. The results are shown in Table 1.
The hardness and oil resistance (weight increment / ASTM No. 1 oil, 150 ° C. × 70 hours) of the obtained cured product were measured in the same manner as in Example 1, and the results are shown in Table 2.
Further, the compression set (25% compression / 150 ° C. × 70 hours) after curing and curing of the cured product was measured in the same manner as in Example 1, and the results are shown in Table 3.

上記結果より、実施例１〜５の本発明の活性エネルギー線硬化型組成物は、比較例１と比べ、低粘度であり硬化物作製時の操作性に優れる上、硬化物の伸びは顕著に向上していた。

From the above results, the active energy ray-curable compositions of the present invention of Examples 1 to 5 have a low viscosity and excellent operability at the time of producing a cured product as compared with Comparative Example 1, and the elongation of the cured product is remarkably increased. It was improving.

The active energy ray-curable composition of the present invention has a low viscosity and particularly excellent elongation of the cured product. Further, since the cured product is excellent in oil resistance and heat resistance due to the polymer structure, it is expected to exhibit excellent sealing properties and adhesiveness when used in the above applications.

Claims (23)

The following three components:
(A) 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)
And two or more groups represented by the general formula (1)
Vinyl polymer having one or more groups represented by
(B) a vinyl monomer having a cyclic structure,
(C) an initiator,
A curable composition containing as an essential component. The curable composition according to claim 1, further comprising (D) a vinyl polymer having one group per molecule represented by the general formula (1) at the molecular end.   The curable composition according to claim 1 or 2, wherein the vinyl polymer as the component (A) and / or (D) is a (meth) acrylic polymer.   The curable composition according to any one of claims 1 to 3, wherein the main chain of the component (A) and / or the component (D) is produced by living radical polymerization of a vinyl monomer.   The curable composition according to claim 4, wherein the living radical polymerization is atom transfer radical polymerization.   The curable composition according to any one of claims 1 to 3, wherein the main chain of the component (A) and / or the component (D) is produced by polymerization of a vinyl monomer using a chain transfer agent.   The curable composition according to any one of claims 1 to 6, wherein the vinyl polymer of the component (A) and / or the component (D) has a number average molecular weight of 3000 or more.   The vinyl polymer as the component (A) and / or (D) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of less than 1.8. The curable composition according to any one of the above.   (E) The curable composition in any one of Claims 1-8 containing the monomer and / or oligomer (however, (B) component is excluded) which has radically polymerizable group.   (E) The curable composition in any one of Claims 1-8 containing the monomer and / or oligomer (however, (B) component is excluded) which has an anion polymerizable group.   The curable composition according to claim 9 or 10, wherein the component (E) is a monomer and / or an oligomer having a (meth) acryloyl group.   The curable composition according to claim 11, wherein the monomer and / or oligomer having the (meth) acryloyl group has a number average molecular weight of 5000 or less.   The curable composition according to any one of claims 1 to 12, wherein the cyclic structure of the component (B) is an aromatic ring and / or an alicyclic structure.   The curable composition according to claim 13, wherein the cyclic structure of the component (B) is at least one selected from the group consisting of a benzene ring, a cyclohexyl ring and an isoboronyl ring.   The curable composition according to claim 13 or 14, wherein the component (B) is a (meth) acrylic acid monomer and / or a styrene monomer.   The curable composition in any one of Claims 1-15 whose said (C) component is a radical initiator.   The curable composition in any one of Claims 1-15 whose said (C) component is an anionic initiator.   The curable composition according to any one of claims 1 to 15, wherein the component (C) is a redox initiator.   Hardened | cured material obtained by hardening the curable composition in any one of Claims 1-18.   Hardened | cured material obtained by irradiating an active energy ray to the curable composition of Claims 1-17.   Hardened | cured material obtained by heat-hardening the curable composition of Claims 1-17.   Hardened | cured material obtained by hardening the curable composition of Claims 17-18 by normal temperature 2 liquid system.   Sealing material, electrical / electronic parts material, electrical insulation material, adhesive, adhesive, potting agent, heat dissipation material, waterproofing material, anti-vibration / vibration control / isolation material, film, marine deck caulking, casting material, or The curable composition according to any one of claims 1 to 18, which is used for a molding material.