JP2003221422A - Polymerizable compound, method for producing the compound, polymerizable composition containing the compound, cured product obtained by curing the composition and method for producing the cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition excellent in adhesion to a substrate such as PET, which can subject to heat curing and/or an active energy ray-curing without polymerization inhibition by oxygen. <P>SOLUTION: A polymerizable compound represented by formula (1) äwherein R<SP>1</SP>is at least one organic residue group selected each independently from the group consisting of an alkylene, a branched alkylene, a cycloalkylene, an aralkylene and an arylene, R<SP>2</SP>is an organic residue group derived from an alcohol compound, a phenol compound or a carboxylic compound, (n) is an integer of 0-20}, a method for producing the compound, the polymerizable composition using the compound, a cured product obtained by curing the composition and a method for producing the cured product are provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymerizable compound, a method for producing the polymerizable compound, a polymerizable composition using the polymerizable compound, and a cured product obtained by curing the polymerizable composition, And a method for producing the cured product.

More specifically, it is provided with radical polymerizability so that it can be cured by heat and / or activated energy rays, and further adheres to a substrate such as polyethylene terephthalate (hereinafter abbreviated as "PET"). Good polymerizable compound, a method for producing the polymerizable compound, a polymerizable composition using the polymerizable compound, and a cured product obtained by curing the polymerizable composition.

The term "active energy rays" used herein means near infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X rays, γ rays,
Electromagnetic waves or particle beams having energy such as electron beams.

The term "thermosetting" as used herein means radical curing by heat to cure.

[0005]

2. Description of the Related Art A typical radical curable resin having a hydroxyl group is, for example, a vinyl ester resin (epoxy acrylate) obtained by reacting an epoxy resin with acrylic acid or methacrylic acid. Vinyl ester resin has radical polymerizability (meth)
Since it has an acrylate group, it can be cured by heat or light, and is widely used as a resin for UV offset printing ink and a resin for artificial marble.

However, since the vinyl ester resin undergoes polymerization inhibition by oxygen during polymerization, it may be insufficiently cured when used as a thin film coating such as a thin film coating.

Attempts have also been made to introduce an allyl ether group in order to avoid inhibition of polymerization of the vinyl ester resin by oxygen. Specifically, for example, Japanese Patent Publication No. 1-51
No. 487 can be cited. However, Tokuhei 1
In the technology of Japanese Patent No. 51487, it cannot be said that the copolymerizability of the (meth) acrylate group and the allyl ether group is necessarily good, and when used as a thin film coating such as a thin film coating, the polymerization rate is sufficient. However, the curing may be insufficient.

As the radical-curable resin having a hydroxyl group other than the vinyl ester resin, an ester of a polyhydric alcohol such as trimethylolpropane di (meth) acrylate or pentaerythritol tri (meth) acrylate and (meth) acrylic acid is used. A compound in which some hydroxyl groups remain is commercially available. However, since these compounds are also subject to polymerization inhibition by oxygen during polymerization, curing may be insufficient when used as a thin film coating such as a thin film coating.

On the other hand, epoxy resin is a coating material,
It is an excellent resin that has a wide range of applications such as electrical insulation materials, laminated structure materials, civil engineering and construction materials, and adhesives. In particular, it is known that the coating material has good adhesiveness. However, there are problems that it takes time to cure and that a large amount of amine used as a curing agent remains and causes coloring.

There is an example in which an epoxy resin is modified to solve these problems. For example, there is a vinyl ester resin (epoxy acrylate) obtained by reacting an epoxy resin with acrylic acid or methacrylic acid. This modification can impart radical polymerizability to shorten the curing time, and eliminates the need to add a curing agent that causes coloring. However, the vinyl ester resin undergoes polymerization inhibition by oxygen during the polymerization, so that the curing is insufficient in the polymerization under air.

Generally, epoxy resin means "2 in 1 molecule.
A general term for compounds having one or more epoxy groups (oxirane rings) ("Encyclopedia of Engineering Plastics", Gihodo Publishing Co., Ltd., December 15, 1988, 1st edition, 1st edition, page 621, "24 Epoxy resin") There is. A typical epoxy resin shown here is bisphenol A-diglycidyl ether produced by condensation of bisphenol A and epichlorohydrin, but in addition, a glycidyl group is added to the terminal hydroxyl group of (poly) ethylene glycol. Examples of epoxy resins include those having relatively low molecular weight, such as those obtained by adding a glycidyl group to the hydroxyl group of 1,6-hexanediol.

On the other hand, allyl glycidyl ether, phenyl glycidyl ether, cresol glycidyl ether which are compounds having one epoxy group in one molecule (specifically, for example, ADEKA GLYCIDOL ED-529 (manufactured by Asahi Denka Co., Ltd.) )) And the like are commercially available as diluents for epoxy resins. According to the section “24 Epoxy resin 1.2 Curing reaction (2) Sub-material” (page 635) in the “Engineering Plastics Encyclopedia”, “This reactive diluent is mixed with the epoxy resin in advance. And the mixture is commercially available as a grade of epoxy resin. ”(Page 636).

Therefore, the epoxy resin in the present specification is defined as "a compound having at least one or more epoxy groups" and is not restricted by the size of the molecular weight.

As described above, attempts have been made to introduce an allyl ether group in order to prevent the polymerization inhibition of oxygen in the vinyl ester resin modified with the epoxy resin. For example, in Japanese Examined Patent Publication No. 1-51487, an allylic group is introduced by reacting an epoxy resin with a trimethylolpropane diallyl ether reaction product of methacrylic acid and phthalic anhydride to avoid polymerization inhibition by oxygen. However, the allyl ether group is poor in radical polymerizability and cannot be said to be sufficient in terms of polymerization rate, and there is a demand for a polymerizable compound having improved polymerizability and a polymerizable composition containing the compound.

[0015]

DISCLOSURE OF THE INVENTION The present invention has solved the above-mentioned problems, and enables thermal curing and / or curing with active energy rays without being hindered by polymerization inhibition by oxygen.
Provide a novel polymerizable compound having good adhesion to a substrate, a polymerizable compound characterized by containing the compound, a method for producing the epoxy resin, a polymerizable using the epoxy resin It is to provide a composition, a cured product obtained by curing the polymerizable composition, and a method for producing the cured product.

[0016]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above problems. As a result, an epoxy compound, particularly an epoxy resin, and a fumaric acid monoester having an allyl group, and in some cases, (meth) acrylic acid is used as a raw material, and a novel polymerizable compound obtained by reacting them is used to generate oxygen. It has been found that a cured product which can be cured by heat and / or activated energy rays without being hindered by polymerization due to the above and can provide a cured product having good adhesion to a substrate such as PET, has completed the present invention.

That is, the present invention (I) is a polymerizable compound represented by the general formula (1). General formula (1)

[0018]

[Chemical 30]

(In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² is an alcohol compound. Represents an organic residue derived from a phenol compound or a carboxylic acid compound, and n represents an integer of 0 to 20. Further, R ² is further represented by the following general formula (2) and / or the following general formula (3). Can be included groups.)

General formula (2)

[Chemical 31]

(In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is 0 to 20. Represents the integer of.)

General formula (3)

[Chemical 32]

(In the formula, R ³ represents either H or CH _3. ) The “polymerizable compound” referred to herein is included in the “epoxy resin” already defined as a part or all of the production raw material. When the compound described above is used, it may be called a "modified epoxy resin". For example, a vinyl ester resin (epoxy acrylate) that is radically polymerized by addition reaction of acrylic acid with an epoxy resin is also included in the “modified epoxy resin”.

The polymerizable compound of the present invention (I) is also radically reacted with a fumaric acid monoester having an allyl group in an epoxy resin or a fumaric acid monoester having an allyl group in an epoxy resin and a (meth) acrylic acid. When it is polymerized, it is included in one of the “modified epoxy resins”.

The term "(meth) acrylic acid" as used herein means any one of acrylic acid, methacrylic acid and a mixture of both.

The present invention (II) also relates to a process for producing the polymerizable compound of the present invention (I), which comprises the following steps.

In the presence of a step catalyst, at least one or more compounds selected from the compounds represented by the following general formula (4) and at least one or more compounds selected from the compounds represented by the following general formula (5) are carried out. Process for obtaining polymerizable compound General formula (4)

[0028]

[Chemical 33]

(In the formula, R ⁴ represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound, and q represents an integer of 1 or more.) General formula (5)

[0030]

[Chemical 34]

(In the formula, each R ⁵ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is 0 to 20. Represents the integer of.)

The present invention (III) also includes the present invention (I).
The present invention relates to a polymerizable composition, which comprises at least one of the above polymerizable compounds as an essential component.

Further, the present invention (IV) corresponds to the present invention (II
The present invention relates to a polymerizable composition containing 0.1 part by mass to 10 parts by mass of at least one radical polymerization initiator with respect to 100 parts by mass of the polymerizable composition of I).

Further, the present invention (V) corresponds to the present invention (II
The present invention relates to a cured product obtained by curing the polymerizable composition according to any one of I) or the present invention (IV), and a method for producing the cured product.

Further, the present invention comprises the following items, for example. [1] A polymerizable compound represented by the following general formula (1). General formula (1)

[Chemical 35] (In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² is an alcohol compound or a phenol compound. Or represents an organic residue derived from a carboxylic acid compound, n represents an integer of 0 to 20, and R ² further represents a group represented by the following general formula (2) and / or the following general formula (3). Can be included.) General formula (2)

[Chemical 36] (In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n represents an integer of 0 to 20. General formula (3)

[Chemical 37] (In the formula, R ³ represents either H or CH _3. )

[2] At least one organic residue selected from the organic residues represented by the following structural formulas (1) to (7), each R ¹ in the general formula (1). The polymerizable compound according to [1], wherein Structural formula (1)

[Chemical 38] Structural formula (2)

[Chemical Formula 39] Structural formula (3)

[Chemical 40]

Structural formula (4)

[Chemical 41] Structural formula (5)

[Chemical 42] Structural formula (6)

[Chemical 43] Structural formula (7)

[Chemical 44]

[3] In the general formula (1), R ² is
Ethylene glycol, propylene glycol, 1,3-
Propanediol, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane,
1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac Selected from the group consisting of resins, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid. The polymerizable compound according to any one of [1] and [2], which is an organic residue derived from the compound described above.

[4] In the general formula (1), R ¹ is at least one or more independently selected from the organic residues represented by the following structural formulas (1) to (7), and R ² is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol , 1,
4-cyclohexanedimethanol, bisphenol A,
Bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin,
1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid,
The polymerizable compound according to any one of [1] to [3], which is an organic residue derived from a compound selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid.

Structural formula (1)

[Chemical formula 45] Structural formula (2)

[Chemical formula 46] Structural formula (3)

[Chemical 47] Structural formula (4)

[Chemical 48]

Structural formula (5)

[Chemical 49] Structural formula (6)

[Chemical 50] Structural formula (7)

[Chemical 51]

[5] The method for producing a polymerizable compound according to any one of [1] to [4], which comprises the following steps. In the presence of a step catalyst, at least one or more compounds selected from the compounds represented by the following general formula (4) and at least one or more compounds selected from the compounds represented by the following general formula (5) are subjected to an addition reaction [1]. To a step of obtaining the polymerizable compound according to any one of [4]

General formula (4)

[Chemical 52] (In the formula, R ⁴ represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound, and q
Represents an integer of 1 or more. )

General formula (5)

[Chemical 53] (In the formula, each R ⁵ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n represents an integer of 0 to 20. Represents.)

[6] The method for producing a polymerizable compound according to any one of [1] to [4], which comprises the following steps. In the presence of a step catalyst, at least one selected from compounds represented by the following general formula (4), at least one selected from compounds represented by the following general formula (5), and represented by the general formula (6) To obtain the polymerizable compound according to any one of [1] to [4] by carrying out at least one addition reaction selected from the compounds described below.

General formula (4)

[Chemical 54] (In the formula, R ⁴ represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound, and q
Represents an integer of 1 or more. )

General formula (5)

[Chemical 55] (In the formula, each R ⁵ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n represents an integer of 0 to 20. Represents.)

General formula (6)

[Chemical 56] (In the formula, R ⁶ represents either H or CH _3. ) [7]
In the general formula (4), R ⁴ is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylol. Propane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, Cresol novolac resin, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,
[5] or [6], which is at least one organic residue derived from 4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid. A method for producing a polymerizable compound according to any one of 1.

[8] In the general formula (5), each R ⁵ is independently at least one selected from the organic residues represented by the following structural formulas (1) to (7). The method for producing a polymerizable compound according to any one of [5] to [7], characterized in that Structural formula (1)

[Chemical 57] Structural formula (2)

[Chemical 58] Structural formula (3)

[Chemical 59] Structural formula (4)

[Chemical 60]

Structural formula (5)

[Chemical formula 61] Structural formula (6)

[Chemical formula 62] Structural formula (7)

[Chemical formula 63]

[0051]

[9] The catalyst contains at least one selected from the group consisting of metal halides, tertiary amines, pyridine compounds, pyridinium salts, quaternary ammonium salts, phosphine compounds and phosphonium salts [5 ] The manufacturing method of the polymeric compound in any one of [8].

[10] The catalyst is tin chloride, pyridine, isoquinoline, quinoline, benzyltrimethylammonium salt, benzyltriethylammonium salt, 2,4,6.
-Containing at least one selected from the group consisting of tris (dimethylaminomethyl) phenol, triethylamine, triphenylphosphine, ethyltriphenylphosphonium salt, tetraphenylphosphonium salt, and benzyltriphenylphosphonium salt. The method for producing a polymerizable compound according to any one of [5] to [8], which is characterized.

[11] The method for producing a polymerizable compound according to any one of [5] to [8], wherein the catalyst is a catalyst having a radically polymerizable functional group.

[12] A catalyst having a radically polymerizable functional group is N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, trimethylmethacryloyloxyethylammonium salt, trimethylacryloyloxyethylammonium salt, 2
-Vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N- (3-N ', N'-dimethylaminopropyl) acrylamide, N- (3-N', N'-dimethylaminopropyl) methacrylamide, trimethyl The method for producing a polymerizable compound according to [11], which is at least one selected from the group consisting of acryloylaminopropylammonium salt, trimethylmethacryloylaminopropylammonium salt, and dimethyldiallylammonium salt.

[13] A polymerizable composition containing at least one of the polymerizable compounds according to any one of [1] to [4] as an essential component.

[14] At least one radical polymerization initiator is contained in an amount of 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of all curable components in the polymerizable composition [13] ] The polymerizable composition as described in.

[15] A cured product obtained by curing the polymerizable composition as described in [13] or [14].

[16] A method for producing a cured product according to the method for curing the cured product according to [15], characterized in that the curing method is heat curing and / or curing with active energy rays.

[0059]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

First, the polymerizable compound of the present invention (I) will be described. The present invention (I) is a polymerizable compound represented by the general formula (1). General formula (1)

[0061]

[Chemical 64]

(In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² is an alcohol compound. Represents an organic residue derived from a phenol compound or a carboxylic acid compound, and n represents an integer of 0 to 20. Further, R ² is further represented by the following general formula (2) and / or the following general formula (3). A group represented by the general formula (2)

[0063]

[Chemical 65]

(In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is 0 to 20. Represents the integer.) General formula (3)

[0065]

[Chemical formula 66]

(In the formula, R ³ represents either H or CH _3. )

In the general formula (1), R ¹ represents an organic residue containing at least one selected from an alkylene group, a branched alkylene group, a cycloalkylene group and an aralkylene group.

Specific examples of R ^{1 in} the general formula (1) include direct groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group and decylene group. Chain-like alkylene groups, cyclopropylene groups, cyclobutylene groups, cyclopentylene groups, cyclohexylene groups, cycloheptylene groups, cyclooctylene groups, dicyclopentylene groups, tricyclopentylene groups and other cycloalkylene groups, methylethylene Examples thereof include branched alkylene groups such as groups, phenylethylene groups, aralkylene groups such as 1,2-diphenylethylene groups, phenylene groups, naphthylene groups, and arylene groups such as anthranylene groups. However, needless to say, it is not limited to these specific examples.

Of these, the following structural formulas (1) to (7) are preferable from the viewpoints of availability of raw materials and ease of synthesis.

Structural formula (1)

[Chemical formula 67]

Structural formula (2)

[Chemical 68]

Structural formula (3)

[Chemical 69]

Structural formula (4)

[Chemical 70]

Structural formula (5)

[Chemical 71]

Structural formula (6)

[Chemical 72]

Structural formula (7)

[Chemical formula 73]

In the general formula (1) and the general formula (2), "independently of R ¹ " means that in all R ¹ in the polymerizable compound of the present invention (I), each R ¹ is different. This means that they may have the same structure or the same structure. That is, all R ¹ may have the same structure, some may have the same structure and the other may have different structures, or all R ¹ may have different structures. To do.

R ² in the general formula (1) represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound. In addition, R ² may further include a group represented by the general formula (2) and / or the general formula (3).

In the present specification, "R ² represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound" means that R ² is derived only from an alcohol compound, a phenol compound or a carbonyl compound. It does not mean that the organic residue is derived from an alcohol compound, a phenol compound, or an organic residue derived from a carbonyl compound in R ² . It also means that it does not matter at all if R ² has an organic residue derived from a compound other than the carbonyl compound.

As the "alcohol compound" referred to here,
The following compounds can be illustrated.

Methanol, ethanol, propanol,
Isopropanol, 1-butanol, 2-butanol,
Monol compounds such as t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 1,2. -Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 Cyclohexanedimethanol, hydrogenated bisphenol A, tricyclo [5.2.1.0
^2,6 ] decane dimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct and other diol compounds, glycerin, trimethylolpropane, trimethylolethane and other triol compounds, pentaerythritol, diglycerin and other tetraol compounds, etc. Can be mentioned. However,
Needless to say, it is not limited to these specific examples.

The following compounds can be exemplified as the "phenol compound" used herein.

Phenol, catechol, resorcinol, hydroquinone, bisphenol A, brominated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin and the like can be mentioned. However, needless to say, it is not limited to these specific examples.

Furthermore, the "carbonyl compound" referred to herein
As the above, the following compounds can be exemplified.

Acetic acid, propionic acid, butyric acid, benzoic acid, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid anhydride, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6 -Naphthalenedicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5
-Benzenetricarboxylic acid and the like can be mentioned.
However, needless to say, it is not limited to these specific examples.

Among these organic residues contained in R ² , particularly preferable ones are ethylene glycol, propylene glycol, 1, and 1, from the viewpoint of easy availability.
3-propanediol, 1,4-butanediol, 1,
6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, Brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3
-Cyclohexene-1,2-dicarboxylic acid, phthalic acid,
Examples thereof include organic residues derived from isophthalic acid and terephthalic acid.

[0087] Preferred combinations of the general formula (1) and organic residues contained in R ² of the general formula (2) R ¹ and the general formula in (1), R ¹ is a methylene group, an ethylene group , Propylene group, butylene group, hexylene group, octylene group, cyclopentylene group, cyclohexylene group, dicyclopentylene group, methylethylene group, phenylethylene group, 1,2-diphenylethylene group, phenylene group, naphthylene group At least one organic residue selected, R ² is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octane Njioru, neopentyl glycol, 1,2-cyclohexanediol, 1,3
Cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide Adjunct,
Glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diglycerin, catechol, bisphenol A, brominated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, maleic acid, maleic anhydride, fumaric acid, 1,2 -Cyclohexanedicarboxylic acid, anhydrous 1,
2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-
Methyl-4-cyclohexene-1,2-dicarboxylic acid,
It preferably contains an organic residue derived from at least one selected from phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid.

Of these, R ¹ is at least one organic residue selected from the following structural formulas (1) to (7), and R ² is ethylene because of easy availability of raw materials and synthesis. Glycol, propylene glycol, 1,3-
Propanediol, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane,
1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac Resin, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid It is preferable to contain an organic residue derived from at least one or more kinds. Structural formula (1)

[0089]

[Chemical 74]

Structural formula (2)

[Chemical 75]

Structural formula (3)

[Chemical 76]

Structural formula (4)

[Chemical 77]

Structural formula (5)

[Chemical 78]

Structural formula (6)

[Chemical 79]

Structural formula (7)

[Chemical 80]

N in the general formulas (1) and (2) is 0.
Represents an integer from 20 to 20. When n is 21 or more, the molecular weight becomes large, so the number of polymerization sites per mass decreases,
Polymerization is likely to be incomplete, and there is a risk that sufficient hardness may not be obtained when a cured product is obtained, which is not preferable.

When n = 0, the polymerizable compound of the present invention (I) contains an allyl ester group, but is slightly more radically polymerizable than the case where n contains an allyl ether group of 1 or more. Since it is inferior, n is preferably 1 or more.

R ² in the general formula (1) may further contain a group represented by the general formula (2) and / or the general formula (3).

Regarding R ¹ and n in the general formula (2),
As described above.

Further, with respect to R ³ in the general formula (3),
Either H or CH ₃ . When R ³ is H, the polymerizable compound of the present invention (I) has an acryloyl group, and when R ³ is CH ₃ , the polymerizable compound of the present invention (I) is a methacryloyl group. Will have a group. The purpose of introducing an acryloyl group or a methacryloyl group into the polymerizable compound of the present invention (I) is to increase the curing rate, and is a very effective means for increasing the curing rate. However, it is not always necessary to introduce an acryloyl group or a methacryloyl group when the compound belongs to the category of the present invention (I) and the curing rate is already sufficiently high.

If the structure of the general formula (2) is excessively substituted with the structure of the general formula (3), the polymerization is inhibited by oxygen, which is not preferable. The ratio of the number of groups represented by the general formula (3) and the number of groups represented by the general formula (2) contained in the polymerizable compound of the present invention (I) is 0.
It is preferably from 10 to 10, more preferably from 0 to 5, and particularly preferably from 0 to 2.

R ³ in the general formula (3) represents either H or CH ₃ . However, the polymerizable compound of the present invention (I) is 1
When a molecule has a plurality of groups represented by the general formula (3), all R ³ 's contained in one molecule are all H's.
Even among all R ³ contained in one molecule,
It does not matter if some are H and the rest are CH _{3 or} all R ³ contained in one molecule are all CH ₃ .

Further, the polymerizable compound of the present invention (I) may contain at least one or more groups represented by the general formula (1) in one molecule. Therefore, for example, it is not necessary that all the epoxy groups present in the epoxy compound as the raw material be the groups represented by the general formula (1), and even if some epoxy groups remain, it does not matter.

For example, when bisphenol A-diglycidyl ether is used as the epoxy compound, even if two epoxy rings are both groups represented by the general formula (1), one is represented by the general formula (1). And the other may leave the epoxy ring as it is.

Particularly in the case of an epoxy resin derived from a compound having a large number of hydroxyl groups in one molecule such as a phenol novolac resin, even if all of the epoxy rings are the groups represented by the general formula (1), One part may be a group represented by the general formula (1) and the other part may leave the epoxy ring as it is. Furthermore, the epoxy resin as a whole may be a mixture of both.

Next, the present invention (II) will be described in more detail.

The present invention (II) relates to a process for producing the polymerizable compound of the present invention (I), which comprises the following steps.

In the presence of a process catalyst, at least one or more compounds selected from the compounds represented by the following general formula (4) and at least one or more compounds selected from the compounds represented by the following general formula (5) are carried out. Process for obtaining polymerizable compound General formula (4)

[0109]

[Chemical 81]

(In the formula, R ⁴ represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound, and q represents an integer of 1 or more.)

General formula (5)

[Chemical formula 82]

(In the formula, each R ⁵ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is 0 to 20. Represents the integer of.)

Further, in the step of the present invention (II), a catalyst is generally used for promoting the reaction.

The catalyst used in the step of the present invention (II) may be any catalyst generally used in the reaction between epoxy and carboxylic acid, and specific examples of the catalyst used include: Metal halides such as aluminum chloride, tin chloride and zinc chloride, pyridine compounds such as pyridine, α-picoline, isoquinoline, quinoline, 2-vinylpyridine, 3-vinylpyridine and 4-vinylpyridine,
N-methylpyridinium chloride, N-methylpyridinium bromide, N-ethylpyridinium chloride, N-ethylpyridinium bromide, 2-vinylpyridinium chloride, 2-vinylpyridinium bromide, 3-vinylpyridinium chloride, 3-vinylpyridinium bromide, 4- Pyridinium salts such as vinylpyridinium chloride and 4-vinylpyridinium bromide, N, N-benzyldimethylamine, N, N-
Dimethylphenylamine, N, N-dimethylcyclohexylamine, 2,4,6-tris (dimethylaminomethyl) phenol, triethylamine, tri-n-butylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylaniline , N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N- (3-N ', N'-dimethylaminopropyl) acrylamide, N- (3-N', N'-
Dimethylaminopropyl) methacrylamide and other tertiary amines, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, trimethylmethacryloyloxyethylammonium chloride, trimethylmethacryloyloxyethylammonium bromide, trimethylacryloyloxyethyl Ammonium chloride, trimethylacryloyloxyethylammonium bromide, trimethylacryloylaminopropylammonium chloride, trimethylacryloylaminopropylammonium bromide, trimethylmethacryloylaminopropylammonium chloride, trimethylmethacryloyl Quaternary ammonium salts such as minopropylammonium bromide, dimethyldiallylammonium chloride and dimethyldiallylammonium bromide, phosphine compounds such as triphenylphosphine, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide and tetraphenylphosphonate. Phosphonium salts such as aluminum chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, sodium hydroxide, potassium hydroxide, hydroxides such as lithium hydroxide, potassium carbonate, Carbonates such as calcium carbonate can be mentioned. However, needless to say, it is not limited to these specific examples.

[0115] Of these, tin chloride, pyridine, isoquinoline, quinoline,
2,4,6-Tris (dimethylaminomethyl) phenol, triethylamine, triphenylphosphine, benzyltrimethylammonium salt such as benzyltrimethylammonium chloride and benzyltrimethylammonium bromide, benzyltriethylammonium such as benzyltriethylammonium chloride and benzyltriethylammonium bromide Ammonium salts, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide and other ethyltriphenylphosphonium salts, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and other tetraphenylphosphonium salts , Benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide Benzyl triphenyl phosphonium salts such as de are preferred.

From the viewpoint of preventing the elution of the catalyst after curing the polymerizable compound of the present invention, it is preferable to use a catalyst having a radically polymerizable functional group as the catalyst.

Specific examples of the catalyst having a radically polymerizable functional group include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N- (3-N ', N'-dimethylaminopropyl) acrylamide, N- (3-N', N'-dimethylaminopropyl) methacrylamide, trimethylmethacryloyloxyethylammonium chloride, trimethylmethacryloyloxyethylammonium bromide, etc. Trimethylmethacryloyloxyethylammonium salt, trimethylacryloyloxyethylammonium chloride, trimethylacryloyloxyethylammonium bromide, etc. Salts, trimethylacryloylaminopropylammonium chloride, trimethylacryloylaminopropylammonium bromide and other trimethylacryloylaminopropylammonium salts, trimethylmethacryloylaminopropylammonium chloride, trimethylmethacryloylaminopropylammonium bromide and other trimethylmethacryloylaminopropylammonium salts, dimethyldiallylammonium Dimethyldiallylammonium salts such as chloride and dimethyldiallylammonium bromide, 2
-Vinylpyridinium chloride, 2-vinylpyridinium bromide, 3-vinylpyridinium chloride,
Examples thereof include vinylpyridinium salts such as 3-vinylpyridinium bromide, 4-vinylpyridinium bromide and 4-vinylpyridinium bromide. However, needless to say, it is not limited to these specific examples.

Further, considering the suppression of elution of the catalyst after curing the polymerizable compound of the present invention, the availability and the rate of addition reaction, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N , N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N- (3-N ', N'-dimethylaminopropyl) acrylamide, N- (3-N', N'-dimethylaminopropyl) methacryl Amides, trimethylmethacryloyloxyethylammonium chloride, trimethylmethacryloyloxyethylammonium bromide and other trimethylmethacryloyloxyethylammonium salts, trimethylacryloyloxyethylammonium chloride, trimethylacryloyloxyethylammonium bromide Trimethylacryloyloxyethylammonium salt such as idide, trimethylacryloylaminopropylammonium chloride, trimethylacryloylaminopropylammonium bromide and other trimethylacryloylaminopropylammonium salt, trimethylmethacryloylaminopropylammonium chloride, trimethylmethacryloylaminopropylammonium bromide and other trimethylmethacryloylamino Dimethyldiallylammonium salts such as propylammonium salt, dimethyldiallylammonium chloride and dimethyldiallylammonium bromide are particularly preferred.

R ⁴ in the general formula (4) represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound.

As the "alcohol compound" referred to here,
The compounds described below can be exemplified.

Methanol, ethanol, propanol,
Isopropanol, 1-butanol, 2-butanol,
Monol compounds such as t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 1,2. -Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 Cyclohexanedimethanol, hydrogenated bisphenol A, tricyclo [5.2.1.0
^2,6 ] decane dimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct and other diol compounds, glycerin, trimethylolpropane, trimethylolethane and other triol compounds, pentaerythritol, diglycerin and other tetraol compounds, etc. Can be mentioned. However,
Needless to say, it is not limited to these specific examples.

The following compounds can be exemplified as the "phenol compound".

Examples thereof include phenol, catechol, resorcinol, hydroquinone, bisphenol A, brominated bisphenol A, bisphenol F, phenol novolac resin and cresol novolac resin. However, needless to say, it is not limited to these specific examples.

Furthermore, the "carbonyl compound" referred to herein
As the above, the following compounds can be exemplified.

Acetic acid, propionic acid, butyric acid, benzoic acid, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6 -Naphthalenedicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5
-Benzenetricarboxylic acid and the like can be mentioned.
However, needless to say, it is not limited to these specific examples.

From the viewpoint of easy availability, R ⁴ in the general formula (4) is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4
-Butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, Bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, 1,2-cyclohexanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-
Particularly preferred is an organic residue derived from a compound selected from the group consisting of dicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid.

The compound represented by the general formula (4) also includes an epoxy resin. The epoxy resin is described in detail in the above "Encyclopedia of Engineering Plastics". Of course, it is not limited to the compounds described therein. When an epoxy resin is used as the compound represented by the general formula (4) as described above, the polymerizable compound of the present invention may be referred to as a “modified epoxy resin” from its raw material.

Q in the compound represented by the general formula (4)
Is not particularly limited as long as it is an integer of 1 or more. Preferably 2
The range is from -20.

In formula (5), each R ⁵ independently represents an organic residue derived from at least one selected from an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group.

Specific examples of R ^{5 in} the general formula (5) include direct groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group and decylene group. Chain-like alkylene groups, cyclopropylene groups, cyclobutylene groups, cyclopentylene groups, cyclohexylene groups, cycloheptylene groups, cyclooctylene groups, dicyclopentylene groups, tricyclopentylene groups and other cycloalkylene groups, methylethylene Examples thereof include branched alkylene groups such as groups, phenylethylene groups, aralkylene groups such as 1,2-diphenylethylene groups, phenylene groups, naphthylene groups, and arylene groups such as anthranylene groups. However, needless to say, it is not limited to these specific examples.

Of these, from the viewpoint of availability of raw materials and easiness of synthesis of the compound represented by the general formula (5), among the organic residues represented by the following structural formulas (1) to (7), It is preferably at least one selected from

Structural formula (1)

[Chemical 83]

Structural formula (2)

[Chemical 84]

Structural formula (3)

[Chemical 85]

Structural formula (4)

[Chemical 86]

Structural formula (5)

[Chemical 87]

Structural formula (6)

[Chemical 88]

Structural formula (7)

[Chemical 89]

In the general formula (5), "R ⁵ is independently of each other" means that n R ^{5 s} may be different from each other. In other words, among n R ⁵ , the same structure may be n, some may be the same structure and the others may be different, or n kinds of structures may be provided one by one. Means that.

In the present invention (II), R of the general formula (4)
⁴ and Preferred combinations in R ⁵ in the general formula (5), R ⁴ is ethylene glycol of the general formula (4), diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol , Tetraethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,2-cyclohexanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
Hydrogenated bisphenol A, tricyclo [5.2.1.0]
^2,6 ] Decanedimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diglycerin, catechol, bisphenol A, brominated bisphenol A, bisphenol F, Phenol novolac resin, cresol novolac resin, benzoic acid, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-
Cyclohexanedicarboxylic acid, 3-cyclohexene-
1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, phthalic acid, phthalic anhydride,
At least one organic residue derived from a compound selected from the group consisting of isophthalic acid and terephthalic acid, and R ⁵ in the general formula (5) is a methylene group, an ethylene group, a propylene group, a butylene group, or hexylene. Group, octylene group, cyclopentylene group, cyclohexylene group, dicyclopentylene group, methylethylene group, phenylethylene group, 1,2-diphenylethylene group, phenylene group, at least one organic residue selected from naphthylene group It is desirable that it is a group.

Of these, R ⁴ in the general formula (4) is particularly ethylene glycol, propylene glycol, 1,3-propanediol, 1, or 3 because of easy availability of raw materials and easy synthesis.
4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct , Bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, 1,2-cyclohexanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-
At least one organic residue derived from a compound selected from the group consisting of dicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid, and R in the general formula (5)
⁵ is preferably at least one or more organic residue selected from an organic residue represented by the following structural formula (1) to the following structural formula (7).

Structural formula (1)

[Chemical 90]

Structural formula (2)

[Chemical Formula 91]

Structural formula (3)

[Chemical Formula 92]

Structural formula (4)

[Chemical formula 93]

Structural formula (5)

[Chemical 94]

Structural formula (6)

[Chemical 95]

Structural formula (7)

[Chemical 96]

In the production method of the present invention (II), the compound represented by the following general formula (6) is used in combination with at least one carboxylic acid of the compound represented by the general formula (5). It can be used in combination and is preferable for the purpose of increasing the curing rate of the polymerizable compound of the present invention (I). General formula (6)

[0150]

[Chemical 97]

R ^{6 in} this general formula (6) represents either H or CH ₃ .

That is, when R ⁶ is H, the general formula (6)
The compound represented by means acrylic acid, and when R ⁶ is CH ₃ , the compound represented by the general formula (6) means methacrylic acid.

In the production method of the present invention (II), when the compound represented by the general formula (6) is used, even if only acrylic acid is used as the compound represented by the general formula (6), methacrylic acid is used. It does not matter whether only acrylic acid and methacrylic acid are used together.

Further, as long as the curability of the polymerizable compound of the present invention (I) is not impaired, the compound of the general formula (6) is used in combination with at least one carboxylic acid of the compound of the general formula (5). You may use together carboxylic acid other than the compound represented by. Examples of the carboxylic acid other than the compound represented by the general formula (6), which is used in combination with at least one carboxylic acid of the compound represented by the general formula (5), include acetic acid, propionic acid, butyric acid, benzoic acid, 1 -Phenylbenzoic acid, 2-phenylbenzoic acid, 4-phenylbenzoic acid,
Examples thereof include diphenylacetic acid. However, needless to say, the present invention is not limited to these specific examples.

The reaction temperature of the addition reaction in the step used in the production method of the present invention (II) is not particularly limited, but is generally 0 ° C to 200 ° C, preferably 20 ° C to 150 ° C.
C., more preferably 50 to 120.degree. If the temperature is lower than 0 ° C, the reaction becomes very slow, and if the temperature is higher than 200 ° C, polymerization or decomposition is caused, which is not preferable.

A solvent can be used for the addition reaction in this step. Particularly when a solid or highly viscous raw material is used, it is difficult to stir, and thus it is preferable to use a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the addition reaction, for example, toluene, xylene, methyl ethyl ketone, methyl acetate, ethyl acetate,
Examples thereof include n-propyl acetate, isopropyl acetate and butyl acetate. These solvents can be used alone or in combination of two or more. Of these, toluene and xylene are particularly preferable.

As a raw material charging ratio for the addition reaction in this step, the compound represented by the general formula (5) and the general formula (6) are used with respect to 1 mol of the epoxy group in the compound represented by the general formula (4). ) The total number of moles of the compound represented by
The amount is 1.5 mol, preferably 0.8 mol to 1.2 mol, and more preferably 0.9 mol to 1.1 mol. The total number of moles of the compound represented by the general formula (5) and the compound represented by the general formula (6) is 0.5 mol with respect to 1 mol of the epoxy group in the compound represented by the general formula (4). Less than,
If the amount of the polymerizable compound of interest is too small to cure sufficiently, and if it exceeds 1.5 moles, the compound of the general formula (5)
There is a possibility that the compound represented by is excessive and the curing becomes insufficient, which is not preferable.

The raw material charging ratio of the compound represented by the general formula (6) to the compound represented by the general formula (5) is arbitrary, but is preferably in the range of 0 to 10, and further,
It is preferably in the range of 0-5.

The amount of the catalyst used in this step is based on the total amount of the compound represented by the general formula (4), the compound represented by the general formula (5) and the compound represented by the general formula (6). 0.01% by mass to 10% by mass, preferably 0.1% by mass to 5% by mass, more preferably 0.1% by mass.
~ 3% by mass. If the amount is less than 0.01% by mass, the reaction rate becomes slow and the heating time becomes long, so that the generated polymerizable compound may be thermally polymerized, which is not preferable. Further, if the amount is more than 10% by mass, coloring may become remarkable, which is not preferable from the economical viewpoint.

Further, in this step, a polymerization inhibitor can be used in order to suppress thermal polymerization of the produced polymerizable compound. The polymerization inhibitor used is not particularly limited, but examples thereof include p-benzoquinone and 2,5-diphenyl-
Quinones such as p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, pt-butylcatechol, 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone and the following structural formula (8) to the following structural formula ( Phenol compounds such as 17) can be mentioned.

Structural formula (8)

[Chemical 98]

Structural formula (9)

[Chemical 99]

Structural formula (10)

[Chemical 100]

Structural formula (11)

[Chemical 101]

Structural formula (12)

[Chemical 102]

Structural formula (13)

[Chemical 103]

Structural formula (14)

[Chemical 104]

Structural formula (15)

[Chemical 105]

Structural formula (16)

[Chemical formula 106]

Structural formula (17)

[Chemical formula 107]

Next, the present invention (III) will be described in more detail. The present invention (III) relates to a polymerizable composition which comprises at least one or more of the polymerizable compounds of the present invention (I).

The polymerizable composition of the present invention (III) is obtained by mixing the polymerizable compound of the present invention (I) with various polymerizable monomers, solvents, photopolymerization sensitizers, etc., if necessary. Can be done.

The polymerizable composition of the present invention (III) may contain a polymerizable monomer. The polymerizable monomer that can be used is not particularly limited as long as it has a polymerizable property, and examples thereof include acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and styrene. , Monoallyl maleate, monoallyl fumarate, diallyl maleate, diallyl fumarate, mono (allyloxyethyl) maleate, mono (allyloxyethyl) fumarate, bis (allyloxyethyl) maleate, bis (allyloxy) fumarate Ethyl) and the like. These polymerizable monomers can be used alone or in combination of two or more.

The polymerizable composition of the present invention (III) may contain a solvent for the purpose of adjusting the viscosity. The solvent that can be used is not particularly limited as long as it is generally used, and examples thereof include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, toluene, and xylene. These solvents may be used alone or in combination of two or more.

Further, the polymerizable composition of the present invention (III) may contain a photopolymerization sensitizer. The photopolymerization sensitizer that can be used is not particularly limited as long as it is generally used, for example, thiopyrylium salt, merocyanine, quinoline, stilquinoline, aryl ketones, aromatic ketones, Examples include ketocoumarins.

The polymerizable composition of the present invention (III) can be heat-cured, electron beam-cured and γ-ray-cured without a catalyst. At times, in the case of thermal curing, a thermal polymerization initiator can be used in order to lower the curing temperature or to accelerate the curing rate, and it is preferable.

Next, the present invention (IV) will be described in more detail.

The present invention (IV) is characterized by containing 0.1 part by mass to 10 parts by mass of at least one radical polymerization initiator with respect to 100 parts by mass of the polymerizable composition of the present invention (III). And a polymerizable composition.

The radical polymerization initiator of the present invention (IV) is not particularly limited as long as it is a commonly used one.

For example, in the case of a thermal polymerization initiator, 2,2 '
-Azobisisobutyro, tolyl, azo initiators such as 2,2'-azobisisovaleronitrile, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide , Diacyl peroxides such as lauroyl peroxide and decanoyl peroxide, peroxyketals such as 1,1-di-t-butylperoxycyclohexane and 2,2-di- (t-butylperoxy) butane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-
t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, Examples thereof include alkyl peroxy esters such as di-t-butyl peroxytrimethyl adipate, peroxy carbonates such as diisopropyl peroxy dicarbonate, di-sec-butyl peroxy dicarbonate and t-butyl peroxy isopropyl carbonate. These thermal polymerization initiators can be used alone or in combination of two or more.

If a redox polymerization initiator is used, polymerization can be carried out at around room temperature. For example, a combination of methyl ethyl ketone peroxide and cobalt naphthenate, a combination of cumene peroxide and manganese naphthenate, a combination of benzoyl peroxide and cobalt naphthenate, a combination of acetoacetic ester peroxide and cobalt naphthenate, and a metal such as ketone peroxide and a metal. Combination with an organic acid salt of benzoyl peroxide and N,
A peroxide and an aromatic tertiary amine such as a combination of N-dimethylaniline, a combination of t-butyl hydroperoxide and N, N-dimethyl-p-toluidine, a combination of dibenzoyl peroxide and N, N-dimethylaniline, and the like. Can be used as a redox polymerization initiator.

Examples of active energy rays include near infrared rays, visible rays, ultraviolet rays, vacuum infrared rays, X rays, γ rays, and electron rays.

Of these, specific examples of the radical polymerization initiator used in the polymerization by visible light or ultraviolet irradiation include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholinopropane, 1,2-benzyl-2-methylamino-1-
(4-morpholinophenyl) butanone, acetophenone such as 1,2-hydroxy-2-methyl-1-phenylpropan-1-one or its derivative, benzophenone, 4,4′-bis (dimethylamino) benzophenone 4-trimethylsilylbenzophenone , Benzophenone such as 4-benzoyl-4′-methyldiphenyl sulfide or a derivative thereof, benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin such as benzoin isopropyl ether or a derivative thereof, methylphenylglyoxylate, benzoin dimethyl Ketal, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) ) -4-Ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6) -Dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide,
Bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -decylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenyl Phosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- 2,5-Dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,
4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5
-Phenylphosphine oxide, bis (2-methyl-
1-naphthoyl) -4-biphenylylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2 -Methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methoxyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methoyl-1-naphthoyl) -4-methoxyphenyl Phosphine oxide, bis (2-methoxyl-1-naphthoyl) -4-biphenylylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,
4,6-trimethylpentylphosphine oxide and the like can be mentioned.

Specific examples of the polymerization initiator which is sensitive to visible light include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1).
H-pyrrol-1-yl) -phenyl) titanium (trade name: IRGACURE784 manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like can be mentioned.

Further, specific examples of the polymerization initiator which is sensitive to visible light and / or near infrared rays include visible light represented by the following general formula (7) which has a photosensitivity in the visible light or near infrared light region. / Or a combination of a near infrared absorptive cation dye and a boron-based compound represented by the following general formula (8). General formula (7) D ⁺ · A ⁻ (In the formula, D ⁺ is a cationic dye having absorption in the near-infrared light region, and A ⁻ is various anions.)

General formula (8)

[Chemical 108]

(In the formula, Z ⁺ represents an arbitrary cation, and R ⁷
To R ¹⁰ are each independently an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group,
Silyl group, heterocyclic group, halogen atom, substituted alkyl group,
Substituted aryl group, substituted allyl group, substituted aralkyl group, substituted alkenyl group, substituted alkynyl group or substituted silyl group)

The cationic dye of the general formula (7) of the present invention is
Specifically, it is usually a dye having absorption in an arbitrary wavelength region in the range of 400 nm to 2000 nm, and preferably 50.
It is in the range of 0 nm to 1500 nm.

Preferred examples of the cation (D ⁺ ) of the present invention include methine, polymethine, indoline, cyanine, xanthene, oxazine, thiazine, diarylmethane, triarylmethane, and cations of pyrylium cation dyes. To be Representative examples of such cation dyes include cations represented by structural formulas (18) to (31).

Structural formula (18)

[Chemical 109]

Structural formula (19)

[Chemical 110]

Structural formula (20)

[Chemical 111]

Structural formula (21)

[Chemical 112]

Structural formula (22)

[Chemical 113]

Structural formula (23)

[Chemical 114]

Structural formula (24)

[Chemical 115]

Structural formula (25)

[Chemical formula 116]

Structural formula (26)

[Chemical 117]

Structural formula (27)

[Chemical 118]

Structural formula (28)

[Chemical formula 119]

Structural formula (29)

[Chemical 120]

Structural formula (30)

[Chemical 121]

Structural formula (31)

[Chemical formula 122] The counter anion A ⁻ is an arbitrary anion, but the tetracoordinated boron anion represented by the following general formula (9) is particularly preferable.

General formula (9)

[Chemical 123]

(In the formula, R ^{11 to} R ¹⁴ are each independently an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group or a substituted alkyl group. Aryl group, substituted allyl group, substituted aralkyl group, substituted alkenyl group, substituted alkynyl group or substituted silyl group)

As specific examples, n-butyltriphenylboron ion, n-octyltriphenylboron ion, triphenylsilyltriphenylboron ion, di-n-dodecyldiphenylboron ion, tetraphenylboron ion, tri-n- Examples thereof include butyl (dimethylphenylsilyl) boron ion, and more specifically, the anion described in the specification of JP-A-6-75374.

In the boron-based catalyst represented by the general formula (8), specific examples of the 4-coordinate boron ion which is an anion include n-butyltriphenylboron ion and n-octyltriphenylboron. Ion, triphenylsilyltriphenylboron ion, n-butyltrianisylboron ion, n-butyltri (p-fluorophenyl) boron ion, n-butyltri (p-trifluoromethylphenyl) boron ion, di-n-dodecyldiphenyl Examples thereof include boron ion, tetraphenylboron ion, triphenylnaphthylboron ion, tetrabutylboron ion, and tri-n-butyl (dimethylphenylsilyl) boron ion. The cation (Z ⁺ ) described in the formula is a quaternary ammonium cation or a quaternary pyridinium cation represented by the following general formula (10), a quaternary quinolinium cation, a diazonium cation, a tetrazolium cation, a phosphonium cation. ion,
(Oxo) sulfonium cation, metal cation such as sodium, potassium, lithium, magnesium, calcium, organic oxygen cation such as flavylium and pyranium salt, carbon cation such as tropylium and cyclopropylium, halogenium cation such as iodonium ,arsenic,
Examples thereof include cations of metal compounds such as cobalt, chromium, palladium, titanium, tin and antimony, which are described in detail in the specification of JP-A-6-75374. These cationic dyes and boron-based catalysts may be used alone or in admixture of two or more.

General formula (10)

[Chemical formula 124]

(In the formula, R ^{15 to} R ¹⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a substituted alkyl group, a substituted aryl group, Indicates a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group or a substituted alkynyl group)

These radical polymerization initiators used in the polymerization with near infrared rays, visible rays or ultraviolet rays can be used alone or in combination of two or more kinds.

Further, a thermal polymerization initiator, a redox polymerization initiator and a radical polymerization initiator which is sensitive to ultraviolet rays, visible rays or near infrared rays can be mixed and used.

These radical polymerization initiators are preferably blended in the range of 0.1 parts by mass to 10 parts by mass, more preferably 100 parts by mass of all the curable components in the polymerizable composition. It is 0.3 parts by mass to 7 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass. If the amount is less than 0.1 part by mass, the composition may be insufficiently cured. Further, it is economically unfavorable to add more than 10 parts by mass.

Further, the present invention (V) corresponds to the present invention (II
The present invention relates to a cured product obtained by curing the polymerizable composition according to any one of I) or the present invention (IV), and a method for producing the cured product.

That is, the present invention (III) or the present invention (I
The cured product of the present invention (V) can be obtained by radically polymerizing the polymerizable composition according to any one of V).

Examples of the curing method of the present invention (V) include thermal curing and / or curing with active energy rays. Thermal curing and / or near infrared ray, visible light ray, ultraviolet ray,
Curing with an electron beam is preferable, and curing with heat and / or visible light or ultraviolet rays is particularly preferable. Further, a cured product can be obtained by combining two or more different curing methods.

The reaction temperature for heat curing of the polymerizable composition containing no radical polymerization initiator is usually 50 ° C. to 300 ° C.,
It is preferably 100 ° C to 250 ° C. If the temperature is 50 ° C. or lower, curing is difficult to proceed, and if the temperature is 300 ° C. or higher, the polymerizable composition and the cured product may deteriorate, which is not preferable.

In curing with a thermal polymerization initiator or a redox polymerization initiator, the optimum temperature for curing depends on the temperature at which radicals are generated.

Of the active energy rays, the light source for curing by visible light or ultraviolet rays is, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a deuterium lamp, a metal halide lamp, a halogen lamp, a xenon lamp, a tungsten lamp, a gallium lamp. , A carbon arc lamp, an incandescent lamp, a fluorescent lamp, an excimer lamp, a laser, etc. can be used. Among these light sources, a high pressure mercury lamp and a metal halide lamp are particularly preferable.

As a wavelength of a visible light or ultraviolet curing light source
Usually 200 nm to 750 nm, preferably 200 n
m-450 nm, and the irradiation dose is usually 10 mJ /
cm ²~ 1000mJ / cm², Preferably 100 mJ /
cm²~ 700 mJ / cm²Is.

In the curing using an electron beam, the irradiation method can be a scanning method, a broad beam method, a curtain beam method, an ion plasma method or the like, and the irradiation amount is usually 0.1 Gy to 200 kGy.
And 1 Gy to 100 kGy is preferable.

[0221]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these. The measurement of various physical properties was performed as follows. 1. Using a refractive index (n _D) (Co.) Atago Ltd. "Abbe refractometer 1T", a refractive index was measured at room temperature (n _D).

2. Acid value Measured by the acid value test method described in JIS K 0070. The conversion rate, yield, and purity of the reaction were determined by quantifying each component by an absolute calibration curve method using a high performance liquid chromatogram device using a calibration curve prepared in advance. The column used was Showdex (registered trademark) F-4.
11A (manufactured by Showa Denko KK), solvent is 1% by weight phosphoric acid aqueous solution / methanol = 7/3, flow rate is 1.0 ml / min, and detection device is SPD-10AVvp (manufactured by Shimadzu Corporation) at 210 nm. The peak of each component was detected.

(Production Example-1) Monoallyl fumarate (hereinafter
Below, it is abbreviated as "H-DAF". ) Synthesis of maleic anhydride 474.25 g in a 2 liter flask
(4.837 mol), allyl alcohol 260.69
g (4.833 mol) and 500 ml of toluene were charged, and the reaction solution was heated to 60 ° C. in an oil bath under a nitrogen stream while stirring with a magnetic stirrer. After 14 hours, heating was stopped and the flask was cooled. To this reaction product, 500 ml of toluene and 1 liter of water were added for liquid separation, and the toluene layer was concentrated with an evaporator to obtain 279.01 g of a desired monoallyl maleate (hereinafter, abbreviated as "H-DAM"). . The yield was 37.0%.

In a 300 ml flask equipped with a reflux device, 100.04 g of H-DAM synthesized above
(0.64 mol), 50.00 g of toluene, 1.01 g of concentrated hydrochloric acid (1 mass% with respect to H-DAM), and 0.01 g of hydroquinone monomethyl ether were charged, and the reaction solution was stirred with a magnetic stirrer under a nitrogen stream. While heating at 140 ° C. in an oil bath, the toluene was refluxed. After 4 hours, heating was stopped and the flask was cooled. 2 for this reaction
00 ml of toluene was added and the crystals were filtered to obtain 100 ml.
The crystals were washed twice with toluene. The crystals were dissolved in 150 ml of ethyl acetate, and insoluble materials were removed by filtration. The filtrate was concentrated with an evaporator to give the desired H-DAF at 38.
39 g were obtained. The yield was 38.4%.

(Production Example-2) Monoallyloxy fumarate
Synthesis of ethyl (hereinafter abbreviated as "H-BAF") 500 g of maleic anhydride (5.
10 mol), 573 g (5.61 mol) of ethylene glycol monoallyl ether, and 0.05 g of hydroquinone monomethyl ether were charged, and the reaction solution was heated to 50 ° C. in an oil bath under a nitrogen stream while stirring with a magnetic stirrer. After 24 hours, heating was stopped and the flask was cooled.
When this reaction liquid was analyzed by a high performance liquid chromatogram, the conversion rate of maleic anhydride was 95%.

Further, in a 2 liter flask equipped with a reflux device, 499.54 g of the above reaction solution was charged, and 215.07 g of toluene, 4.99 g of concentrated hydrochloric acid (1% by mass relative to the raw material), and hydroquinone monomethyl ether 0.2
5 g was charged and the reaction solution was stirred with a magnetic stirrer under a nitrogen stream and heated at 140 ° C. in an oil bath to reflux toluene. After 3 hours, heating was stopped and the flask was cooled. To this reaction solution, 500 ml of toluene was added and filtered to remove insoluble materials. Add 50 to this filtrate to remove hydrochloric acid.
0 ml of water was added and the mixture was separated with a separating funnel. The toluene layer was concentrated with an evaporator to obtain the desired H-BAF 428.
g was obtained. The yield based on maleic anhydride was 90%.

Example 1 40 g of H-BAF (2.0 mo) was added to a 1 l flask.
l), Adeka Resin (registered trademark) EP-4100G (bisphenol A diglycidyl ether, epoxy equivalent 1
85, Asahi Denka Kogyo Co., Ltd.) 374.0 g, TPP-Z
c (benzyltriphenylphosphosphonium chloride, manufactured by Hokuko Kagaku Kogyo Co., Ltd.) 5.73 g, IRGANO
X1010 (pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] and Ciba Specialty Chemicals Co., Ltd. 0.4 g were charged, and the reaction solution was heated to 100 ° C. in an oil bath under a nitrogen stream while stirring with a magnetic stir bar. After 9 hours, heating was stopped and the flask was cooled. This compound is designated as "Sample A". Sample A had a refractive index of 1.544 and an acid value of 1.7. The ¹ H-NMR spectrum and IR spectrum of Sample A are shown in FIGS. 1 and 2, respectively.

Example 2 H-BAF 400.4 g (2.0 mo) was added to a 1-liter flask.
l), ADEKA GLYSILOL (registered trademark) ED-505
(Trimethylolpropane triglycidyl ether, epoxy equivalent 153, Asahi Denka Kogyo KK) 307.6
g, TPP-Zc (benzyltriphenylphosphonium chloride, manufactured by Hokuko Chemical Industry Co., Ltd.) 4.25 g, IR
GANOX (registered trademark) 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.42 g was charged and nitrogen was added. The reaction solution was heated to 100 ° C. in an oil bath while stirring with a magnetic stirrer under an air stream. This compound is "Sample B"
And The refractive index of this sample B is 1.500,
The acid value was 17.4. The ¹ H-NMR spectrum and IR spectrum of sample B are shown in FIGS. 3 and 4, respectively.
Shown in.

Example 3 40 g of H-BAF (2.0 mo) was added to a 1 l flask.
1), Adeka Resin (registered trademark) EP-4080E (hydrogenated bisphenol A diglycidyl ether, epoxy equivalent 214, manufactured by Asahi Denka Co., Ltd.) 446.0 g, TP
6.26 g of P-Zc (benzyltriphenylphosphosphonium chloride, manufactured by Kitako Chemical Co., Ltd.), IRGA
NOX (registered trademark) 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.4 g was charged and nitrogen was added. The reaction solution was heated to 100 ° C. in an oil bath while stirring with a magnetic stirrer under an air stream. This compound is designated as "Sample C". The refractive index of this sample C was 1.507 and the acid value was 0.7.

Example 4 In a 1-liter flask, 400.4 g of H-BAF (2.0 mo)
l), Adekaresin (registered trademark) EP-4088S (tricyclo [5.2.1.0 ^2,6 ] decane dimethanol diglycidyl ether, epoxy equivalent 178, Asahi Denka Kogyo KK) 446.0 g, TPP- Zc (benzyltriphenylphosphosphonium chloride, manufactured by Hokuko Kagaku Kogyo Co., Ltd.) 6.26 g, IRGANOX 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate],
0.4 g of Ciba Specialty Chemicals Co., Ltd. was charged and the reaction solution was heated to 100 ° C. in an oil bath under a nitrogen stream while stirring with a magnetic stirrer. This compound is designated as "Sample D". The refractive index of this sample D is 1.
It was 511 and the acid value was 12.3. Of sample D
^{The 1} H-NMR spectrum and IR spectrum are shown in FIGS. 5 and 6, respectively.

Example 5 40 g of H-BAF (2.0 mo) was added to a 1 l flask.
l), Adeka Resin (registered trademark) EP-4085S
(1,4-cyclohexanedimethanol diglycidyl ether, epoxy equivalent 146, manufactured by Asahi Denka Kogyo Co., Ltd.) 2
92 g, TPP-Zc (benzyltriphenylphosphosphonium chloride, manufactured by Hokko Chemical Industry Co., Ltd.) 5.12
g, IRGANOX (registered trademark) 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.4 g The mixture was heated to 100 ° C. in an oil bath while being stirred with a magnetic stirrer under a nitrogen stream. This compound is designated as "Sample E". The refractive index of this sample E was 1.511, and the acid value was 12.3. Sample E ¹ H-N
The MR spectrum and IR spectrum are shown in FIGS. 7 and 8, respectively.

Example 6 H-BAF 48.39 g (0.
242 mol), Araldite ECN (registered trademark) 12
73 (cresol novolac type epoxy resin, epoxy equivalent 214, manufactured by Asahi Ciba Co., Ltd.) 51.70 g, toluene 43.42 g, DMP-30 (2,4,6-tris (dimethylaminomethyl) phenol, Wako Pure Chemical Industries, Ltd. (stock)
0.50 g of hydroquinone monomethyl ether and 0.02 g of hydroquinone monomethyl ether were charged, and the reaction solution was heated to 100 ° C. in an oil bath under a nitrogen stream while stirring with a magnetic stirrer. Two
After 2 hours, heating was stopped and the flask was cooled. When this reaction solution was analyzed by high performance liquid chromatography, it was found that 0.92 g of H-BAF as a raw material remained and the conversion rate of H-BAF was 98.1%. This compound is designated as "Sample F".

Example 7 12.90 g of H-BAF (0.
064 mol), acrylic acid 4.62 g (0.064 m)
ol), Araldite EPN (registered trademark) 1180 (phenol novolac type epoxy resin, epoxy equivalent 17)
9, Asahi Ciba Co., Ltd.) 22.91 g, toluene 48.2
4 g, DMP-30 (2,4,6-tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.)
49 g, hydroquinone monomethyl ether 0.02 g
Was heated in an oil bath at 100 ° C. while stirring the reaction solution with a magnetic stirrer under a nitrogen stream. 13 hours later
The heat was turned off and the flask was cooled. When this reaction solution was analyzed by high performance liquid chromatography, it was found that the starting material, H-BA
It was found that 0.06 g of F and 1.21 g of acrylic acid remained. The conversion rate of H-BAF was 99.5%, and the conversion rate of acrylic acid was 76.0%. This compound is designated as "Sample G".

Example 8 12.90 g of H-BAF (0.
064 mol), acrylic acid 4.63 g (0.064 m)
ol), Araldite ECN (registered trademark) 1273 (cresol novolac type epoxy resin, epoxy equivalent 21
4, Asahi Chiba Co., Ltd.) 30.75 g, toluene 48.2
4 g, DMP-30 (2,4,6-tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.)
49 g, hydroquinone monomethyl ether 0.02 g
Was heated in an oil bath at 100 ° C. while stirring the reaction solution with a magnetic stirrer under a nitrogen stream. 13 hours later
The heat was turned off and the flask was cooled. When this reaction solution was analyzed by high performance liquid chromatography, it was found that the starting material, H-BA
It was found that 0.06 g of F and 1.21 g of acrylic acid remained. The conversion rate of H-BAF was 99.5%, and the conversion rate of acrylic acid was 76.0%. This compound is designated as "Sample H".

Example 9 58.10 g of H-BAF (0.
290 mol), ADECA GLYSILOL ED-507 (glycerin triglycidyl ether, epoxy equivalent 14
5, Asahi Denka Kogyo Co., Ltd.) 42.02 g, DMP-30
(2,4,6-Tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.) 0.50 g and hydroquinone monomethyl ether 0.02 g were charged and the reaction solution was stirred with a magnetic stirrer under a nitrogen stream. While heating to 100 ° C. in an oil bath. After 20 hours, heating was stopped and the flask was cooled. This compound is referred to as "Sample I". This sample I has a refractive index of 1.497 and an acid value of 2.
It was 14.

Example 10 31.28 g of H-BAF (0.
156 mol), acrylic acid 11.28 g (0.156
mol), Araldite AER (registered trademark) 2502
(Diglycidyl bisphenol A, epoxy equivalent 18
5, Asahi Ciba Co., Ltd.) 57.68 g, DMP-30
(2,4,6-Tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.) 0.50 g and hydroquinone monomethyl ether 0.02 g were charged and the reaction solution was stirred with a magnetic stirrer under a nitrogen stream. While heating to 80 ° C. in an oil bath. After 11 hours, heating was stopped and the flask was cooled. When this reaction liquid was analyzed by high performance liquid chromatography, it was found that H-BAF as a raw material had disappeared and that 1.21 g of acrylic acid remained. H
-BAF conversion is 100%, acrylic acid conversion is 8
It was 9.3%. This compound is designated as "Sample J".

Example 11 40 g of H-BAF (2.0 mo) in a 1 l flask.
l), Adeka Resin (registered trademark) EP-4100G (bisphenol A diglycidyl ether, epoxy equivalent 1
85, Asahi Denka Kogyo Co., Ltd. 374.0 g, N, N-dimethylaminoethyl methacrylate (Kyoeisha Chemical Co., Ltd.)
8.0 g, IRGANOX 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Ciba Specialty Chemicals Co., Ltd.) 0.4 g were charged. Under a nitrogen stream, the reaction solution was heated to 110 ° C. in an oil bath while being stirred by a magnetic stirrer. After 6 hours, heating was stopped and the flask was cooled. This compound is "Sample K"
And Sample K had a refractive index of 1.544 and an acid value of 6.5.

Example 12 40 g of H-BAF (2.0 mo) was added to a 1 l flask.
l), Adeka Resin (registered trademark) EP-4100G (bisphenol A diglycidyl ether, epoxy equivalent 1
85, Asahi Denka Kogyo KK, 374.0 g, trimethylmethacryloyloxyethyl ammonium chloride (Kyoeisha Chemical Co., Ltd.) 8.00 g, IRGANOX
1010 (pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] and Ciba Specialty Chemicals Co., Ltd. 0.4 g were charged and the reaction solution was heated to 110 ° C. in an oil bath while stirring the reaction solution with a magnetic stir bar under a nitrogen stream. After 7 hours, heating was stopped and the flask was cooled. This compound is designated as "Sample L". Sample L had a refractive index of 1.544 and an acid value of 6.5.

Example 13 H-BAF 400.4 g (2.0 mo)
l), Adeka Resin (registered trademark) EP-4100G (bisphenol A diglycidyl ether, epoxy equivalent 1
85, Asahi Denka Kogyo Co., Ltd.) 374.0 g, DMP-3
0 (2,4,6-tris (dimethylaminomethyl) phenol, Wako Pure Chemical Industries, Ltd.) 5.00 g, IRGA
NOX1010 (pentaerythrityl-tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.4 g was charged and the reaction solution was stirred with a magnetic stirrer under a nitrogen stream. It heated at 110 degreeC with the oil bath. After 6 hours, heating was stopped and the flask was cooled.
This compound is designated as "Sample M". Sample M had a refractive index of 1.544 and an acid value of 1.7.

Comparative Example 1 In a 200 ml flask, 7.24 g (0.1%) of acrylic acid was added.
00 mol), Araldite AER (registered trademark) 250
2 (diglycidyl bisphenol A, epoxy equivalent 18
5, Asahi Ciba Co., Ltd.) 18.53 g, DMP-30
(2,4,6-tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.) 0.14 g and hydroquinone monomethyl ether 5 mg were charged, and under a nitrogen stream,
While stirring the reaction solution with a magnetic stirrer, use an oil bath to
Heated to 0 ° C. After 6 hours, heating was stopped and the flask was cooled. When this reaction liquid was analyzed by high performance liquid chromatography, it was found that 0.15 g of acrylic acid as a raw material remained and the conversion rate of acrylic acid was 98.0%. This compound is designated as "Sample P".

Comparative Example 2 8.60 g of methacrylic acid (0.
100 mol), Araldite AER (registered trademark) 25
02 (diglycidyl bisphenol A, epoxy equivalent 1
85, Asahi Ciba Co., Ltd.) 18.54 g, DMP-30
(2,4,6-tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.) 0.14 g and hydroquinone monomethyl ether 5 mg were charged, and under a nitrogen stream,
Stir the reaction solution with a magnetic stirrer while stirring in an oil bath.
Heated to 0 ° C. After 10 hours, heating was stopped and the flask was cooled. When this reaction solution was analyzed by high performance liquid chromatography, 0.43 g of methacrylic acid as a raw material remained, and it was found that the conversion rate of methacrylic acid was 95.0%. This compound is designated as "Sample Q".

Curing Experiment 1 (non-catalytic heat curing) Sample A, Sample B, Sample C, Sample D, Sample E, Sample F, Sample G, Sample H, Sample I, Sample J, Sample K, Sample L, Sample M , Sample P and Sample Q were dropped on a glass plate with a drop of a few drops, respectively, and heated in a gear oven (Perfect Oven PV-110, manufactured by Tabai Espec Co., Ltd.) at 150 ° C for 1 hour to perform non-catalytic thermosetting. I tried.
The results are shown in Table 1.

[0243]

[Table 1]

Test samples A, B, E, F, G, H, pentaerythritol triacrylate (hereinafter abbreviated as “PETA”) and pentaerythritol tetraacrylate ( using a coating film on PET ). Below, "PET
Abbreviated as "A". 1 g of each of the above) was diluted with toluene so that the content of toluene was 50% by mass, and IRGACURE (registered trademark) 184 as a photopolymerization initiator was added thereto.
(1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to each sample so as to be 5% by mass and dissolved.
Polyethylene terephthalate film (hereinafter referred to as "PET film")
Abbreviated. ) By the bar coating method (Meyer bar # 12), and this is applied to an ultraviolet irradiation device Toscure 401 (Co., Ltd.)
Curing was carried out using (Toshiba). Cured samples were prepared by irradiating with UV light until each sample was scraped with a finger and prevented from peeling. The test described in Table 2 below was performed on the samples of these eight types of cured products. The results are also shown in Table 2.

[0245]

[Table 2]

As can be seen from the results in Table 2, the compounds of the present invention have good adhesion to PET films, and
It can be seen that a film having good tensile strength and extensibility is formed.

Test of cast polymer product Sample A, sample B, sample C, sample D and vinyl ester (VE) resin (trade name; Lipoxy VR-
77 Showa Highpolymer Co., Ltd.): Styrene = 70:30
(Mass ratio) Dicumyl peroxide was dissolved in the mixed solution in an amount of 2% by mass with respect to each resin, and these solutions were mixed to a thickness of 4
Pour into a mm PET mold. For sample A to sample D, 0.5 hours at 100 ° C + 1 hour at 130 ° C
It was cured under conditions of time + 160 ° C. for 1 hour. Also, V
The E resin (trade name; Lipoxy VR-77 Showa Highpolymer Co., Ltd.): Styrene = 70: 30 (mass ratio) mixture was cured under conditions of 130 ° C. for 1 hour and 160 ° C. for 1 hour.

UP resin (trade name; Yupika 6424)
2% by mass of Percure HO was dissolved in UP resin in Niupika Japan Co., Ltd., and these solutions were poured into a glass mold having a thickness of 4 mm. This liquid at 60 ° C for 1 hour +16
It was cured at 0 ° C. for 1 hour. The mechanical properties, thermal properties, electrical properties, optical properties, etc. of these cured products were measured. The results are shown in Table 3.

[0249]

[Table 3]

As can be seen from the results in Table 3, the cured product of the present invention is a cured product having excellent mechanical properties, particularly impact resistance.

2 mass% of dicumyl peroxide was dissolved in each of the test polymer K, sample L and sample M of the cast polymer product with respect to each resin, and these solutions were put into a glass mold having a thickness of 4 mm. Poured. For samples A to D, 120
5 hours at ℃ + 5 hours at 130 ℃ + 5 hours at 140 ℃ +1
It was cured under the conditions of 50 ° C. for 5 hours and 160 ° C. for 2 hours.

The cured products of Sample K, Sample L and Sample M cured under the above conditions were 10 mm × 10 mm × 4.
Cut into 5 mm-sized test pieces, and put each of these 5 test pieces into a 300 ml eggplant-shaped flask, and then,
Chloroform (150 ml) was added, a reflux condenser was attached, and the mixture was heated to reflux chloroform for 3 hours. Then, the mixture was cooled to room temperature, and gel permeation chromatography (column: F-801 (Showa Denko KK) was used to determine whether the catalyst was extracted into chloroform.
(Manufactured by, eluent: chloroform, detector: RI detector). As a result, no catalyst was detected in the chloroform used to extract the test piece prepared from the cured product of sample K and the chloroform used to extract the test piece prepared from the cured product of sample L. However, from the chloroform used to extract the test pieces prepared from the cured product of sample M, the catalyst 2,4,6
-Tris (dimethylaminomethyl) phenol was detected.

From the above results, when a polymerizable composition was produced using a catalyst having a radically polymerizable functional group, the catalyst was not eluted from the cured product obtained by curing the polymerizable composition. I understand.

[0254]

EFFECTS OF THE INVENTION According to the present invention, a radical polymerizable property is imparted to enable heat curing and / or active energy ray curing, and further, adhesion to a substrate such as PET, tensile strength and elongation are improved. Novel polymerizable compound capable of forming a good film and capable of producing a molded article having good impact resistance, method for producing the compound, polymerizable composition using the compound, and polymerization It is obvious that a cured product obtained by curing the resin composition and a method for producing the cured product can be provided.

[0255]

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR spectrum of Sample A.

FIG. 2 is an IR spectrum of sample A.

FIG. 3 is a ¹ H-NMR spectrum of Sample B.

FIG. 4 is an IR spectrum of Sample B.

FIG. 5 is a ¹ H-NMR spectrum of Sample C.

FIG. 6 is an IR spectrum of Sample C.

FIG. 7 is a ¹ H-NMR spectrum of Sample D.

FIG. 8 is an IR spectrum of Sample D.

Continued front page    (72) Inventor Kazuhiko Oga             Showa Denko Co., Ltd.             Company Oita Production and Technology Division (72) Inventor Kazumi Kai             Showa Denko Co., Ltd.             Company Oita Production and Technology Division (72) Inventor Hiroshi Uchida             Showa Denko Co., Ltd.             Company Oita Production and Technology Division F-term (reference) 4J005 AA12 BB02 BD02                 4J027 AC02 AC03 AC04 AC06 AC07                       AJ02 CB04 CB10 CC02 CC05                       CC06 CC07 CC08                 4J036 AB01 AB02 AB07 AD05 AD08                       AF06 AF08 AG06 AG07 CA20                       CD12 HA02 HA03                 4J100 AB02Q AL92P CA01 CA04                       JA07

Claims (16)

[Claims] 1. A polymerizable compound represented by the following general formula (1): General formula (1) (In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² is an alcohol compound or a phenol compound. Or represents an organic residue derived from a carboxylic acid compound, n represents an integer of 0 to 20, and R ² further represents a group represented by the following general formula (2) and / or the following general formula (3). Can be included.) General formula (2) (In the formula, each R ¹ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n represents an integer of 0 to 20. General formula (3) (In the formula, R ³ represents either H or CH _3. ) 2. In the general formula (1), each R ¹ is independently at least one organic residue selected from the organic residues represented by the following structural formulas (1) to (7). The polymerizable compound according to claim 1, wherein the polymerizable compound is present. Structural formula (1) Structural formula (2) Structural formula (3): Structural formula (4) Structural formula (5) Structural formula (6) Structural formula (7): 3. In the general formula (1), R ² is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin or triglyceride. Methylol ethane, trimethylol propane, 1,4
-Cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, 1 , 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid, and a compound selected from the group consisting of terephthalic acid. 2. A derived organic residue.
Alternatively, the polymerizable compound according to claim 2. 4. In the general formula (1), R ¹ is at least one or more independently selected from the organic residues represented by the following structural formulas (1) to (7), and R 1 ² is ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol,
Glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A,
Hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, 1,2
Derived from a compound selected from the group consisting of cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid. The polymerizable compound according to any one of claims 1 to 3, which is an organic residue. Structural formula (1) Structural formula (2) Structural formula (3): Structural formula (4): Structural formula (5) Structural formula (6) Structural formula (7): 5. The method for producing a polymerizable compound according to any one of claims 1 to 4, which comprises the following steps. In the presence of a process catalyst, at least one or more compounds selected from the compounds represented by the following general formula (4) and at least one or more compounds selected from the compounds represented by the following general formula (5) are subjected to an addition reaction. To the step of obtaining the polymerizable compound according to any one of claims 4 to 4, general formula (4): (In the formula, R ⁴ represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound, and q
Represents an integer of 1 or more. ) General formula (5): (In the formula, each R ⁵ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n represents an integer of 0 to 20. Represents.) 6. The method for producing a polymerizable compound according to any one of claims 1 to 4, which comprises the following steps. In the presence of a process catalyst, at least one or more compounds selected from the compounds represented by the following general formula (4), at least one or more compounds selected from the compounds represented by the following general formula (5), and the following general formula (6): A step of performing at least one addition reaction selected from the compounds represented to obtain the polymerizable compound according to any one of claims 1 to 4, general formula (4): (In the formula, R ⁴ represents an organic residue derived from an alcohol compound, a phenol compound or a carbonyl compound, and q
Represents an integer of 1 or more. ) General formula (5): (In the formula, each R ⁵ independently represents at least one organic residue selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n represents an integer of 0 to 20. General formula (6) (In the formula, R ⁶ represents either H or CH _3. ) 7. In the general formula (4), R ⁴ is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin or triglyceride. Methylol ethane, trimethylol propane, 1,4
-Cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, 1 , 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid, organic residues derived from terephthalic acid At least 1 type or more, The manufacturing method of the polymeric compound in any one of Claim 5 or Claim 6 characterized by the above-mentioned. 8. In the general formula (5), each R ⁵ is independently at least one selected from the organic residues represented by the following structural formulas (1) to (7). The method for producing a polymerizable compound according to any one of claims 5 to 7, which is characterized. Structural formula (1) Structural formula (2) Structural formula (3) Structural formula (4): Structural formula (5): Structural formula (6) Structural formula (7): 9. The catalyst contains at least one selected from the group consisting of metal halides, tertiary amines, pyridine compounds, pyridinium salts, quaternary ammonium salts, phosphine compounds and phosphonium salts. A method for producing the polymerizable compound according to any one of claims 5 to 8. 10. The catalyst is tin chloride, pyridine, isoquinoline, quinoline, benzyltrimethylammonium salt,
Group consisting of benzyltriethylammonium salt, 2,4,6-tris (dimethylaminomethyl) phenol, triethylamine, triphenylphosphine, ethyltriphenylphosphonium salt, tetraphenylphosphonium salt, benzyltriphenylphosphonium salt 9. The method for producing a polymerizable compound according to claim 5, further comprising at least one selected from the group consisting of: 11. The method for producing a polymerizable compound according to claim 5, wherein the catalyst is a catalyst having a radically polymerizable functional group. 12. A catalyst having a radically polymerizable functional group is N, N-dimethylaminoethyl methacrylate,
N, N-dimethylaminoethyl acrylate, trimethylmethacryloyloxyethylammonium salt, trimethylacryloyloxyethylammonium salt, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N- (3-N ', N'-dimethyl Aminopropyl)
At least one selected from the group consisting of acrylamide, N- (3-N ', N'-dimethylaminopropyl) methacrylamide, trimethylacryloylaminopropylammonium salt, trimethylmethacryloylaminopropylammonium salt, and dimethyldiallylammonium salt. The method for producing a polymerizable compound according to claim 11, wherein: 13. A polymerizable composition comprising at least one or more of the polymerizable compounds according to claim 1 as an essential component. 14. A total curable component 100 in a polymerizable composition.
The polymerizable composition according to claim 13, which contains 0.1 to 10 parts by mass of at least one radical polymerization initiator with respect to parts by mass. 15. A cured product obtained by curing the polymerizable composition according to claim 13 or 14. 16. The method for curing a cured product according to claim 15, wherein the curing method is heat curing and / or curing with an active energy ray.