JP2008308420A - Carboxylic acid ester compound having alicyclic epoxy group and vinyl ether group, and method for producing the ester compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cationic polymerization-based polymerizable composition having a low smelling property and low skin irritating property, and also giving a material excellent in tackiness, having a low shrinkage and mechanical characteristics, and also a cured material obtained by curing the polymerizable composition. <P>SOLUTION: This new carboxylic acid ester having both of an alicyclic epoxy group and a vinyl ether group, the method for producing the same, the polymerizable composition containing the same, and the cured material obtained by curing the same are provided. The carboxylic acid ester having both of the alicyclic epoxy group and vinyl ether group has the low smelling property and low skin irritating property, and the polymerizable composition containing the same is very useful in various fields such as coating agents, ink, paint, adhesives, resists, printing plate materials, insulating materials, optical materials, etc. The polymerizable composition has a low shrinkage on curing, and especially the polymerizable composition containing a photo-cationic polymerization initiator shows a characteristic of having almost no polymerization inhibition by oxygen on its curing. Also, since it has low viscosity, it is excellent in dilution property and processability. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a novel carboxylic acid ester compound having an alicyclic epoxy group and a vinyl ether group, a polymerizable composition containing the compound, and a cured product thereof.
The ester compound having an alicyclic epoxy group and a vinyl ether group of the present invention is a highly reactive monomer. In addition to being used as various crosslinking agents and reactive diluents, the polymer itself is excellent in electrical properties, dimensional stability, heat resistance, weather resistance, chemical resistance, mechanical properties, and as various molded products or optical materials. Use is also expected.

  Currently, polymerizable compositions such as ultraviolet curable resins and electron beam curable resins are mainly used in many fields such as inks, paints, adhesives, resists, and platemaking materials. As the main component of this polymerizable composition, acrylic monomers and polyfunctional acrylates are the most common.

  However, acrylic monomers have various problems associated with skin irritation, odor and oxygen-induced polymerization inhibition. On the other hand, cationically polymerizable compounds such as alicyclic epoxy compounds and vinyl ether compounds have the characteristics of low skin irritation, low odor, and little influence of oxygen. There are few examples of obtaining a polymerized cured product.

For example, as an ester compound having both an alicyclic epoxy group and a vinyl ether group in one molecule, JP-A-11-171967 discloses 4-vinyloxymethylcyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate. However, it does not show a curable composition that gives a cured product excellent in tackiness, low shrinkage, or mechanical properties.
Japanese Patent Laid-Open No. 11-171967

It is an object of the present invention to provide a cationically polymerizable composition that has low odor and low skin irritation, and that provides an excellent effect in terms of tackiness, low shrinkage and mechanical properties.
Moreover, it aims at providing the hardened | cured material which hardened | cured the polymeric composition.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel compound that can provide a composition that satisfies the above requirements and is extremely useful in various fields, and has completed the present invention.

  That is, the present invention relates to a novel carboxylic acid ester compound having an alicyclic epoxy group and a vinyl ether group and a method for producing the same. Moreover, this invention relates to the polymeric composition which uses this compound as an essential component, and its hardened | cured material.

  Furthermore, the present invention relates to a carboxylic acid ester compound having an alicyclic epoxy group and a vinyl ether group shown in [1] below, a method for producing a carboxylic acid ester shown in [2] to [5], [6] ] The polymerizable composition shown by [7] and the cured product shown by [7].

[1] Carboxylic acid ester represented by the following general formula (1) or the following general formula (2).
General formula (1)

(In the formula, R ¹ represents the following general formula (3) or an alkylene group having 2 to 9 carbon atoms. In the formula, R ^{2 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, and a carbon number of 1; Represents an atom or atomic group selected from alkyl groups of -4.
General formula (3)

（式中、ｎは１〜４の整数を表す。）
一般式（２）

(In the formula, n represents an integer of 1 to 4.)
General formula (2)

（式中、Ｒ^１１は、下記一般式（４）又は炭素数２〜９のアルキレン基を表す。式中、Ｒ^１２〜Ｒ^２０は、それぞれ独立に、水素原子、ハロゲン原子、及び炭素数１〜４のアルキル基から選ばれる原子または原子団を表す。）
一般式（４）

^{(Wherein, R 11} is in. The formula which represents the following general formula (4) or alkylene group of 2 to 9 carbon ^atoms, R 12 ^{to R 20} are independently a hydrogen atom, a halogen atom, and 1 carbon atoms Represents an atom or atomic group selected from alkyl groups of -4.
General formula (4)

（式中、ｍは１〜４の整数を表す。）
［２］ エステル交換触媒の存在下、下記一般式（５）又は（６）で表されるヒドロキ
シル基含有ビニルエーテル化合物の群から選ばれる少なくとも１種と、下記一般式（７）
又は下記一般式（８）で表される脂環式エポキシ基含有カルボン酸エステルの群から選ばれる少なくとも１種を反応させて、［１］に記載のカルボン酸エステルを製造する方法。一般式（５）

(In the formula, m represents an integer of 1 to 4.)
[2] In the presence of a transesterification catalyst, at least one selected from the group of hydroxyl group-containing vinyl ether compounds represented by the following general formula (5) or (6), and the following general formula (7)
Or the method of making at least 1 sort (s) chosen from the group of the alicyclic epoxy group containing carboxylic acid ester represented by following General formula (8) reacting, and manufacturing the carboxylic acid ester as described in [1]. General formula (5)

（式中、ｐは０〜４の整数を表す。）
一般式（６）

(In the formula, p represents an integer of 0 to 4.)
General formula (6)

（式中、Ｒ^２１は炭素数２〜９のアルキレン基を表す。）
一般式（７）

(In the formula, R ²¹ represents an alkylene group having 2 to 9 carbon atoms.)
General formula (7)

（式中、Ｒ^２２は炭素数１〜４のアルキル基又は炭素数３〜４のアルケニル基を表す。）
一般式（８）

(In the formula, R ²² represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)
General formula (8)

(In the formula, R ²³ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)
[3] The transesterification catalyst is a dialkyl tin oxide, a tetraalkyl titanate,
[2], which is at least one compound selected from the group consisting of a metal acetylacetonate complex, an alkali metal hydroxide, an alkaline earth metal hydroxide, and potassium carbonate The manufacturing method of carboxylic acid ester of this.

[4] The method according to [2] or [3], wherein the alkyl alcohol having 1 to 4 carbon atoms or the alkenyl alcohol having 3 to 4 carbon atoms generated during the reaction is reacted while distilling out of the reaction system. The manufacturing method of carboxylic acid ester of this.

[5] Hydroxy group-containing vinyl ether represented by the general formula (5) or (6) having a boiling point higher than that of the alkyl alcohol having 1 to 4 carbon atoms or the alkenyl alcohol having 3 to 4 carbon atoms generated during the reaction. [4] The method for producing a carboxylic acid ester according to [4].

[6] A polymerizable composition comprising the carboxylic acid ester according to [1] as an essential component.
[7] A cured product obtained by curing the polymerizable composition as described in [6].

  The carboxylic acid ester containing an alicyclic epoxy group and a vinyl ether group of the present invention has low odor and low skin irritation, and the polymerizable composition containing the carboxylic acid ester includes a coating agent, an ink, a paint, an adhesive, It is extremely useful in various fields such as resists, plate-making materials, insulating materials and optical materials. This polymerizable composition has a small cure shrinkage ratio, and the polymerizable composition of the present invention containing a cationic polymerization initiator, particularly a photocationic polymerization initiator, has a feature that there is almost no inhibition of polymerization by oxygen during curing. Moreover, since it is low-viscosity, it is excellent also in dilution property and workability.

  The cured product of the present invention is excellent in terms of tackiness, low shrinkage and mechanical properties.

The present invention will be specifically described below.
The present invention (I) relates to a carboxylic acid ester represented by the following general formula (1) or the following general formula (2).

The present invention (II) relates to a method for producing a carboxylic acid ester containing the alicyclic epoxy group and vinyl ether group of the present invention (I).
The present invention (III) is a polymerizable composition comprising the carboxylic acid ester containing the alicyclic epoxy group and vinyl ether group of the present invention (II).

The present invention (IV) is a cured product obtained by curing the polymerizable composition of the present invention (III).
First, the present invention (I) will be described.

The present invention (I) is a carboxylic acid ester containing an alicyclic epoxy group and a vinyl ether group, which is represented by the following general formula (1) or the following general formula (2).
General formula (1)

（式中、Ｒ^１は、下記一般式（３）又は炭素数２〜９のアルキレン基を表す。式中、Ｒ^２〜Ｒ^１０は、それぞれ独立に、水素原子、ハロゲン原子、及び炭素数１〜４のアルキル基から選ばれる原子または原子団を表す。）
一般式（３）

(In the formula, R ¹ represents the following general formula (3) or an alkylene group having 2 to 9 carbon atoms. In the formula, R ^{2 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, and a carbon number of 1; Represents an atom or atomic group selected from alkyl groups of -4.
General formula (3)

（式中、ｎは１〜４の整数を表す。）
一般式（２）

(In the formula, n represents an integer of 1 to 4.)
General formula (2)

（式中、Ｒ^１１は、下記一般式（４）又は炭素数２〜９のアルキレン基を表す。式中、Ｒ^１２〜Ｒ^２０は、それぞれ独立に、水素原子、ハロゲン原子、及び炭素数１〜４のアルキル基から選ばれる原子または原子団を表す。）
一般式（４）

^{(Wherein, R 11} is in. The formula which represents the following general formula (4) or alkylene group of 2 to 9 carbon ^atoms, R 12 ^{to R 20} are independently a hydrogen atom, a halogen atom, and 1 carbon atoms Represents an atom or atomic group selected from alkyl groups of -4.
General formula (4)

（式中、ｍは１〜４の整数を表す。）
一般式（１）において、Ｒ^２〜Ｒ^１０は、それぞれ独立に、水素原子、ハロゲン原子、及び炭素数１〜４のアルキル基から選ばれる原子または原子団を表す。ここでいう「炭素数１〜４のアルキル基」としては、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基が挙げられる。また、ここでいう「それぞれ独立に」とは、Ｒ^２〜Ｒ^１０のそれぞれが、
まったく異なる構造の基であっても、すべてが同じ基であっても、また、一部が同じ基で、その他が異なる基であってもよいこと意味する。他の一般式についても同様である。

(In the formula, m represents an integer of 1 to 4.)
In General Formula (1), R ^{2 to} R ¹⁰ each independently represents an atom or an atomic group selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms. Specific examples of the “alkyl group having 1 to 4 carbon atoms” herein include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert- A butyl group is mentioned. In addition, “independently” here means that each of R ^{2 to} R ¹⁰ is
It means that even if they are groups having completely different structures, all may be the same group, or some may be the same group and others may be different groups. The same applies to other general formulas.

In General Formula (1), R ¹ represents the following General Formula (3) or an alkylene group having 2 to 9 carbon atoms.
General formula (3)

（式中、ｎは１〜４の整数を表す。）
なお、ここでいう「炭素数２〜９のアルキレン基」は、直鎖状のアルキレン基であっても分岐状のアルキレン基であってもいっこうに差し支えない。

(In the formula, n represents an integer of 1 to 4.)
The “C2-C9 alkylene group” herein may be a linear alkylene group or a branched alkylene group.

  Examples of the alkylene group having 2 to 9 carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, isopropylene group, isobutylene group, and the like. it can.

In General formula (2), R < ¹² > -R < ²⁰ > represents the atom or atomic group chosen from a hydrogen atom, a halogen atom, and a C1-C4 alkyl group each independently. Specific examples of the “alkyl group having 1 to 4 carbon atoms” herein include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert- A butyl group is mentioned.

In General Formula (2), R ¹¹ represents the following General Formula (4) or an alkylene group having 2 to 9 carbon atoms.
General formula (4)

（式中、ｍは１〜４の整数を表す。）
ここでいう「炭素数２〜９のアルキレン基」は、直鎖状のアルキレン基であっても分岐状のアルキレン基であってもいっこうに差し支えない。

(In the formula, m represents an integer of 1 to 4.)
As used herein, the “C2-C9 alkylene group” may be a linear alkylene group or a branched alkylene group.

  Examples of the alkylene group having 2 to 9 carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, isopropylene group, isobutylene group, and the like. it can.

Next, the manufacturing method of this invention (II) is demonstrated.
In the present invention (II), in the presence of a transesterification catalyst, at least one selected from the group of hydroxyl group-containing vinyl ether compounds represented by the following general formula (5) or (6), and the following general formula (7) or The alicyclic epoxy group described in the present invention (I) and a vinyl ether group are contained by reacting at least one selected from the group of alicyclic epoxy group-containing carboxylic acid esters represented by the following general formula (8). This is a method for producing a carboxylic acid ester.
General formula (5)

（式中、ｐは０〜４の整数を表す。）
一般式（６）

(In the formula, p represents an integer of 0 to 4.)
General formula (6)

（式中、Ｒ^２１は炭素数２〜９のアルキレン基を表す。）
一般式（７）

(In the formula, R ²¹ represents an alkylene group having 2 to 9 carbon atoms.)
General formula (7)

（式中、Ｒ^２２は炭素数１〜４のアルキル基又は炭素数３〜４のアルケニル基を表す。）
一般式（８）

(In the formula, R ²² represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)
General formula (8)

(In the formula, R ²³ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)
As the transesterification catalyst, basically any catalyst can be used as long as it activates an ester group to cause a reaction with an alcohol. For example, alkali metals, alkaline earth metals and alkali metals, oxides of alkaline earth metals, weak acid salts of alkali metals and alkaline earth metals, alcoholates of alkali metals and alkaline earth metals, potassium hydroxide, sodium hydroxide, etc. Alkali metal hydroxides, alkaline earth metal hydroxides such as calcium hydroxide, Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn oxides, Hf, Mn , U, Zn, Cd, Zr, Pb, Ti, Co and Sn hydroxides, Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn inorganic acid salts, Hf, Mn, U , Zn, Cd, Zr, Pb, Ti, Co and Sn alkoxides, Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn organic acid salts, Hf, Mn, U, Organic complexes such as acetylacetonate of n, Cd, Zr, Pb, Ti, Co and Sn, organic tin compounds such as dibutyltin oxide, dioctyltin oxide, dibutyltin dichloride, dimethylaniline, 1,4-diazabicyclo [2 2.2] Tertiary amines such as octane.

  Among these, dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide, dibutyltin dichloride, tetraalkyl titanates such as tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, manganese acetylacetonate, zirconium acetylacetonate, hafnium It is preferable to use a metal acetylacetonate complex such as acetylacetonate, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, or potassium carbonate. .

  Among these, particularly preferred are dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide and dibutyltin dichloride, metal acetylacetonates such as manganese acetylacetonate, zirconium acetylacetonate and hafnium acetylacetonate. It is a complex.

In General formula (5), p represents the integer of 0-4.
Specific examples of the hydroxyl group-containing vinyl ether compound represented by the general formula (5) include compounds represented by the following general formulas (9) to (12).
General formula (9)

一般式（１０）

General formula (10)

一般式（１１）

Formula (11)

一般式（１２）

Formula (12)

Considering the physical properties of the cured product or the availability of raw materials, preferred compounds among these include:
General formula (9)

及び
一般式（１０）

And general formula (10)

Can be mentioned.
In the general formula (6), R ²¹ represents an alkylene group having 2 to 9 carbon atoms. In addition, the “C2-C9 alkylene group” herein may be a linear alkylene group or a branched alkylene group.

As specific examples of the hydroxyl group-containing vinyl ether compound represented by the general formula (6),
2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 9-hydroxynonyl vinyl ether, 2-hydroxypropyl vinyl ether, 3-hydroxybutyl vinyl ether, 3-hydroxy-2-methylpentyl A vinyl ether etc. can be mentioned.

  Among these, preferred are hydroxy group-containing vinyl ether compounds having a primary hydroxyl group such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 9-hydroxynonyl vinyl ether and the like. Can be mentioned.

In the general formula (7), R ²² represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms. Specific examples of R ²² include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an n-butyl group, an allyl group, and a methallyl group. In view of the reactivity of the transesterification reaction, an allyl group and a methallyl group are preferable.

In General Formula (7), R ^{2 to} R ¹⁰ each independently represent an atom or an atomic group selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms. In addition, the “C1-C4 alkyl group” herein may be a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group.

In the general formula ^{(8), R 23} represents an alkyl group or an alkenyl group of 3-4 carbon atoms having 1 to 4 carbon atoms. Specific examples of R ³⁴ include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an n-butyl group, an allyl group, and a methallyl group. In view of the reactivity of the transesterification reaction, an allyl group and a methallyl group are preferable.

In General formula (8), R < ¹² > -R < ²⁰ > represents the atom or atomic group chosen from a hydrogen atom, a halogen atom, and a C1-C4 alkyl group each independently as above-mentioned. In addition, the “C1-C4 alkyl group” herein may be a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group.

  The form of the reaction of the present invention (II) is represented by the alicyclic epoxy group-containing carboxylic acid ester represented by the general formula (7) or the general formula (8) and the general formula (5) or the general formula (6). The hydroxyl group-containing vinyl ether compound is heated in the presence of a transesterification catalyst. The reaction temperature varies depending on the type of transesterification catalyst used, but is selected from the range of 30 to 200 ° C., preferably 50 to 150 ° C., and is inert under normal pressure or increased pressure, or under reduced pressure as necessary. It is desirable to be performed in a gas atmosphere. Furthermore, since the transesterification reaction is an equilibrium reaction, in order to advance the reaction efficiently, it is better to distill the produced alcohol quickly out of the reaction system.

  Moreover, in order to advance reaction efficiently, it is desirable that the produced | generated alcohol is rapidly distilled out of a reaction system, but in that case, it is general formula (5) or general formula (6) used as a raw material in that case It is desirable that the hydroxyl group-containing vinyl ether compound represented by) is not distilled off as much as possible. Therefore, it is desirable to use a hydroxy group-containing vinyl ether having a boiling point higher than that of the alcohol produced during the reaction as a raw material. If such a compound is used, the reaction is carried out while maintaining the hydroxy group-containing vinyl ether in the reaction system by performing the above reaction at a temperature higher than the boiling point of the alcohol produced during the reaction and lower than the boiling point of the hydroxy group-containing vinyl ether. The alcohol produced therein can be quickly distilled out of the reaction system.

  As a usage-amount of the hydroxyl group containing vinyl ether compound represented by General formula (5) or General formula (6), the alicyclic epoxy group represented by General formula (7) or General formula (8) which is a raw material is used. The theoretical amount is at least necessary for the carboxylic acid ester, and it is better to use an excess molar amount in consideration of reaction rate, equilibrium and the like. However, even if this hydroxyl group-containing vinyl ether compound is used in an excessive amount, an effect commensurate with the excess amount cannot be obtained, which is economically undesirable. Therefore, the hydroxyl group-containing vinyl ether compound represented by the general formula (5) or the general formula (6) usually has an alicyclic epoxy group represented by the general formula (7) or the general formula (8) as a raw material. About 1.0-5 times mole is used with respect to the theoretical amount of carboxylic acid ester, preferably about 1.1-4 times mole. As a charging method at that time, the charging may be performed at the beginning of the reaction or may be sequentially added during the reaction.

  The amount of the transesterification catalyst used is about 0.01 to 3 parts by mass, preferably about 0.05 to 2 parts by mass with respect to 100 parts by mass of the raw material ester. In this case as well, if the amount is too small, the reaction rate slows down.If the amount is too large, not only the effect corresponding to the amount can be obtained, but also the coloration becomes severe, and the yield decreases due to side reactions. There is even a case. Further, depending on the type of transesterification catalyst to be used, excessive use has a problem that it takes a lot of time and labor to separate from the transesterification catalyst.

  The method for isolating the carboxylic acid ester of the present invention (I) varies depending on the type of catalyst used. For example, when dibutyltin dioxide is used, the generated alcohol and the excess hydroxyl group-containing vinyl ether compound are distilled. In the case where the produced carboxylic acid ester containing an alicyclic epoxy group and a vinyl ether group is a distillable compound, a purified product that can be used as a product can be obtained only by distillation purification. Moreover, in the case of a compound in which the produced carboxylic acid ester containing an alicyclic epoxy group and a vinyl ether group cannot be distilled, it can be purified using means such as washing with water.

Next, the polymerizable composition of the present invention (III) will be described.
The present invention (III) is a polymerizable composition comprising the carboxylic acid ester containing the alicyclic epoxy group and vinyl ether group described in the present invention (I) as essential components.

  The polymerizable composition of the present invention (III) often contains a polymerization initiator, but it is confused with a maleimide compound and irradiated with light, or in special cases such as electron beam curing. May not require a polymerization initiator.

In the polymerizable composition of the present invention (III), various polymerizable compounds, curing accelerators, dyes, pigments, plasticizers, inorganic fillers, solvents and the like may be mixed as required in addition to the polymerization initiator. it can.
The polymerization initiator that can be used is not particularly limited as long as it can cause cationic polymerization such as a thermal polymerization initiator and a photopolymerization initiator. The vinyl ether group can be radically polymerized when mixed with maleic anhydride, tetrafluoroethylene, etc. In such a case, a radical polymerization initiator can be used.

  Specific examples of the thermal polymerization initiator that can be used include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis-2,4-dimethyl. In addition to radical initiators such as valeronitrile and azobiscyclohexanecarbonitrile, cationic polymerization initiators such as Lewis acids such as boron trifluoride, zinc dichloride, and aluminum trichloride are listed.

  Specific examples of the photo radical polymerization initiator that can be used include 2,4-diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate, 4-dimethylaminoethylbenzoate, and the like.

Specific examples of the cationic photopolymerization initiator that can be used include Japanese Patent Publication No. 53-32831, Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, Japanese Patent Publication No. 52-25686, and Japanese Patent Publication No. Sho. 61-34752, JP-A-54-53181, JP-A-54-95686, JP-B-61-36530, JP-B-59-19581, JP-B-63-65688, JP-A-55-164204, JP-B 60-30690, JP-B 63-36332, JP-B 1-33923, JP-B 2-10171, JP-B 5-15721, JP-B 4-62310, JP-B 62-57653, JP-B No. 3-12081, No. 3-12082, No. 3-16361, No. 63-12092, No. 63-12093, No. 6 No. -12095, Japanese Patent Publication No. 63-12094, Japanese equity 2-37924 Patent, Kokoku 2-35764 Patent, Kokoku 4-13374 Patent, Kokoku 4-759
08, JP-B-4-73428, JP-B-53-32831, JP-A-2-150848, JP-A-2-296514, US Pat. No. 4,069,055, US Pat. No. 4,069,056 And sulfonium salts, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, arsonium salts and iron / arene complexes described in US Pat. No. 3,703,296.

  These polymerization initiators are usually 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable components contained in the polymerizable composition of the present invention (III). Partly used, and may be mixed immediately before obtaining the cured product of the present invention (IV) described later, or may be mixed in advance in the polymerizable composition of the present invention (III).

Finally, the cured product of the present invention (IV) will be described.
The present invention (IV) is a cured product obtained by curing the polymerizable composition of the present invention (III).

Examples of the curing method of the polymerizable composition of the present invention (III) include thermal curing and / or curing with active energy rays, and thermal curing and / or curing with near infrared rays, visible rays, ultraviolet rays, and electron beams. Thermal curing and / or curing with visible light or ultraviolet light is particularly preferable. Also, a cured product can be obtained by combining two or more different curing methods.

  Among the active energy rays, the light source for curing by visible light or ultraviolet light 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. A lamp, an incandescent bulb, a fluorescent lamp, an excimer lamp, a laser, or the like can be used. Of these light sources, a high-pressure mercury lamp and a metal halide lamp are particularly preferable.

The wavelength of the visible light or ultraviolet curing light source is usually 200 nm to 750 nm, preferably 200 nm to 450 nm, and the irradiation amount is usually 50 mJ / cm ^{2 to} 2000 mJ / cm ² , preferably 100 mJ / cm ^{2 to} 1500 mJ / cm ^2. It is.

  In curing using an electron beam, examples of the irradiation method include a scanning method, a broad beam method, a curtain beam method, and an ion plasma method, and the irradiation amount is usually 0.1 Gy to 200 kGy, and 1 Gy to 100 kGy is preferred.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.
(Execution synthesis example 1)
In a 500 ml three-necked round bottom flask equipped with a thermometer and rectifying column, 251 g (1.38 mol) of allyl 3,4-epoxycyclohexane-1-carboxylate and 4-hydroxybutyl vinyl ether containing 100 ppm KOH (boiling point 187 ° C.) 200 g (1.72 mol) and 0.5 g of dibutyltin oxide were added, and the temperature was raised to 120 ° C. using an oil bath while stirring. With the progress of the reaction, allyl alcohol (boiling point 96.90 ° C.) produced was distilled from the rectification column and obtained in a 100 ml eggplant type flask, and reacted for 6 hours. After completion of the reaction, it was confirmed by GC analysis that 97.0% of the compound of the following structural formula 1 was formed with respect to allyl 3,4-epoxycyclohexane-1-carboxylate. Thereafter, excess hydroxybutyl vinyl ether was distilled off under reduced pressure. Thereafter, the contents in the three-necked round bottom flask were replaced with an eggplant-shaped flask and distilled under reduced pressure to obtain 310.0 g (yield 93.7%) of a colorless and transparent compound of the following structural formula 1, which is a carboxylic acid ester of the present invention. Got.
(Structural formula 1)

400Mz ¹ H-NMR spectrum and IR spectrum of the compound of structural formula 1 are shown in FIG. 1 and FIG. 2, respectively.
(Execution synthesis example 2)
In a 500 ml three-necked round bottom flask equipped with a thermometer and rectifying column, 186 g (1.02 mol) of allyl 3,4-epoxycyclohexane-1-carboxylate and 2- (hydroxyethoxy) ethyl vinyl ether (boiling point) with 100 ppm KOH (208 ° C.) 168.6 g (1.28 mol) and dibutyltin oxide 0.5 g were added, and the temperature was raised to 120 ° C. using an oil bath while stirring. With the progress of the reaction, allyl alcohol produced was distilled from the rectifying column and obtained in a 100 ml eggplant type flask, and reacted for 6 hours. After completion of the reaction, it was confirmed by GC analysis that 90.0% of the compound of the following structural formula 2 was formed with respect to allyl 3,4-epoxycyclohexane-1-carboxylate. Thereafter, excess hydroxybutyl vinyl ether was distilled off under reduced pressure. Thereafter, the contents in the three-necked round-bottom flask were replaced with an eggplant-shaped flask and distilled under reduced pressure, and 210.0 g (yield: 85.6%) of a colorless and transparent compound of the following structural formula 2, which is a carboxylic acid ester of the present invention. Got.
(Structural formula 2)

400Mz ¹ H-NMR spectrum and IR spectrum of the compound of Structural Formula 2 are shown in FIGS. 3 and 4, respectively.
(Execution synthesis example 3)
In a 500 ml three-necked round bottom flask equipped with a thermometer and a rectifying column, 215 g (1.38 mol) of methyl 3,4-epoxycyclohexane-1-carboxylate and 200 g (1.72 mol) of 4-hydroxybutyl vinyl ether containing 100 ppm of KOH were added. ) And 0.5 g of dibutyltin oxide were added, and the temperature was raised to 140 ° C. using an oil bath while stirring. With the progress of the reaction, the produced methyl alcohol (boiling point 64.65 ° C.) was distilled from the rectification column and obtained in a 100 ml eggplant type flask and reacted for 10 hours. After completion of the reaction, 92.0% based on GC analysis based on methyl 3,4-epoxycyclohexane-1-carboxylate
It was confirmed that a compound of the following structural formula 1 was produced. Thereafter, excess hydroxybutyl vinyl ether was distilled off under reduced pressure. Thereafter, the contents in the three-necked round bottom flask were replaced with an eggplant-shaped flask and distilled under reduced pressure to obtain 290.0 g (yield: 87.6%) of a colorless and transparent compound 1 having the following structure 1, which is a carboxylic acid ester of the present invention. Obtained.
(Structural formula 1)

The compounds of structural formulas 1 and 2 had a weak odor and little irritation to the skin.
Example 1-A
Curing test:
2 parts by mass of a cationic polymerization initiator (trade name: CPI-101A) manufactured by San Apro Co., Ltd. was mixed with 100 parts by mass of the compound of Structural Formula 1 to obtain the polymerizable composition 1 of the present invention. The polymerizable composition 1 was applied to a polyimide film (trade name; Kapton 150EN manufactured by Toray DuPont Co., Ltd.) so as to have a thickness of about 30 μm using a bar coater.

Thereafter, an ultraviolet exposure apparatus (Model: QRU-2161-J (Ltd.) Oak Seisakusho) ^{using, 600mJ / cm 2, 900mJ /} cm 2, 1200mJ / cm 2 and irradiation amount of 1500 mJ / cm ² (365 nm values ) Was exposed to cure the polymerizable composition 1 to obtain a cured product 1 of the present invention.

Thereafter, the presence or absence of tack of the cured product 1 and the folding resistance test were evaluated. The evaluation results are shown in Table 1.
(Example 2-A)
Curing test:
Similarly, 100 parts by mass of the compound of Structural Formula 2 was mixed with 2 parts by mass of CPI-101A to obtain a polymerizable composition 2 of the present invention. The cured product 2 obtained by curing the polymerizable composition 2 in the same manner as in Example 1-A was also evaluated for the presence or absence of tack and the folding resistance test. The results are shown in Table 1.

(Comparative Example 1-A)
In 100 parts by mass of 1,4-butanediol diacrylate (trade name: V # 195, manufactured by Osaka Organic Chemical Co., Ltd.), 2 masses of photopolymerization initiator (trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) Part was dissolved to obtain a polysynthetic composition 5. The polysynthesize composition 5 was applied to a polyimide film (trade name; Kapton 150EN manufactured by Toray DuPont Co., Ltd.) so as to have a thickness of about 30 μm using a bar coater.

Thereafter, an ultraviolet exposure apparatus (Model: QRU-2161-J (Ltd.) Oak Seisakusho) ^{using, 600mJ / cm 2, 900mJ /} cm 2, 1200mJ / cm 2 and irradiation amount of 1500 mJ / cm ² (365 nm values ) Was exposed to cure the polymerizable composition 5 to obtain a cured product 5.

Thereafter, the presence or absence of tack of this cured product 5 and the folding resistance test were evaluated. The evaluation results are shown in Table 1.
Moreover, the presence or absence of tack and the evaluation method of folding resistance are described below.
Assessment of the presence or absence of tack:
The cured product was cooled in a room at room temperature of 25 ° C., and after the surface of the coating film reached 25 ° C., the coating film was pushed with an index finger to confirm the presence or absence of tack. The results are shown in Table 1.
Folding test evaluation:
Polyimide film (trade name; Kapton 150EN, manufactured by Toray DuPont Co., Ltd.) with the cured product of the present invention (IV) facing outward, folded by hand, sandwiched between thumb and index finger, and then using an optical microscope Thus, it was evaluated whether or not a crack occurred at the bent part.

○: No cracks occurred in the bent part.
X: A crack occurred in the bent part.

(Example 1-B)
A polymerizable composition 3 of the present invention was obtained by mixing 50 parts by mass of the compound of Structural Formula 1 with 1.5 parts by mass of a cationic polymerization initiator (Sun Aid SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.). The polymerizable composition 3 is poured into a casting plate in which a 1 mm thick silicone tube is sandwiched between two glass plates coated with a release agent (Daikin Kogyo Co., Ltd., trade name: Die Free) on the inner surface, and an oven is used. Then, curing was performed over a total of 15 hours of 70 ° C. for 4 hours, 80 ° C. for 4 hours, 90 ° C. for 5 hours, and 95 ° C. for 2 hours to obtain a cured product 3 of the present invention. This hardened | cured material 3 was used for the sample for calculating | requiring a cure shrinkage rate.

(Example 2-B)
A polymerizable composition 4 was obtained by mixing 50 parts by mass of the compound of Structural Formula 2 with 1.5 parts by mass of a cationic polymerization initiator (Sun Aid SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.). Thickness of 1m between two glass plates coated with release agent (Daikin Industries, Ltd., trade name: Die Free) on the inner surface
The polymerizable composition 4 is poured into a casting plate sandwiching m silicone tubes, and cured using an oven for 8 hours at 70 ° C. for 4 hours and 80 ° C. for 4 hours to obtain the cured product 4 of the present invention. Obtained. This hardened | cured material 4 was used for the sample for calculating | requiring a cure shrinkage rate.

(Comparative Example 1-B)
A polysynthetic composition comprising 50 parts by mass of 1,4-butanediol diacrylate (trade name: V # 195, manufactured by Osaka Organic Chemical Co., Ltd.) and 1 part by mass of dilauroyl peroxide as a radical polymerization initiator. 6 was obtained. The polymerizable composition 4 is poured into a casting plate having a 1 mm-thick silicone tube sandwiched between two glass plates coated with a release agent (Daikin Kogyo Co., Ltd., trade name: Die Free) on the inner surface, and an oven is used. The cured product 6 was obtained by curing for 8 hours at 70 ° C. for 4 hours and 100 ° C. for 4 hours. This hardened | cured material 6 was used for the sample for calculating | requiring a cure shrinkage rate.

Measurement of cure shrinkage The cure shrinkage was calculated according to the method described below.
[Calculation method]
Curing shrinkage = (D ₂ -D ₁ ) / D ₂
D ₁ : Density of resin before curing, D ₂ : Density of resin after curing The density was measured according to the following method.
(Measurement of density)
Resin before curing: Measured using a specific gravity bottle in accordance with JIS K 7112.
Resin after curing: Measured by an underwater displacement method according to JIS K 7112.
The measurement results of the curing shrinkage rate of Example 1-B and Example 2-B are shown in Table 2.

  As apparent from the above results, the carboxylic acid ester containing an alicyclic epoxy group and a vinyl ether group of the present invention has low odor and low skin irritation. The polymerizable composition containing the carboxylic acid ester has a small curing shrinkage rate, and can suppress warping of the substrate when a cured product is formed on the substrate. The polymerizable composition of the present invention containing a cationic polymerization initiator, particularly a photocationic polymerization initiator, has a feature that there is almost no inhibition of polymerization by oxygen at the time of curing. This is thought to have led to a reduction in tack. Moreover, since it is low-viscosity, it is excellent also in dilution property and workability. A cured product obtained by curing this polymerizable composition is less prone to tack. In addition, it has excellent mechanical properties such as being hard to crack even when bent. Thus, the carboxylic acid ester of the present invention, the polymerizable composition containing the carboxylic acid ester, and the cured product thereof are used in various fields such as coating agents, inks, paints, adhesives, resists, plate-making materials, insulating materials, and optical materials. Very useful.

FIG. 1 is a 400 Mz ¹ H-NMR spectrum of the compound of structural formula 1. FIG. 2 is an IR spectrum of the compound of structural formula 1. FIG. 3 is a 400 Mz ¹ H-NMR spectrum of the compound of structural formula 2. FIG. 4 is an IR spectrum of the compound of structural formula 2.

Claims (7)

Carboxylic acid ester represented by the following general formula (1) or the following general formula (2).
General formula (1)

(In the formula, R ¹ represents the following general formula (3) or an alkylene group having 2 to 9 carbon atoms. In the formula, R ^{2 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, and a carbon number of 1; Represents an atom or atomic group selected from alkyl groups of -4.
General formula (3)

(In the formula, n represents an integer of 1 to 4.)
General formula (2)

^{(Wherein, R 11} is in. The formula which represents the following general formula (4) or alkylene group of 2 to 9 carbon ^atoms, R 12 ^{to R 20} are independently a hydrogen atom, a halogen atom, and 1 carbon atoms Represents an atom or atomic group selected from alkyl groups of -4.
General formula (4)

(In the formula, m represents an integer of 1 to 4.) In the presence of a transesterification catalyst, at least one selected from the group of hydroxyl group-containing vinyl ether compounds represented by the following general formula (5) or (6), and the following general formula (7) or the following general formula (8): The method of manufacturing the carboxylic acid ester of Claim 1 by making at least 1 sort (s) chosen from the group of the alicyclic epoxy group containing carboxylic acid ester represented.
General formula (5)

(In the formula, p represents an integer of 0 to 4.)
General formula (6)

(In the formula, R ²¹ represents an alkylene group having 2 to 9 carbon atoms.)
General formula (7)

(In the formula, R ²² represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.) General formula (8)

(In the formula, R ²³ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)   The transesterification catalyst is at least one selected from the group consisting of dialkyl tin oxide, tetraalkyl titanate, metal acetylacetonate complex, alkali metal hydroxide, alkaline earth metal hydroxide and potassium carbonate. It is a compound, The manufacturing method of carboxylic acid ester of Claim 2 characterized by the above-mentioned.   The carboxylic acid ester according to claim 2 or 3, wherein the reaction is carried out while distilling out the alkyl alcohol having 1 to 4 carbon atoms or the alkenyl alcohol having 3 to 4 carbon atoms generated during the reaction. Production method.   Use of a hydroxy group-containing vinyl ether represented by the general formula (5) or (6) having a boiling point higher than that of an alkyl alcohol having 1 to 4 carbon atoms or an alkenyl alcohol having 3 to 4 carbon atoms generated during the reaction. The method for producing a carboxylic acid ester according to claim 4.   A polymerizable composition comprising the carboxylic acid ester according to claim 1 as an essential component.   A cured product obtained by curing the polymerizable composition according to claim 6.

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