JP2000239254A - Imido(meth)acrylate compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound, capable of giving a resin composition curable with activated energy rays, fast curable and excellent in resistance to heat, and useful for, e.g. ink. SOLUTION: This compound is shown by formula I [R1 is H or methyl; X is O is R2-O (R2 is a 2-5C straight-chain alkylene or the like), R3 is shown by formula II (R4 and R5 are each H or methyl) or the like, when X is O], e.g. N-((meth)acryloyloxy)-4-methylhexahydrophthalimide. It is obtained by reacting (A) an N-hydroxyimide or N-(hydroxyalkyl)imide compound with (B) (meth)acrylic acid in a solvent (e.g. toluene) in the presence of acid catalyst (e.g. sulfuric acid) under a vacuum at a reaction temperature of 50 to 120 deg.C, while removing water from the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel imide (meth) acrylate compound and a method for producing an imide (meth) acrylate compound.

[0002]

2. Description of the Related Art Hitherto, imide (meth) acrylate compounds have been used as a curing component of a curable composition by active energy rays such as ultraviolet rays. Such a curable composition is useful for applications such as inks, paints, resins for protecting printed wiring boards, coating agents, and adhesives.
In addition, imide (meth) acrylate compounds are excellent in fast-curing properties, heat resistance, chemical resistance, adhesion to various substrates, and the like, and are being studied for application to various fields.

Examples of the curable composition containing an imide (meth) acrylate compound include, for example, N-acryloyloxyethylhexahydrophthalimide and N-acryloyloxyethyl-3-methylhexahydrophthalimide. An ultraviolet curable resin composition suitable for a solder resist ink having excellent solder resistance and electrical insulation used as a permanent protective film for a printed wiring board has been proposed (JP-A-1-242569).

Further, an active energy ray-curable composition using N-acryloyloxyethylhexahydrophthalimide, which is excellent in fast-curing property, flexibility and elongation rate (Japanese Patent Laid-Open No.
No. 36462), a long-chain alkyl acrylate and N
A method of using a copolymer with -acryloyloxyethyl-4-methylhexahydrophthalic acid imide or the like as a leveling agent for powder coating (JP-A-2-102275), N-acryloyloxyethyl-bis ( A charge-controllable toner resin composition containing a polymer having a constituent component such as (methylsilyloxy) hexahydrophthalimide as a binder resin (JP-A-62-81643) is provided. However, the imide (meth) acrylate compounds proposed above have a problem in that they require copolymerization with other (meth) acrylates having high heat resistance because of insufficient heat resistance.

As a method for producing an imide (meth) acrylate such as N-acryloyloxyethylhexahydrophthalimide, for example, Japanese Patent Application Laid-Open No. 1-2425
As described in JP-A-69, an imide (meth) acrylate compound is produced by reacting an N-hydroxyalkylphthalimide compound with (meth) acrylic acid in the presence of an acid catalyst while removing generated water. There are known ways to do this.

However, according to this method, a large amount of a dimer or more addition polymer of (meth) acrylic acid as a raw material or a formed imide (meth) acrylate and other by-products are generated in a large amount. Will be lower. Moreover, since the obtained imide (meth) acrylate contains many impurities, when the imide acrylate obtained by this method is used as an active energy ray-curable resin composition, the curability is reduced or the physical properties of the cured product are reduced. Invites decline,
Further, there is a problem that the cured molded body is colored.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an imide (meth) acrylate compound which is expected to provide an active energy ray-curable resin composition which has fast curing properties and excellent heat resistance. That is. Another object of the present invention is to provide a method for producing a high-purity imide (meth) acrylate compound with high yield.

The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, it has been found that an imide () capable of providing an active energy ray-curable resin composition which has fast curing properties and excellent heat resistance is provided. As the meth) acrylate compound, an imide (meth) acrylate compound having a structure such as hexahydrophthalimide has been found. Furthermore, the present inventors, when reacting an N-hydroxyimide compound or an N- (hydroxyalkyl) imide compound with (meth) acrylic acid in the presence of an acid catalyst, remove water from the reaction system under reduced pressure. By reacting while
The inventors have found that a high-purity imide (meth) acrylate compound can be produced with a high yield, and have completed the present invention based on these findings.

[0009]

According to the present invention, there is provided an imide (meth) acrylate compound represented by the following general formula 1.

Embedded image (In the general formula 1, R ¹ represents a hydrogen atom or a methyl group, and X is an oxygen atom or —R ² —O—. R ²
Represents a chained alkylene group having 2 to 5 carbon atoms or an alkylene group having 3 to 10 carbon atoms having an alicyclic structure.

R ³ is represented by the following general formula 2 or 3 when X is an oxygen atom. R ³ is represented by the following general formula 4 when R ² is an ethylene group. R ³ is represented by the following general formula 2 or 3 when R ² is either a chained alkylene group having 3 to 5 carbon atoms or an alkylene group having 3 to 10 carbon atoms having an alicyclic structure. You.

[0011]

Embedded image (In the general formula 2, R ⁴ and R ⁵ represent a hydrogen atom or a methyl group.)

[0012]

Embedded image (In the general formula 3, m is 0 or 1.)

[0013]

Embedded image (In the general formula 4, m is 0 or 1.)

In the presence of an acid catalyst, an N-hydroxyimide compound or N- (hydroxyalkyl)
An imide (meth) acrylate compound production method for producing an imide (meth) acrylate compound by reacting an imide compound with (meth) acrylic acid,
A method for producing an imide (meth) acrylate compound, characterized in that the reaction is carried out under reduced pressure while removing water from the reaction system, is provided.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The imide (meth) acrylate compound of the present invention is represented by the following general formula 1.

Embedded image (In the general formula 1, R ¹ represents a hydrogen atom or a methyl group, and X is an oxygen atom or —R ² —O—. R ²
Represents a chained alkylene group having 2 to 5 carbon atoms or an alkylene group having 3 to 10 carbon atoms having an alicyclic structure.

R ³ is represented by the following general formula 2 or 3 when X is an oxygen atom. R ³ is represented by the following general formula 4 when R ² is an ethylene group. R ³ is represented by the following general formula 2 or 3 when R ² is either a chained alkylene group having 3 to 5 carbon atoms or an alkylene group having 3 to 10 carbon atoms having an alicyclic structure. You.

[0017]

Embedded image (In the general formula 2, R ⁴ and R ⁵ represent a hydrogen atom or a methyl group.)

[0018]

Embedded image (In the general formula 3, m is 0 or 1.)

[0019]

Embedded image (In the general formula 4, m is 0 or 1.)

In the present invention, the imide (meth) acrylate compound means an imide acrylate compound and an imide methacrylate compound. X is -R ² -
When represented by O—, R ² is any of a chained alkylene group having 2 to 5 carbon atoms or an alkylene group having 5 to 10 carbon atoms having an alicyclic structure. The chain alkylene group having 2 to 5 carbon atoms may be linear or branched. Further, the alkylene group having 3 to 10 carbon atoms having an alicyclic structure means a cycloalkylene group or a cycloalkylene group in which a chain alkylene group is bonded to a cycloalkylene group.

Specific examples of the imide (meth) acrylate compound represented by the general formula 1 include N-((meth) acryloyloxy) -4-methylhexahydrophthalimide and N-((meth) acryloyloxy) -3 -Methylhexahydrophthalimide, N-((meth) acryloyloxy) dihydronadiimide, N-((meth) acryloyloxyethyl) dihydronadiimide, N- (2-
(Meth) acryloyloxypropyl) -4-methylhexahydrophthalimide, N- (1-methyl-2- (meth) acryloyloxyethyl) -4-methylhexahydrophthalimide, N- (2- (meth) acrylic Loyloxycyclopentyl) -4-methylhexahydrophthalimide, N-((meth) acryloyloxyethyl) -tetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodecyl-3,4-dicarboximide and the like. The imide (meth) acrylate compound represented by the general formula 1 of the present invention can be suitably produced by the method of the present invention described below.

Production of imide (meth) acrylate compound
Method The method of the present invention comprises producing an imide (meth) acrylate compound by reacting an N-hydroxyimide compound or an N- (hydroxyalkyl) imide compound with (meth) acrylic acid in the presence of an acid catalyst. A method for producing a meth (acrylate) compound, wherein the reaction is carried out under reduced pressure while removing water from the reaction system.

In the method of the present invention, using a solvent,
When reacting an N-hydroxyimide compound or an N- (hydroxyalkyl) imide compound with (meth) acrylic acid in the presence of an acid catalyst, the reaction is carried out under reduced pressure while removing water from the reaction system. An imide (meth) acrylate compound is produced. In the method of the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, and imide (meth) acrylate compound means imide acrylate compound or imide methacrylate compound.

In the method of the present invention, the molar ratio of the N-hydroxyimide compound or N- (hydroxyalkyl) imide compound to (meth) acrylic acid is usually 0.3
To 1.0, preferably 0.5 to 1.0.
The acid catalyst used in the method of the present invention is a Bronsted acid, a Lewis acid, a strongly acidic ion exchange resin, a heteropoly acid, or the like. Examples of Bronsted acids include sulfuric acid, paratoluenesulfonic acid, benzenesulfonic acid and the like; examples of Lewis acids include trifluoroborane diethyl ether complex and the like; examples of heteropolyacids include tungstic acid and the like. Can be. Of these, sulfuric acid is preferred. These acid catalysts are generally used in a proportion of 0.1 to 100 mol%, preferably 1.0 to 30 mol%, based on (meth) acrylic acid.

In the method of the present invention, it is preferable to use a polymerization inhibitor to suppress polymerization of the starting materials and products during the reaction. Examples of polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, 2,6
-Di-t-butyl-4-methylphenol, phenothiazine, copper chloride and the like are preferable, and p-methoxyphenol is preferable. The amount of polymerization inhibitor used is (meta)
It is usually 0.1 to 10% by weight based on acrylic acid.

The solvent used in the method of the present invention is an aromatic hydrocarbon or an aliphatic hydrocarbon. Examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like. Examples of the aliphatic hydrocarbon include n-hexane, isohexane, cyclohexane, methylcyclohexane and the like. Among them, toluene, xylene and the like are preferable. The solvent is used usually in a proportion of 100 to 1000% by weight, preferably 100 to 500% by weight, based on the total amount of the N-hydroxyimide compound or N- (hydroxyalkyl) imide compound and (meth) acrylic acid. You.

The process of the present invention is usually carried out at a temperature of 50 to 120 ° C., preferably 60 to 100 ° C. The reaction pressure of the method of the present invention is usually 50 to 500 Torr,
Preferably 100 to 400 Torr, more preferably 1
00 to 300 Torr. By reducing the reaction pressure, generation of by-products can be suppressed. The method of the present invention can be completed under such conditions, usually in about 0.5 to 10 hours.

N-hydroxyimide compound or N-hydroxyimide compound
After completion of the reaction between the (hydroxyalkyl) imide compound and (meth) acrylic acid, the reaction solution is usually washed with an alkaline aqueous solution.

The alkaline aqueous solution used is usually an aqueous solution of an alkali metal or alkaline earth metal bicarbonate; an aqueous solution of an alkali metal or alkaline earth metal carbonate; an alkali metal or alkaline earth metal hydroxide. Aqueous solution; and the like, and preferably an aqueous solution of an alkali metal bicarbonate or an alkali metal hydroxide.

Examples of the alkali metal hydrogencarbonate include sodium hydrogencarbonate and potassium hydrogencarbonate, and preferably sodium hydrogencarbonate. The concentration of the aqueous solution of the alkali metal bicarbonate is usually 1 to 10% by weight, preferably 2 to 5% by weight. The amount of the aqueous solution of the alkali metal bicarbonate used depends on the amount used in the reaction.
It is determined according to the amounts of acrylic acid and acid catalyst.

Examples of the alkali metal hydroxide include, for example, sodium hydroxide and potassium hydroxide, and preferably sodium hydroxide. The concentration of the aqueous solution of the alkali metal hydroxide is usually 1 to 10% by weight,
Preferably it is 1 to 5% by weight. By washing with such a low concentration of alkali metal hydroxide aqueous solution,
Unreacted hydroxy (alkyl) imide and the like can be removed, and the color number of the imide (meth) acrylate compound can be reduced.

When the reaction solution is separately washed with an aqueous solution of an alkali metal bicarbonate and an aqueous solution of an alkali metal hydroxide, the aqueous layer is separated after washing with an aqueous solution of an alkali metal bicarbonate. Then, the remaining organic layer is preferably washed with an aqueous solution of an alkali metal hydroxide. After washing the reaction solution with an alkaline aqueous solution, the organic layer is washed with saturated saline, the organic layer is separated, and the remaining solvent is distilled off from the organic layer to obtain an imide (meth) acrylate compound. Further, if necessary, it may be further purified by column chromatography.

The N-hydroxyimide compound or N- (hydroxyalkyl) imide compound used as a raw material in the method of the present invention is obtained by substituting two hydrogen atoms of ammonia with two acyl groups, Is a structure substituted with a hydroxyl group or a hydroxyalkyl group. At this time, the hydrocarbon group of the acyl group is not particularly limited, and may be any of an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Further, the hydrocarbon groups of two acyl groups may be bonded to each other to form a ring. The hydrocarbon groups of the two acyl groups at this time are
An alkylene group having 2 to 3 carbon atoms is preferred.

The alkylene group having 2 to 3 carbon atoms may be substituted by a hydrocarbon group. Such hydrocarbon groups are chain-like,
Any of a ring shape may be sufficient. Alternatively, the above-mentioned 2-3 carbon atoms
Has two carbon atoms different from each other in the alkylene group
30 alkylene groups may combine to form a condensed ring. The hydrocarbon group of the two acyl groups is an alkylene group having 2 to 3 carbon atoms, and an alkylene group having 4 to 30 carbon atoms is further substituted on two different carbon atoms of the alkylene group having 2 to 3 carbon atoms. The specific N-hydroxyimide compound or N- (hydroxyalkyl) imide compound bonded is represented by the following general formula 5.

[0035]

Embedded image (In the general formula 5, R ⁶ represents a hydrogen atom or an alkyl group, and R ⁷ represents a single bond, a chain alkylene group having 2 to 6 carbon atoms, or an alkylene group having 3 to 10 carbon atoms having an alicyclic structure.) Represents.)

Specific examples of the N-hydroxyimide compound represented by the general formula 5 include, for example, N-hydroxyhexahydrophthalimide, N-hydroxy-3-methylhexahydrophthalimide, N-hydroxy-4-methylhexahydrophthalimide And the like.

Specific examples of the N- (hydroxyalkyl) imide compound represented by the general formula 5 include, for example, N- (hydroxyalkyl) imide
(Hydroxyethyl) hexahydrophthalimide, N-
(Hydroxyethyl) -3-methylhexahydrophthalimide, N- (hydroxyethyl) -4-methylhexahydrophthalimide, N- (hydroxypropyl) -4
-Methylhexahydrophthalimide, N- (2-hydroxypropyl) -4-methylhexahydrophthalimide, N- (1-methyl-2-hydroxyethyl) -4-
Methyl hexahydrophthalimide, N- (4-hydroxycyclohexyl) -4-methylhexahydrophthalimide, N- (2-hydroxycyclopentyl) -4-methylhexahydrophthalimide, N- (hydroxypropyl) -3-methylhexahydrophthalimide , N-
(2-hydroxypropyl) -3-methylhexahydrophthalimide, N- (1-methyl-2-hydroxyethyl) -3-methylhexahydrophthalimide, N- (4
-Hydroxycyclohexyl) -3-methylhexahydrophthalimide, N- (2-hydroxycyclopentyl) -3-methylhexahydrophthalimide, N- (hydroxypropyl) -hexahydrophthalimide, N-
(2-hydroxypropyl) -hexahydrophthalimide, N- (1-methyl-2-hydroxyethyl) -hexahydrophthalimide, N- (4-hydroxycyclohexyl) -hexahydrophthalimide, N- (2-hydroxycyclopentyl)- Hexahydrophthalimide and the like.

Further, the hydrocarbon groups of the two acyl groups are linear alkylene groups having 2 to 3 carbon atoms, and two different linear alkylene groups having 2 to 3 carbon atoms are different from each other. A specific N-hydroxyimide compound or N- (hydroxyalkyl) imide compound in which a condensed ring having 4 to 30 carbon atoms is bonded to a carbon atom is represented by, for example, the following general formula 6.

[0039]

Embedded image (In the general formula 6, ^{R 7} is .n is the same as ^{R 7} in the general formula 5 is an integer of 1-3.)

Specific examples of the N-hydroxyimide compound represented by the general formula 6 include, for example, N-hydroxydihydronadiimide, N-hydroxytetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -dodecane-3,4-
Dicarboximide and the like.

Specific examples of the N- (hydroxyalkyl) imide compound represented by the general formula 6 include, for example, N- (hydroxyalkyl) imide compound.
(Hydroxyethyl) dihydronadiimide, N- (hydroxypropyl) dihydronadiimide, N- (hydroxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -dodecane-3,4-dicarboximide;
N- (hydroxypropyl) tetracyclo [4.4.
0.1 ^2,5 . ^{17, 10} ] -dodecane-3,4-dicarboximide and the like.

N-hydroxyimide compound or N-
Method for Producing (Hydroxyalkyl) imide Compound The N-hydroxyimide compound or N- (hydroxyalkyl) imide compound can be obtained by a known method described in JP-A-10-36462 and the like. It can also be produced by reacting an acid anhydride with an amino alcohol in water.

N-hydroxyimide compound or N-
The solvent used in the method for producing the (hydroxyalkyl) imide compound is water. Water is used in a proportion of 30 to 200% by weight, preferably 50 to 100% by weight, based on the total amount of dicarboxylic anhydride and amino alcohol.

N-hydroxyimide compound or N-
The method for producing the (hydroxyalkyl) imide compound is preferably performed at room temperature to 100 ° C. under normal pressure. N
The method for producing the -hydroxyimide compound or N- (hydroxyalkyl) imide compound can be completed under such conditions, usually in 0.5 to 3 hours.

N-hydroxyimide compound or N-hydroxyimide compound
The dicarboxylic anhydride used in the method for producing a (hydroxyalkyl) imide compound is preferably a hydrocarbon group bonded to a carbon atom of a carbonyl group of the dicarboxylic anhydride, wherein the N-hydroxyimide compound or N- (hydroxyalkyl) The same applies to the hydrocarbon of the acyl group of the imide compound.

The dicarboxylic anhydride is a dicarboxylic anhydride represented by the general formula 7 or 8.

Embedded image (In the general formula 7, R ⁶ represents a hydrogen atom or an alkyl group.) As a specific example of the dicarboxylic anhydride represented by the general formula 7, for example, hexahydrophthalic anhydride, 3- Methyl hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride and the like can be mentioned. The dicarboxylic anhydride represented by the general formula 7 can be obtained by a Diels-Alder reaction between maleic anhydride and isoprene or piperylene.

[0047]

Embedded image (In general formula 8, n shows the integer of 1-3.)

Specific examples of the dicarboxylic acid anhydride represented by the general formula 8 include, for example, dihydronadic anhydride, tetracyclo [4.4.0.1 ^2,5 .
[ ^17,10 ] -dodecane-3,4-dicarboxylic anhydride and the like. When n = 0, the dicarboxylic anhydride represented by the general formula 8 is obtained by a Diels-Alder reaction between maleic anhydride and cyclopentadiene. When n = 1, the product can be obtained by further subjecting the product of n = 0 to a Diels-Alder reaction with cyclopentadiene and hydrogenating it.

N-hydroxyimide compound or N-hydroxyimide compound
The amino alcohol used as a raw material in the method for producing the (hydroxyalkyl) imide compound may have at least one hydroxyl group and at least one amino group in the molecule, and each of the hydroxyl group and the amino group may be any one of the molecules. May be bonded to a carbon atom of

A specific example of the amino alcohol is an amino alcohol represented by the following general formula 9.

Embedded image (In the general formula 9, ^{R 7} is the same as ^{R 7} in the general formula 5.)

The amino alcohol represented by the general formula 9 is
Examples thereof include hydroxylamine, chain amino alcohol, and cyclic amino alcohol. Specific examples of the chain amino alcohol include, for example, 2-aminoethanol, 3
-Amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-
1-butanol, 2-amino-1-butanol and the like; specific examples of the cyclic amino alcohol include, for example, 2-aminocyclopentanol, 2-aminocyclohexanol, 4-aminocyclohexanol and the like.

These amino alcohols are used in a proportion of usually 1.0 to 2.0 equivalents, preferably 1.0 to 1.3 equivalents, of the dicarboxylic anhydride of the formula (5). After completion of the reaction, the reaction solution is acidified with an acidic aqueous solution such as hydrochloric acid, and then the desired product is extracted with an organic solvent such as chloroform. The organic solvent is dried to obtain an N-hydroxyimide compound or an N- (hydroxyalkyl) imide compound. To manufacture.
Alternatively, when the target substance is precipitated in the reaction solution, the precipitate is separated by filtration or the like to produce an N-hydroxyimide compound or an N- (hydroxyalkyl) imide compound.

(Preferred Embodiment) Hereinafter, preferred embodiments of the present invention will be described. 1. A specific imide (meth) acrylate compound represented by the general formula 1 is N-((meth) acryloyloxy)-
4-methylhexahydrophthalimide, N-((meth)
(Acryloyloxy) -3-methylhexahydrophthalimide, N-((meth) acryloyloxy) dihydronadiimide, N-((meth) acryloyloxyethyl) dihydronadiimide, N- (2- (meth) acryloyloxypropyl) -4-methylhexahydrophthalimide, N
-(1-methyl-2- (meth) acryloyloxyethyl) -4-methylhexahydrophthalimide, N- (2
- (meth) acryloyloxy cyclopentylmethyl) -4-methyl hexahydrophthalimide, N - ((meth) acryloyloxyethyl) - tetracyclo [4.4.0.1 ^{2
, 5} . [ ^17,10 ] dodecyl-3,4-dicarboximide.

2. In the production method of the present invention, when reacting an N-hydroxyimide compound or an N- (hydroxyalkyl) imide compound with (meth) acrylic acid in the presence of an acid catalyst, water is removed from the reaction system under reduced pressure. By reacting while removing, imide (meth)
This is a method for producing an imide (meth) acrylate compound for producing an acrylate compound. 1. In the above production method 2, the molar ratio of the N-hydroxyimide compound or the N- (hydroxyalkyl) imide compound to (meth) acrylic acid is from 0.3 to 1.
0, preferably 0.5 to 1.0. 2. In the above method 2, a polymerization inhibitor is used.

5. The solvents used in the production method 2 are toluene and xylene, and the amount of the solvent used is N-
Usually, 100 to 1000% by weight, preferably 100% by weight, based on the total amount of the hydroxyimide compound or N- (hydroxyalkyl) imide compound and (meth) acrylic acid.
５００500% by weight. 6. The temperature in the production method 2 is usually 50 to 120.
° C, preferably 60 to 100 ° C. 7. The reaction pressure of the above production method 2 is usually 50 to 50.
0 Torr, preferably 100 to 400 Torr
r, more preferably 100 to 300 Torr.

8. In the above method 2, the N-hydroxyimide compound or N- (hydroxyalkyl)
After reacting the imide compound with (meth) acrylic acid, the reaction solution is washed with an aqueous solution of an alkali metal bicarbonate, the aqueous layer is separated, and the remaining organic layer is washed with an aqueous solution of an alkali metal hydroxide. Wash. 9. The alkali metal bicarbonate described in the above item 8 is sodium hydrogen carbonate or potassium bicarbonate, and the concentration of the aqueous solution of the alkali metal bicarbonate is usually 1 to 10% by weight.
And preferably 2 to 5% by weight.

10. The alkali metal hydroxide according to the above item 8 is sodium hydroxide or potassium hydroxide, and the concentration of the aqueous solution of the alkali metal hydroxide is usually 1 to 10
%, Preferably 1 to 5% by weight. 11. The order of washing the reaction solution described in the above item 8 with an aqueous solution of an alkali metal bicarbonate and an aqueous solution of an alkali metal hydroxide is as follows. Wash with an aqueous solution of

[0058]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to only these Examples. The parts and percentages in the examples are on a weight basis unless otherwise specified. The methods for measuring physical properties in Examples and Comparative Examples are as follows.

(1) By-product component The by-product component contained in the obtained imide (meth) acrylate compound was measured by high performance liquid chromatography. The measurement conditions are as follows. Column: TSK G-2500H _HR manufactured by Tosoh Corporation,
G-1000H _{H R} solvent: chloroform Flow rate: 1 ml / min Detector: differential refractive index detector (Showa Denko Co., Ltd.
exRI71)

(2) Number of colors The number of formulas of the obtained imide (meth) acrylate compound is
Based on ASTM D1209-54, it was measured by SM color computer model SM4 manufactured by Suga Test Instruments Co., Ltd.

Example 1 N- (acryloyloxy) -4
Synthesis of methylhexahydrophthalimide In a 100 ml flask was added hydroxylamine (5
16 ml (0.26 mol) of 0% aqueous solution was charged, and 33.4 g (0.2 mol) of 4-methylhexahydrophthalic anhydride was added dropwise with stirring at room temperature. After the completion of the dropwise addition, the mixture was gradually heated and reacted at 100 ° C. for 1 hour. After completion of the reaction, a 4N aqueous hydrochloric acid solution was added to the reaction solution to make the reaction solution acidic. The desired product was extracted from the resulting reaction mixture with chloroform, the organic layer was separated, the organic layer was dried over anhydrous magnesium sulfate, and chloroform was removed from the organic layer to remove N-hydroxy-4, a colorless and transparent viscous liquid. −
32.4 g of methylhexahydrophthalimide (yield 8
9%).

Next, the N-
Hydroxy-4-methylhexahydrophthalimide 1
0.07 g (0.055 mol), triethylamine 15
Ml (0.11 mol) and 50 ml of 1,2-dichloroethane were charged, and 7.2 ml of acrylic acid chloride (0.0 ml) was stirred at room temperature under nitrogen.
90 mol) was slowly added dropwise. After the dropwise addition, the mixture was reacted at room temperature for 1 hour, and then the reaction mixture was washed with water to separate an organic layer, and then the organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution. The organic layer separated from the 5% aqueous sodium hydrogencarbonate solution was dried over magnesium sulfate, and then the solvent was removed from the organic layer to obtain a dark yellow viscous liquid N-.
11.8 g of (acryloyloxy) -4-methylhexahydrophthalimide was obtained. IR spectrum, ¹ H-NM
Table 1 shows the results of R spectrum and mass spectrometry.

Example 2 N- (acryloyloxy) -3
Synthesis of -methylhexahydrophthalimide The 4-methylhexahydrophthalic anhydride of Example 1 was
Example 1 except for replacing with 3-methylhexaphthalic anhydride
10.5 g of the target compound N- (acryloyloxy) -3-methylhexahydrophthalimide
I got Table 1 shows the results of the IR spectrum, ¹ H-NMR spectrum, and mass spectrometry.

Example 3 N- (acryloyloxy) dihi
Synthesis of Dronadimide Hydroxylamine (5
8% (0.13 mol) of 1% dihydronadic acid while stirring at room temperature.
(0.1 mol) was added dropwise. After completion of the dropwise addition, the mixture was gradually heated and reacted at 100 ° C. for 1 hour. After the reaction, add 4
The reaction solution was acidified by adding an aqueous solution of N hydrochloric acid to obtain N-hydroxydihydronadiimide as a colorless solid.

A 100 ml flask was charged with 12.7 g (0.070 mol) of N-hydroxydihydronadiimide, 15 ml (0.11 mol) of triethylamine, and 50 ml of 1,2-dichloroethane. Underneath, 7.2 ml (0.090 mol) of acrylic acid chloride were slowly added dropwise. After the dropwise addition, the mixture was reacted at room temperature for 1 hour, and then the reaction mixture was washed with water to separate an organic layer.
Washed with aqueous sodium bicarbonate. The organic layer separated from the 5% aqueous sodium hydrogen carbonate solution was dried over magnesium sulfate, and then the solvent was removed from the organic layer.
14.8 g of N- (acryloyloxy) dihydronadiimide, which is a dark yellow viscous liquid, was obtained. IR spectrum, ¹
Table 1 shows the results of the H-NMR spectrum and the mass spectrometry.

Example 4 N- (2-acryloyloxye)
Synthesis of tyl) dihydronadiimide In a 100 ml flask, 6 ml (0.1 mol) of hydroxyethylamine and 10 ml of water were charged, and 16.6 g (0.1 mol) of dihydronadic anhydride was added dropwise with stirring at room temperature. . After completion of the dropwise addition, the mixture was gradually heated and reacted at 100 ° C. for 1 hour. After the reaction,
4N hydrochloric acid aqueous solution was added to the reaction solution to make the reaction solution acidic,
A colorless solid was obtained. The obtained colorless solid was separated by filtration to obtain 18.4 g of N- (hydroxyethyl) dihydronadiimide.

In a 100 ml flask, 10.51 g of N- (hydroxyethyl) dihydronadiimide (0.
05 mol), 11 ml of triethylamine (0.
(08 mol), 1,2-dichloroethane (50 ml) was charged, and acrylic acid chloride (5.3 ml, 0.065 mol) was slowly added dropwise with stirring at room temperature under nitrogen. After the dropwise addition, the mixture was reacted at room temperature for 1 hour, and then the reaction mixture was washed with water to separate an organic layer, and then the organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution. The organic layer separated from the 5% aqueous sodium hydrogencarbonate solution was dried over magnesium sulfate, and then the solvent was removed from the organic layer to give 12.3 g of N- (acryloyloxyethyl) dihydronadiimide, which is an orange viscous liquid. Obtained. Table 1 shows the results of the IR spectrum, ¹ H-NMR spectrum, and mass spectrometry.

Example 5 N- (2-acryloyloxyp)
Synthesis of ropyl) -4-methylhexahydrophthalimide In a 100 ml flask, 15.4 ml (0.2 mol) of 2-hydroxypropylamine and 12 ml of water were charged, and stirred at room temperature while stirring 4-methylhexahydrophthalic anhydride. 33.4 g (0.2 mol) of the product were added dropwise. After completion of the dropwise addition, the mixture was gradually heated and reacted at 100 ° C. for 1 hour. After completion of the reaction, a 4N aqueous hydrochloric acid solution was added to the reaction solution to make the reaction solution acidic. After extracting the target substance from the obtained reaction mixture with chloroform and separating the organic layer, the organic layer is dried over anhydrous magnesium sulfate, and chloroform is removed from the organic layer to obtain N- ( 43.5 g of 2-hydroxypropyl) -4-methylhexahydrophthalimide was obtained.

In a 100 ml flask, N- (2-
Hydroxypropyl) -4-methylhexahydrophthalimide (22.5 g, 0.10 mol), triethylamine (22 ml, 0.16 mol) and 1,2-dichloroethane (100 ml) were charged, and the mixture was stirred at room temperature under a nitrogen atmosphere to form an acrylic resin. 10.6 ml (0.13 mol) of acid chloride was slowly added dropwise. After the dropwise addition, the mixture was reacted at room temperature for 1 hour, then the reaction mixture was washed with water, the organic layer was separated, and the organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution. The organic layer separated from the 5% aqueous sodium hydrogencarbonate solution was dried over magnesium sulfate, and then the solvent was removed from the organic layer to obtain a dark yellow viscous liquid, N- (2-acryloyloxypropyl) -4-methyl. 22.9 g of hexahydrophthalimide was obtained. Table 1 shows the results of IR spectrum, ¹ H-NMR spectrum, and mass spectrometry.

[0070]

[Table 1]

Example 6 N- (1-methyl-2-acrylic acid)
(Lyloxyethyl) -4-methylhexahydrophthalyi
Synthesis of amide Example 5 was repeated except that 2-hydroxypropylamine in Example 5 was replaced with 2-hydroxy-1-methylethylamine.
20. N- (1-Methyl-2-acryloyloxyethyl) -4-methylhexahydrophthalimide
5 g were obtained. Table 2 shows the results of IR spectrum, ¹ H-NMR spectrum and mass spectrometry.

Example 7 N- (4-acryloyloxy)
Clohexyl) -4-methylhexahydrophthalimide
Outside was replaced in 2-hydroxypropyl amine of Example 5 4-hydroxy cyclohexylamine, in the same manner as in Example 5 N-(4-acryloyloxy-cyclohexyl)
23.3 g of -4-methylhexahydrophthalimide was obtained. Table 2 shows the results of IR spectrum, ¹ H-NMR spectrum and mass spectrometry.

Example 8 N- (2-acryloyloxy)
Clopentyl) -4-methylhexahydrophthalimide
Outside was replaced in 2-hydroxypropyl amine of Example 5 2-hydroxycyclopentyl amine, in the same manner as in Example 5 N-(2-acryloyloxyethyl cyclopentyl)
21.0 g of -4-methylhexahydrophthalimide was obtained. Table 2 shows the results of IR spectrum, ¹ H-NMR spectrum and mass spectrometry.

Example 9 N- (acryloyloxyethyl)
Le) - tetracyclo [4.4.0.1 ^2, 5. 1
^7,10 ] dodecyl-3,4-dicarboximide
Dihydro nadic anhydride formed Example 4 tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodecyl-3,
Outside was replaced with 4-dicarboxylic anhydride in the same manner as in Example 4 N-(acryloyloxyethyl) - tetracyclo [4.4.0.1 ^2, 5. 1 ^7,10 ] dodecyl-3,
13.5 g of 4-dicarboximide were obtained. Table 2 shows the results of IR spectrum, ¹ H-NMR spectrum and mass spectrometry.

[0075]

[Table 2]

Example 10 N- (2-Acryloyloxy)
Ethyl) -4-methylhexahydrophthalimide 176.3 g (1.05 mol) of 4-methylhexahydrophthalic anhydride and toluene 420
Then, 63.4 ml (1.05 mol) of ethanolamine was added dropwise while stirring at room temperature. After the dropwise addition, the mixture was heated and reacted under reflux for 7 hours.
8.9 g were distilled off. After the reaction vessel was cooled to room temperature, 420 ml of toluene, 2 g of p-methoxyphenol, 144 ml (2.1 mol) of acrylic acid, and 20.6 g of sulfuric acid were further added to the reaction vessel, and then 70 ° C. under reduced pressure (105 Torr). The reaction was carried out while removing the water generated in the above.

After 6 hours, the reaction solution was cooled to room temperature, the reaction solution was washed with 2 liters of a 5% by weight aqueous sodium hydrogen carbonate solution to separate a toluene solution, and then the toluene solution was washed with a saturated saline solution. The toluene solution separated from the saturated saline was dried over anhydrous magnesium sulfate, and toluene was removed from the toluene solution to remove N-, a yellow transparent viscous liquid.
242 g of (2-acryloyloxyethyl) -4-methylhexahydrophthalimide was obtained. The ratio of by-product components contained in the obtained imide (meth) acrylate compound and the number of colors of the imide (meth) acrylate compound were evaluated. Table 3 shows the evaluation results together with the yield and purity.

Example 11 The same operation as in Example 10 was performed, except that after washing with a 5% by weight aqueous solution of sodium hydrogencarbonate, the substrate was further washed with 1 liter of a 2% by weight aqueous solution of sodium hydroxide. The obtained toluene solution was dried over anhydrous magnesium sulfate, and toluene was removed from the toluene solution to obtain N- (2-acryloyloxyethyl) -4-, a pale yellow transparent viscous liquid.
227.1 g of methylhexahydrophthalimide were obtained.
Table 3 shows the yield, by-product component ratio, and color number.

COMPARATIVE EXAMPLE 1 Acrylic acid was reacted with 72 ml (1.05 mol) under reduced pressure at 70 ° C. for 6 hours.
After reacting for 5 hours, the same operation as in Example 10 was carried out except that the mixture was washed with a 10% by weight aqueous sodium hydroxide solution, and N- (2-acryloyloxyethyl) -4 as a viscous liquid was used.
89.1 g of -methylhexahydrophthalimide were obtained.
Table 3 shows the yield, purity, by-product component ratio, and color number.

[0080]

[Table 3]

[0081]

According to the present invention, there is provided an imide (meth) acrylate compound which is expected to provide an active energy ray-curable resin composition having fast curing properties, excellent heat resistance and excellent flexibility. be able to. The imide (meth) acrylate compound of the present invention can be used as a diluting monomer, a homopolymerizing monomer, a copolymerizing monomer, or the like.

Examples of the diluting monomer include: coating of building materials and furniture; glossy varnish of paper; printing and plate making materials; materials for thermal transfer recording paper; printing ink;
For coating optical lenses, dental materials, optical fibers, etc .; plastic films, plastic molding materials, optical discs,
For hard coats such as metal materials; Pressure sensitive adhesives; Sealants for electronic components; Binders for magnetic recording media; Solder resists for printed circuit boards; Interphase insulating materials for multilayer printed circuit boards;
It can be used for manufacturing various coating films of liquid crystal displays and plasma display panels.

The homopolymerizable monomer or the copolymerizable monomer can be used, for example, for producing optical lens resins, toner resins, heat-resistant resins, water-resistant resins, insulating resins and the like. Further, according to the present invention, there is provided a method for producing a high-purity imide (meth) acrylate compound with high yield.

Claims (2)

[Claims] 1. An imide (meth) represented by the following general formula 1.
Acrylate compounds. Embedded image (In the general formula 1, R ¹ represents a hydrogen atom or a methyl group, and X is an oxygen atom or —R ² —O—. R ²
Represents a chained alkylene group having 2 to 5 carbon atoms or an alkylene group having 3 to 10 carbon atoms having an alicyclic structure. R
³ is represented by the following general formula 2 or 3 when X is an oxygen atom. R ³ is represented by the following general formula 4 when R ² is an ethylene group. R ³ is such that R ² has a chain carbon number of 3 to
5 to 3 carbon atoms having an alkylene group or an alicyclic structure of 5
When any one of the alkylene groups represented by formula (1) is
Or it is represented by general formula 3. Embedded image (In the general formula 2, R ⁴ and R ⁵ represent a hydrogen atom or a methyl group.) (In the general formula 3, m is 0 or 1.) (In the general formula 4, m is 0 or 1.) 2. An imide (meth) which produces an imide (meth) acrylate compound by reacting an N-hydroxyimide compound or an N- (hydroxyalkyl) imide compound with (meth) acrylic acid in the presence of an acid catalyst. ) A method for producing an acrylate compound, wherein the reaction is carried out under reduced pressure while removing water from the reaction system.