JP2002179742A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition having excellent curability and hardness of the cured product. SOLUTION: This curable composition comprises (A) a poly(meth)acrylate having four or more cyclic imide groups and (B) a di(meth)acrylate having two cyclic imide groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition containing a (meth) acrylate having two kinds of cyclic imide groups, preferably an active energy ray-curable composition. The curable composition of the present invention can be used for a coating agent, an adhesive, a resist agent, an electronic material, a molding material, and the like, and is particularly useful as an optical material such as a lens and a prism and a material for a 3D modeling system. And can be awarded in these technical fields.

[0002]

2. Description of the Related Art UV-curable resins not only greatly reduce the energy and time required for drying, but also save space during drying, as well as use less solvent than conventional solvent-dried resins due to their rapid curing properties. The amount of use is increasing year by year as a coating agent which is friendly to the global environment, and can be used in a small amount or not at all. In recent years, line speed has been further increased in order to cope with products of a small quantity and many kinds by utilizing the speed of production.
However, some UV curable resins have skin irritation and those with odor.If the line speed is increased and curing is insufficient, skin irritation and odor may become a problem. It has been desired to improve the properties and coating film hardness.

[0003]

As an active energy ray-curable composition having excellent curability, an active energy ray-curable composition comprising a di (meth) acrylate having two cyclic imide groups in a molecule [hereinafter referred to as a diimidedi (meth) acrylate]. An energy ray-curable composition is known (JP-A-3-2712).
No. 72, No. 7-300459). However, the composition may have insufficient curability,
The hardness of the cured product was insufficient. The present inventors have made intensive studies to find a curable composition having excellent curability and hardness of a cured product.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of such a situation. As a result, (A) poly (meth) acrylate having four or more cyclic imide groups and (B) cyclic imide Curable composition comprising di (meth) acrylate having two groups, (A) di (meth) acrylate having four or more cyclic imide groups, and (B) two or more cyclic imide groups.
A curable composition comprising a di (meth) acrylate having one (C) and a mono (meth) acrylate having one (C) cyclic imide group was found to be fast-curing and the cured product was excellent in hardness, and completed the present invention. did. In this specification,
Acrylate and / or methacrylate are referred to as (meth) acrylate, acryloyl and / or methacryloyl groups as (meth) acryloyl groups, and acrylic acid and / or methacrylic acid as (meth) acrylic acid.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS 1. Curable Composition 1-1. Component (A) The component (A) is a poly (meth) having at least four cyclic imide groups.
Acrylate, a preferred example is the following general formula
The di (meth) acrylate represented by (1) is exemplified.

[0006]

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[Wherein, in the formula (1), R ₁ is a residue of a tetracarboxylic anhydride, R ₂ is a residue of a diamine, R ₃ is an alkylene group, and R ₄ is hydrogen or methyl. Group. l and m are integers of 1-6. ]

Preferred examples of R ₁ include the following formulas (4) to (4).
And the group represented by (9).

[0009]

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[However, in the formula (4), R ₇ and R ₈ are
Is a hydrogen atom or a linear or branched alkyl group having 9 or less carbon atoms, X is _{-O -, - SO 2 -,} - C (= O) -,
—C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ — and the like. ]

[0011]

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[However, in the formula (5), R ₉ is a hydrogen atom or a linear or branched alkyl group having 9 or less carbon atoms. ]

[0013]

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[However, in the formula (6), R ₁₀ and R
₁₁ is a hydrogen atom or a linear or branched alkyl group having 9 or less carbon atoms. ]

[0015]

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[0016]

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[0017]

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Among these, R ₁ is preferably a group in which X is —O— or —SO ₂ — in the formula (4), and groups represented by the formulas (7) and (8).

Examples of the diamine residue of R ₂ include an alkylene group, a divalent cyclic alkyl group and a divalent aryl group. As the alkylene group, an alkylene group having 6 or less carbon atoms is preferable, and an ethylene group and a propylene group are more preferable. Examples of the divalent cyclic alkyl group include a cyclohexyl group and an isophorone group. Examples of the divalent aryl group include a phenylene group and a diphenylmethane group.

The alkylene group represented by R ₃ is preferably an alkylene group having 6 or less carbon atoms, more preferably an ethylene group and a propylene group.

1-2. Component (B) The component (B) is a di (meth) acrylate having two cyclic imide groups, and is preferably represented by the following general formula (2)
And a di (meth) acrylate represented by

[0022]

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[However, in the formula (2), R ₁ is a residue of a tetracarboxylic anhydride, R ₃ is an alkylene group, and R ₄ is hydrogen or a methyl group. m is an integer of 1 to 6. Preferred examples of R ₁ include the above formulas (4) to (9)
And the like. As the alkylene group for R _3, an alkylene group having 6 or less carbon atoms is preferable, and an ethylene group and a propylene group are more preferable.

1-3. Component (C) In the present invention, the component (C) preferably contains a mono (meth) acrylate having one cyclic imide group. Preferred examples of the component (C) include a mono (meth) acrylate represented by the following general formula (3).

[0025]

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[However, in the formula (3), R ₃ is an alkylene group, and R ₄ is hydrogen or a methyl group. R ₅ and R ₆
Is independently an alkyl group having 4 or less carbon atoms, or R ₅ and R ₆ are a group which together form a carbocyclic ring. n is an integer of 1 to 6. The dotted line in the 5-membered imide ring means a single bond or a double bond. ]

Examples of the group in which R ₅ and R ₆ together form a carbocyclic ring include —CH ₂ CH ₂ CH ₂ — and a group —CH ＝.
CHCH ₂ —, group —CH ₂ CH ₂ CH ₂ CH ₂ —, group —CH ₂
CH = CHCH ₂ — or a group —CH ＝ CHCH ＝ CH—.

As R ₅ and R ₆ , at least one of which is an alkyl group or a group which forms a carbon ring together is preferable in that the resulting cured film has excellent water resistance.

The alkylene group for R ₃ is preferably an alkylene group having 6 or less carbon atoms, more preferably an ethylene group and a propylene group.

The proportions of the components (A) and (B) are as follows:
And 5 to 85% by mass and 95 to 15% by mass, respectively, based on the total amount of the components (B) and (B). When the proportion of the component (A) is less than 5% by mass, the curability and the hardness of the cured product may be insufficient. On the other hand, when the proportion is more than 85% by mass, the viscosity of the composition may be too high to be difficult to handle. is there. (C)
When the components are blended, the ratio is based on the total amount of the components (A), (B) and (C). 15-9
0% by mass is preferred. If the proportion of the component (C) is less than 15% by mass, the viscosity of the composition may be too high to make it difficult to handle, or the flexibility of the cured product may be reduced. And the hardness of the cured product may be insufficient.

1-4. Other Components In the composition of the present invention, in addition to the above essential component (meth) acrylate, other compounds having a radical polymerizable unsaturated double bond (hereinafter referred to as “methacrylate”) for various purposes. Other monomers). Other monomers include vinyl monomers, and oligomers such as urethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate.

Examples of vinyl monomers include amide compounds such as N-vinylpyrrolidone, N-vinylcaprolactam and (meth) acryloylmorpholine; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as 2-hydroxy-3-phenylpropyl acrylate; acrylates of alkylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and their halogen nuclei; mono- or di- (meth) acrylates of ethylene glycol Glycols such as acrylates, mono (meth) acrylates of methoxyethylene glycol, mono or di (meth) acrylates of tetraethylene glycol, mono or di (meth) acrylates of tripropylene glycol Mono- or di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Polyols such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate and (meth) alkylene oxides thereof
Acrylates; and isocyanuric acid ethylene oxide-modified di- or tri (meth) acrylates.

Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a polyol and an organic polyisocyanate reaction product. Here, examples of the polyol include low molecular weight polyols, polyethylene glycol, and polyester polyol, and examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol. And polyether polyols such as polyethylene glycol and polypropylene glycol. Polyester polyols include these low molecular weight polyols and / or polyether polyols and adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid. And a reaction product with an acid component such as a dibasic acid or an anhydride thereof. Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Examples of the polyester (meth) acrylate oligomer include a dehydration condensate of a polyester polyol and (meth) acrylic acid. As the polyester polyol, ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-
Low molecular weight polyols such as 1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and polyols such as alkylene oxide adducts thereof, and adipic acid, succinic acid, phthalic acid, A reaction product from a dibasic acid such as hexahydrophthalic acid and terephthalic acid or an acid component such as an anhydride thereof is exemplified.

Epoxy acrylate is obtained by adding an unsaturated carboxylic acid such as (meth) acrylic acid to an epoxy resin, and is an epoxy (meth) acrylate of bisphenol A type epoxy resin, phenol or epoxy of cresol novolac type epoxy resin. (Meth) acrylate and (meth) acrylic acid addition reactant of diglycidyl ether of polyether and the like can be mentioned.

The preferred ratio of other monomers is as follows:
It is 300 parts by mass or less based on 100 parts by mass of the total amount of the components (A) and (B) or the total amount of the components (A), (B) and (C).

The composition of the present invention can be easily cured by irradiation with an active energy ray such as an ultraviolet ray and an electron beam or by heating, and is preferably one which is cured by an active energy ray.

When the composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator is blended. Examples of photopolymerization initiators include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenyl. Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2 Anthraquinones such as -methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; Tons, 2,4-diethyl thioxanthone, 2-chlorothioxanthone and 2,4-di iso pills thioxanthone such as thioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,
Monoacylphosphine oxides such as 4,6-trimethylbenzoyldiphenylphosphine oxide or bisacylphosphine oxides; benzophenones such as benzophenone; and xanthones. These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiator. The preferred mixing ratio of the photopolymerization initiator is 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the composition.

When the composition of the present invention is cured by heating, a thermal polymerization initiator is added to the composition. Examples of the thermal polymerization initiator include an azo thermal polymerization initiator such as azobisisobritylonitrile and a peroxide thermal polymerization initiator such as benzoyl peroxide. A preferred blending ratio of the thermal polymerization initiator is 0.01 to 5 parts by mass with respect to 100 parts by mass of the composition.

2. Method for Producing Composition The composition of the present invention can be obtained by producing the component (A) and the component (B) or, if necessary, the component (C) according to a conventional method, and mixing them. However, with conventional manufacturing methods
When component (A) or component (B) is manufactured, component (A) or component (B)
It had problems of component yield, purity and odor. Further, when the component (A) is blended with another compound to form a composition, there is a problem that the component (A) or the component (B) is hardly dissolved in the other compound.

A preferred method of producing a composition which can solve these problems is to heat a tetracarboxylic anhydride, a dicarboxylic anhydride, a polyamine and a monoamino alcohol to form a polyol having four or more cyclic imide groups (hereinafter referred to as polyimide polyol). ), A mixture of a diol having two cyclic imide groups (hereinafter, referred to as diimide diol) and a monool having one cyclic imide group (hereinafter, referred to as imide monool), and then adding a (meth) acryloyl group to these compounds. It is a method to introduce. According to the present production method, the components (A) and (B) can be produced in good yield, and the components (A), (B) and (C) can be produced simultaneously, and the resulting composition is obtained. Is easy to handle because it can be obtained as a solution or slurry. Hereinafter, the present manufacturing method will be described.

2-1. Addition and Ring Closure Reaction of Polyamine and Monoamino Alcohol In this production method, first, an addition reaction of tetracarboxylic anhydride with polyamine and monoamino alcohol is carried out, and dicarboxylic anhydride and monoamino alcohol are added. In order to cause the addition reaction of the above, the mixture is heated under stirring, followed by dehydration and ring closure to produce a mixture of polyimide polyol, diimide diol and imide monol. Examples of the tetracarboxylic anhydride include a tetracarboxylic anhydride represented by the following general formula (10).

[0043]

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[However, in the formula (10), R ₁ has the same meaning as in the general formula (1). Preferred examples of R ₁ in the tetracarboxylic anhydride include groups represented by the above formulas (4) to (9). Preferred examples of the dicarboxylic anhydride include a compound represented by the following general formula (11).

[0045]

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[However, in the formula (11), R ₅ and R ₆ have the same meaning as in the general formula (3). Preferred specific examples of the dicarboxylic anhydride include acid anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, and succinic acid, and alkyl group-substituted products thereof. Preferred examples of the monoamino alcohol include ethanolamine, propanolamine, ethoxyethanolamine, and propoxypropanolamine. Preferred examples of the polyamine include ethylenediamine having a plurality of primary amines, propanediamine,
Diamines such as hexamethylenediamine, isophoronediamine, diaminodiphenylmethane and the like can be mentioned.

The addition reaction and the dehydration ring closure reaction are carried out by heating and stirring tetracarboxylic anhydride, dicarboxylic anhydride, polyamine and monoamino alcohol. in this case,
The reaction may be carried out without a catalyst, or a catalyst may be used if necessary. When a catalyst is used, examples of the catalyst include acid catalysts such as sulfuric acid, methanesulfonic acid, and paratoluenesulfonic acid. The reaction temperature may be appropriately set depending on the compound used and the purpose, but is preferably 70 ° C.
~ 140 ° C. When the reaction temperature is lower than 70 ° C., the reaction becomes slow. On the other hand, when the reaction temperature exceeds 140 ° C., the reaction system becomes unstable and impurities may be generated.

The reaction is preferably performed in an organic solvent. In the dehydration ring closure reaction, it is preferable to use an organic solvent having low solubility with water, and to promote the dehydration reaction while azeotropically evaporating water.
Preferred are aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and ketones such as methyl ethyl ketone and cyclohexanone.

By the addition reaction and the dehydration ring closure reaction, a mixture of polyimide polyol, diimide diol and imide monool is obtained. Preferred examples of the polyimide polyol, diimide diol and imide monool include compounds represented by the following formulas (12), (13) and (14).

[0050]

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[However, in the formula (12), R ₁ , R ₂ ,
R ₃ , l and m have the same meaning as in the above formula (1). ]

[0052]

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[However, in the formula (13), R ₁ , R ₃ and m
Has the same meaning as in the general formula (2). ]

[0054]

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[However, in the formula (14), R ₃ , R ₅ , R ₆
And n have the same meaning as in the general formula (3). ]

2-2. Introduction of (meth) acryloyl group As a method for introducing a (meth) acryloyl group into the polyimide polyol, diimidediol and imide monool obtained above, polyimide polyol, diimide diol and imide monool can be used. And a (meth) acrylic acid, and a transesterification reaction of reacting a polyimide polyol, diimidediol and imide monool with an alkyl (meth) acrylate.

An example of a production method employing a dehydration esterification reaction is a method in which (meth) acrylic acid is added to the reaction solution containing diimide diol and imide monool, and the mixture is heated and stirred in the presence of an acid catalyst. And the like. Examples of the acid catalyst include an acid catalyst such as sulfuric acid, methanesulfonic acid, and paratoluenesulfonic acid. The reaction temperature is
The temperature may be appropriately set depending on the compound to be used and the purpose, but is preferably from 70 ° C to 140 ° C. Reaction temperature 7
When the reaction temperature is lower than 0 ° C., the reaction becomes slow. On the other hand, when the reaction temperature exceeds 140 ° C., the reaction system becomes unstable, and impurities may be generated or gelation may occur.

In the reaction, it is preferable to use an organic solvent having low solubility in water generated by the esterification reaction, and to promote dehydration while azeotropically evaporating water. Preferred organic solvents are the same as those described above. Things. or,
The organic solvent may be distilled off under reduced pressure after the reaction, and when a solvent having no odor problem is used, it may be used as it is without distilling it off for adjusting the viscosity of the composition.

As a production example in which a transesterification reaction is adopted, an alkyl (meth) acrylate is added to the above reaction solution containing a polyimide polyol, diimide diol and imide monool, and the mixture is heated and stirred in the presence of a catalyst. Method. Preferred examples of the alkyl (meth) acrylate include methyl (meth) acrylate and ethyl (meth) acrylate. As the catalyst, those usually used in a transesterification reaction may be employed, and examples thereof include tetrabutyl titanate.
The reaction temperature and the reaction time may be appropriately set according to the raw materials used and the purpose.

In order to suppress radical polymerization of the (meth) acryloyl group during the reaction, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether and phenothiazine may be added to the reaction solution.

According to the present production method in which a dicarboxylic acid anhydride, an amic acid or an imide monool which is a precursor of an imide monool coexists in a reaction between a tetracarboxylic acid anhydride, a polyamine and an amino alcohol, the tetracarboxylic acid anhydride is used. The polyimide polyol and diimide diol, which are adducts of the product, polyamine and monoamino alcohol, are easily dissolved in the organic solvent, and the reaction proceeds smoothly. This is because amic acid or imide monool, which is a precursor of imide monol which is an adduct of dicarboxylic anhydride and amino alcohol, has an intermediate polarity between polyimide polyol and diimide diol and an organic solvent, and is used as a compatibilizer. Therefore, it is presumed that the solubility of the polyimide polyol and the diimide diol in the organic solvent is improved.

According to the production method, (A), (B) and
The component (C) can be produced at the same time, and the resulting composition is in a liquid state, a slurry state or a soft wax state, so that it is very easy to handle and further contains other (meth) acrylates and the like in the composition. Also in this case, the solubility of other components is improved. Again, for the same reasons as above,
It is presumed that the component (C) functions as a compatibilizer.

3. Method of Use and Use As a method of using the composition of the present invention, for example, after applying to a substrate to be applied by a usual coating method, irradiation with active energy rays such as ultraviolet rays and electron beams is performed. A general method such as curing by heating or curing by heating can be employed. In addition, applications of the composition of the present invention include coating agents, adhesives, resist agents, electronic materials and molding materials. Particularly, the cured product of the composition of the present invention has an excellent refractive index, and thus can be suitably used for optical materials such as lenses and prisms. The lens can be preferably used as a composition for producing a lens sheet such as a funnel lens. Further, the cured product of the composition of the present invention is excellent in heat resistance and chemical resistance, so that the 3D
It can be preferably used as a composition for a modeling system.

[0064]

The present invention will be described more specifically with reference to the following examples and comparative examples. In the following, "%" means mass%. Production Example 1 76.7 g (0.5 mol) of hexahydrophthalic anhydride and 280 g of xylene were charged into a flask equipped with a stirrer, cooling tube and Dean-Stark trap (water separator), and heated to 50 ° C. Dissolved in ethanolamine.
4 g (0.5 mol) was added dropwise over 30 minutes, and the mixture was refluxed for 3 hours while maintaining the liquid temperature at 140 to 145 ° C.
g of water distilled off in the water separator. After cooling the reaction solution,
-Dicarboxy-1,2,3,4-tetrahydro-1-
83.8 g (0.28 mol) of naphthalene succinic dianhydride [Likacid TDA-100 manufactured by Nippon Rika Co., Ltd.] was charged, and the mixture was heated to 70 ° C. and ethanol amine 24.8 was added.
g (0.41 mol) was added dropwise over 30 minutes, then 4.6 g (0.076 mol) of ethylenediamine was added dropwise over 10 minutes, and the mixture was refluxed for 6 hours while maintaining the liquid temperature at 140 to 145 ° C. 9.0 g of water distill off in the water separator. After cooling the reaction solution, 78.1 g (1.09 mol) of acrylic acid was added thereto,
0.14 g of hydroquinone and 11.2 g of sulfuric acid were added,
When the liquid temperature was kept at 140 to 145 ° C. and refluxed for 7.0 hours, 17.5 g of water was distilled out into the water separator. After cooling, the reaction solution was transferred to a separating funnel, and once with 80 g of water, 20% Na was added.
The mixture was extracted once with 200 g of an aqueous OH solution. The organic layer was distilled under reduced pressure to remove the solvent.
I got it. According to the results of GPC and NMR analysis, the following compound (1
5) A mixture of the following compound (hereinafter referred to as A-1), the following compound (16) (hereinafter referred to as B-1) and the following compound (17) (hereinafter referred to as C-1) was obtained at a weight ratio of 1: 1: 2. I confirmed that The resulting mixture of compounds had no odor at all.

[0065]

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[0066]

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[0067]

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Production Example 2 The 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride of Production Example 1 was converted to 5-
(2,5-dioxotetrahydro-3-furanyl) -3
-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride [Dai Nippon Ink Chemical Industry Co., Ltd. Epicron B
-4400] The reaction was carried out under the same conditions as in Production Example 1 except that the composition was changed to 73.6 (0.28 mol). as a result,
A light yellow, highly viscous liquid product was obtained in 60% yield. GPC
And NMR analysis result, a mixture of the following compound (18) (hereinafter referred to as A-2), the following compound (19) (hereinafter referred to as B-2) and C-1 was obtained at a weight ratio of 1: 1: 2. Confirmed. The resulting mixture of compounds had no odor at all.

[0069]

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[0070]

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Example 1 The composition obtained in Production Example 1 was further added to acryloyl morpholine [produced by Kojin Co., Ltd.] and benzyl dimethyl ketal photoinitiator [Irgacure 651 manufactured by Ciba Specialty Chemicals Co., Ltd.] ] And mixed by stirring to produce an active energy ray-curable composition. According to the following methods, the curability and pencil hardness of the obtained composition were evaluated. Table 1 shows the results.

Curable Bonderite steel sheet [Nippon Test Panel Co., Ltd.]
PB-144], and the obtained composition was applied thereto at a film thickness of 10 μm, and passed under a condensing high-pressure mercury lamp of 80 W / cm (one lamp) at a conveyor speed of 10 m / min. It was evaluated by the number of passes until it was touched by hand and tack on the surface disappeared.

Pencil hardness: Pencil hardness was measured by a hand-drawing method according to the test method of JIS K-5400.

[0074]

[Table 1]

Examples 1 and 2 An active energy ray-curable composition was produced in the same manner as in Example 1 except that the components used were changed as shown in Table 1. The obtained composition was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Examples 1 to 3 An active energy ray-curable composition was produced in the same manner as in Example 1 except that the components used were changed as shown in Table 2. The obtained composition was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0077]

[Table 2]

[0078]

The composition of the present invention is fast-curing, and its cured product is excellent in hardness, so that it is useful for coatings, paints, printing inks, adhesives, fillers, molding materials and resists. Things. Further, according to the method for producing the composition of the present invention, the components (A), (B) and (C) can be produced simultaneously with high purity and high concentration, and the resulting composition is curable. It is very easy to handle because it is excellent in odor, has no problem of odor, and becomes liquid, slurry or soft wax.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA13 AB14 AB20 AC01 AD01 BC14 BC38 BC42 BC49 BC83 FA03 4J100 AL08R AL66P AL66Q BA02P BA02Q BA02R BA12P BA12Q BA58P BA58Q BC23P BC23Q BC43P BC43Q BC48P BC48Q BC66P JA03 BC66 JA38 JA43

Claims (6)

[Claims] 1. A curable composition comprising (A) a poly (meth) acrylate having four or more cyclic imide groups and (B) a di (meth) acrylate having two cyclic imide groups. 2. The curable composition according to claim 1, further comprising (C) a mono (meth) acrylate having one cyclic imide group. 3. The curable composition according to claim 1, wherein the component (A) is a di (meth) acrylate represented by the following general formula (1). Embedded image [However, in the formula (1), R ₁ is a residue of a tetracarboxylic anhydride, R ₂ is a residue of a diamine, R ₃ is an alkylene group, and R ₄ is hydrogen or a methyl group. . l and m are integers of 1-6. ] 4. The curable composition according to claim 2, wherein the component (B) is a di (meth) acrylate represented by the following general formula (2). Embedded image [However, in the formula (1), R ₁ is a residue of a tetracarboxylic anhydride, R ₃ is an alkylene group, and R ₄ is hydrogen or a methyl group. m is an integer of 1 to 6. ] 5. The curable composition according to claim 2, wherein the component (C) is a mono (meth) acrylate represented by the following general formula (3). Embedded image [However, in the formula (3), R ₃ is an alkylene group;
₄ is hydrogen or a methyl group. Or R ₅ and R ₆ are each independent alkyl group having 4 or less carbon atoms, or R ₅
And R ₆ are a group which together form a carbocyclic ring. n
Is an integer of 1 to 6. The dotted line in the 5-membered imide ring means a single bond or a double bond. ] 6. A tetracarboxylic acid anhydride, a dicarboxylic acid anhydride, a polyamine and an amino alcohol are heated to form a polyol having four or more cyclic imide groups, a diol having two cyclic imide groups, and one cyclic imide group. After obtaining a mixture of monools containing
The method for producing a composition according to any one of claims 2 to 5, wherein an acryloyl group is introduced.