JP2001172336A - Activated energy ray-curing type resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an activated energy ray-curing type resin composition wherein a curing velocity is still more improved. SOLUTION: This activated energy ray-curing type resin composition comprises 0.1-20 pts.wt. of a compound (B) having a maleimido group and an ethylenic unsaturated group represented by formulas 2 and 3 per 100 pts.wt. of a compound (A) having a maleimido group and an ethylenic unsaturated group represented by formula 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a compound having a specific maleimide group and an ethylenically unsaturated group as a main component.
Cured by irradiation with active energy rays such as electron beams or ultraviolet rays. It can be used, for example, for coatings, paints, printing inks, adhesives, fillers, molding materials, stereolithography (3D modeling) systems, lens sheets, electronic materials or resist materials. In this specification, acrylate and / or methacrylate are referred to as (meth)
An acrylate, an acryloyl group and / or a methacryloyl group, a (meth) acryloyl group, an acrylic acid and / or
Alternatively, methacrylic acid is expressed as (meth) acrylic acid.

[0002]

2. Description of the Related Art Compared with conventional solvent-drying resins, ultraviolet-curing resins not only significantly reduce the energy and time required for drying, but also save space during drying and use little or no solvent. The amount used as a coating agent that is friendly to the global environment is increasing year by year. However, in recent years, there has been a situation in which the curability of the curable resin cannot keep up with the demand for increasing the line speed of coating and curing using the same. When the line speed is increased, the curing becomes insufficient. As a result, skin irritation or odor caused by the curable resin may become a problem. Therefore, it is desired to further improve the curability of the ultraviolet curable resin. ing.

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, with respect to the maleimide compound represented by the following formula 9, a specific amount per 100 parts by weight of the maleimide compound is specified. The content of impurities is 0.1
When the resin composition is suppressed to the range of ~ 20 parts by weight,
The inventors have found that the curing speed upon irradiation with active energy rays and the hardness of the resulting cured product are excellent, and have completed the present invention. That is, the present invention provides a maleimide group and an ethylenically unsaturated group represented by any of Chemical Formulas 10 to 14 per 100 parts by weight of the compound (A) having a maleimide group and an ethylenically unsaturated group represented by Chemical Formula 9 below. Is an active energy ray-curable resin composition containing 0.1 to 20 parts by weight of a compound (B) having

[0004]

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[0005]

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[0006]

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[0007]

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[0008]

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[0009]

Embedded image (In the above chemical formulas 9 to 14, R ₁ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or an aryl group.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As the preferable compound (A) in the present invention, a compound in which a structural unit represented by the above formula (9) and an ethylenically unsaturated group are linked by a polyoxyalkylene group is mentioned. And the like. Further, specific compounds belonging to compound (B) include compounds represented by the following chemical formulas in Production Examples.
Or the above-mentioned chemical formula 10 to chemical formula 1 represented by the chemical formula 17
And a compound in which the structural unit represented by 4 and an ethylenically unsaturated group are bonded by a polyoxyalkylene group.

Next, these synthesizing methods will be described.
The compound (A) or (B) in which the ethylenically unsaturated group is a (meth) acryloyl group is synthesized by a method using an acid anhydride, an amino alcohol and (meth) acrylic acid as exemplified below. That is, an alcohol having an imide group is produced by an addition reaction between an acid anhydride and an amino alcohol, followed by a dehydration ring closure reaction. The target substance is obtained by esterifying the obtained alcohol with (meth) acrylic acid, transesterifying (meth) acrylic acid ester with the alcohol, or reacting (meth) acryloyl chloride with the alcohol. Examples of the acid anhydride include phthalic anhydride and its derivatives, 1,2,3,6-tetrahydrophthalic anhydride and its derivatives, 3,4,5,6-tetrahydrophthalic anhydride and its derivatives, 2,3,4-
Tetrahydrophthalic anhydride and its derivatives, 2,3
4,5-tetrahydrophthalic anhydride and derivatives thereof,
Hexahydrophthalic anhydride and its derivatives. Examples of the amino alcohol include alkanolamines such as ethanolamine, propanolamine and hexanolamine, and substituted alkanolamines such as ethoxyethanolamine and propoxypropanolamine.

The addition and dehydration ring-closing reaction for obtaining an alcohol having an imide group is carried out at a temperature of 70 ° C. to 140 ° C. with stirring, as a non-catalytic reaction system or as a catalyst, a sulfonic acid such as sulfuric acid, methanesulfonic acid or paratoluenesulfonic acid. The reaction can be carried out in a reaction system using In the above addition and dehydration ring closure reaction, it is preferable to use an organic solvent as a reaction solvent, and it is preferable to proceed while refluxing the used organic solvent. By removing water generated in the reaction concurrently with the reflux of the organic solvent, the yield of the reaction is increased. The reaction time is preferably about 3 to 10 hours.
As the organic solvent to be used, those which form an azeotrope with water are preferable.Specifically, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane and methyl ethyl ketone and cyclohexanone And the like.

(Meth) acrylic acid is added to the organic solvent solution of the imide group-containing alcohol obtained by the above method, and the dehydration esterification reaction is performed again. In this reaction, it is desirable to use a catalyst such as sulfuric acid, methanesulfonic acid, and paratoluenesulfonic acid. In order to promote the reaction, it is preferable to perform the same dehydration operation as employed in the production of the imide group-containing alcohol. The reaction is carried out at 70 ° C to 140 ° C with stirring. 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 or gelation may occur. In order to suppress radical polymerization of the (meth) acryloyl group during the reaction, it is preferable to add a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and phenothiazine to the reaction system in advance. After completion of the reaction, the organic solvent may be distilled off under reduced pressure, or may be left as it is for adjusting the viscosity of the composition.

The compound (A) or (B) in which the ethylenically unsaturated group is a substituted vinyl group or an unsubstituted vinyl group can be obtained by an addition reaction of the above acid anhydride with an aminoalkyl vinyl ether described below and a subsequent dehydration reaction. Can be synthesized. In such addition reaction and dehydration reaction, the same conditions as in the case of the synthesis of the compound in which the ethylenically unsaturated group is a (meth) acryloyl group can be employed. Aminoalkyl vinyl ethers include aminomethyl vinyl ether, aminoethyl vinyl ether, aminobutyl ether, aminohexyl vinyl ether, aminocyclohexyl vinyl ether, aminononyl vinyl ether, and those in which an alkyl or aryl group is substituted at the α-position or β-position of the vinyl group. And examples thereof include aminoalkylpropenyl ether, aminoalkylisopropenyl ether and aminoalkylstyryl ether.

Specific reaction conditions and the like in the above-mentioned synthesis method are also given as examples in the examples described later, but they are also described in detail in the publicly known documents listed below. it can. -Kiyoshi Kato et al., Journal of the Society of Synthetic Organic Chemistry, 30 (10), 89
7, (1972)-Javier de Abajo et al., Polymer, vol33.
(5), (1992)-JP-A-56-53119, JP-A-1-2425
No. 69

In the present invention, the amount of the compound (B) contained in the compound (A) is 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the compound (A).
Parts by weight. With a resin composition having a compound (B) content of more than 20 parts by weight, the curing rate is insufficient. On the other hand, the smaller the content of the compound (B), the better the curing speed of the resin composition, but it is difficult to completely remove the compound (B) mixed as an impurity during the synthesis of the compound (A),
Even after purification, about 0.1 part by weight of the compound (B) remains. In order to reduce the amount of the compound (B) contained in the compound (A), a method of increasing the purity by distilling the acid anhydride used as a raw material for synthesizing the compound (A) or the method of reducing the acid anhydride And the like by recrystallization. The alcohol addition compound of the compound (B) can be prepared by utilizing the difference in reactivity between the alcohol and the compound (A) or the compound (B), that is, the property that the compound (B) and the alcohol easily undergo an addition reaction. After the formation, the compound (A) which does not undergo the addition reaction is distilled off to separate it from the alcohol-added compound of the compound (B) remaining in the bottom liquid (JP-A-11-180969).
Can also be used.

The resin composition containing the compound (B) in the compound (A) in the above ratio (hereinafter referred to as a specific composition) can be used alone as an active energy ray-curable material. Components other than the compound (B) (hereinafter referred to as other components) may be contained. Other components include the above-mentioned organic solvent and other radically polymerizable compounds. The preferred compounding ratio of the specific composition and the other radical polymerizable compound is 5 to 9 for the specific composition.
5% by weight to 95-5% by weight of other radically polymerizable compounds.

Other radically polymerizable compounds include amide monomers, (meth) acrylate monomers, urethane acrylates, polyester (meth) acrylates, and epoxy (meth) acrylates. Examples of the amide monomer include amide compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholine. As the (meth) acrylate monomer, 2-hydroxyethyl (meth) acrylate, 2
Hydroxyalkyl (meth) acrylates such as -hydroxypropyl (meth) acrylate and 2-hydroxy-3-phenylpropyl acrylate; acrylates of phenol alkylene oxide adducts such as phenoxyethyl (meth) acrylate and halogen nucleus-substituted products thereof Mono- or di- (meth) acrylates of ethylene glycol, 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) acrylates; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate Acrylate, polyol and (meth) acrylic acid esters of alkylene oxide such as dipentaerythritol hexaacrylate, isocyanuric acid EO-modified di- or tri (meth) acrylate.

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 subjecting an epoxy resin to an addition reaction with an unsaturated carboxylic acid such as (meth) acrylic acid, and epoxy (meth) acrylate of bisphenol A type epoxy resin.
Examples include epoxy (meth) acrylate of phenol or cresol novolak type epoxy resin, and (meth) acrylic acid addition reactant of polyglycidyl ether of polyether.

When the composition of the present invention is cured by ultraviolet rays, it is preferable to use a photoinitiator, such as benzoin, benzoin methyl ether or benzoin methyl ether.
Benzoin such as benzoin ethyl ether and benzoin isopropyl ether and its alkyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone Acetophenones such as, 1-hydroxycyclohexylphenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2-methylanthraquinone,
Anthraquinones such as -ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
-Thioxanthones such as chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal;
Monoacyl phosphine oxide or bisacyl phosphine oxide such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzophenones such as benzophenone; and xanthones.
These photoinitiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator. A preferable mixing ratio of the photoinitiator is 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the composition.

The composition may contain, if necessary, a filler such as barium sulfate, silicon oxide, talc, clay and calcium carbonate; a coloring pigment such as phthalocyanine blue, phthalocyanine green, titanium oxide and carbon black; Various additives such as a property imparting agent and a leveling agent, and polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, phenothiazine and aluminum N-nitrosophenylhydroxylamine can also be blended. When these are blended, the blending ratio is preferably 100 parts by weight or less based on the present composition. When the polymerization inhibitor is blended, the blending ratio is preferably 0.00001 to 2% by weight based on the composition.

[0023]

The present invention will be specifically described below with reference to examples. Production Example 1 152 g of 3,4,5,6-tetrahydrophthalic anhydride (99.9% purity) was placed in a flask equipped with a stirrer, a condenser, and a Dean-Stark trap (water separator).
0 mol) and 300 g of toluene, and dissolved by heating at 50 ° C.
When the mixture was refluxed for 3 hours while maintaining the liquid temperature at 115 to 125 ° C., 17.5 g of water was distilled out into the water separator. After cooling the reaction solution, 72 g (1.0 mol) of acrylic acid, 0.15 g of hydroquinone, and 8.4 g of concentrated sulfuric acid were added, and the mixture was refluxed for 3.5 hours while maintaining the solution temperature at 115 to 125 ° C. to obtain 17.5 g. Water distills off in the water separator. After cooling the reaction solution, it was transferred to a separating funnel, and once with 50 g of water, 20%
The mixture was extracted once with 200 g of an aqueous NaOH solution. The solvent was distilled off from the organic layer under reduced pressure to obtain 202 g of a pale yellow solid product. 1H
-NMR and GPC confirmed that the compound of formula 15 was obtained.

[0024]

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Production Example 2 7.4 g of phthalic anhydride was placed in a flask equipped with a stirrer, cooling tube and Dean-Stark trap (water separator).
(0.05 mol) and a mixture of 3,4,5,6-tetrahydrophthalic anhydride (144.4 g, 0.95 mol) and toluene (300 g) were charged, heated to 50 ° C. and dissolved, and ethanolamine (61 g) was dissolved. (1.0 mol) was added dropwise over 30 minutes, and then the mixture was refluxed for 3 hours while maintaining the liquid temperature at 115 to 125 ° C., whereby 17.6 g of water was distilled out into the water separator. After cooling the reaction solution, 72 g (1.0 mol) of acrylic acid, 0.15 g of hydroquinone, and 8.4 g of concentrated sulfuric acid were added, and the mixture was refluxed for 4 hours while maintaining the solution temperature at 115 to 125 ° C., whereby 16.9 g of water was obtained. Distilled in a water separator. After cooling the reaction solution, it was transferred to a separating funnel, and once with 50 g of water, 20% NaOH
Extracted once with 200 g of aqueous solution. The solvent was distilled off from the organic layer under reduced pressure to obtain 205 g of a pale yellow solid product. 1H-NM
By R and GPC, it was confirmed that a mixture of the compounds of formulas 15 and 16 in a weight ratio of 95: 5 was obtained.

[0026]

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Production Example 3 152 g (1.0 mol) of 1,2,3,6-tetrahydrophthalic anhydride and 300 g of toluene were placed in a flask equipped with a stirrer, a condenser, and a Dean-Stark trap (water separator). Was heated and dissolved at 50 ° C., and 61 g (1.0 mol) of ethanolamine was added dropwise over 30 minutes.
Next, when the liquid temperature was kept at 115 to 125 ° C. and refluxed for 3 hours, 17.0 g of water was distilled out into the water separator. After cooling the reaction solution, 72 g (1.0 mol) of acrylic acid, 0.15 g of hydroquinone, and 8.4 g of concentrated sulfuric acid were added, and the solution was heated to 115-
When refluxed for 3.5 hours while maintaining at 125 ° C., 17.1 g was obtained.
Of water distilled off in the water separator. After cooling the reaction solution, it was transferred to a separating funnel, and once with 50 g of water, 200 g of a 20% aqueous NaOH solution was used.
Extracted once. The solvent was distilled off from the organic layer under reduced pressure to obtain 190 g of a pale yellow solid product. By 1H-NMR and GPC,
It was confirmed that the compound of Chemical Formula 17 was obtained.

[0028]

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[0029]

Examples 1-3 The curability, bending resistance and pencil hardness of the compositions obtained by blending the curable resins in the proportions shown in Table 1 were evaluated by the following methods, and the results are also shown in Table 1. Also described. 〇Curability A 0.2 mm thick electroplated tin plate or aluminum plate is used as a base plate, and a curable resin composition is coated on the base plate using a bar coater so that the coating thickness becomes 10 μm. 80W / cm, 1 from the bottom of the condensing high-pressure mercury lamp
The sheet was repeatedly passed under a mercury lamp at a position of 0 cm and at a conveyor speed of 20 m / min, and evaluated by the number of passes (number of passes) until the surface was free of tackiness.屈曲 Bending resistance According to the bending resistance test of JIS K5400, the diameter is 4mm.
Was evaluated using a mandrel. ：: No cracks or peeling in the coating film Δ: Slight cracks or peeling X: Cracks or peeling were found all over the bent portion 〇 Pencil hardness The coated substrate was evaluated according to JIS K5400.

[0030]

[Table 1] 1) Bifunctional urethane acrylate [Aronix M1600 manufactured by Toagosei Co., Ltd.] 2) Benzyl dimethyl ketal [Irgacure 651 manufactured by Ciba Specialty Chemicals Co., Ltd.]

[0031]

Comparative Example 1 A resin composition consisting of 50 parts by weight of the curable resin obtained in Production Example 1 and 50 parts by weight of the curable resin selected in Production 3 was added to Aronix M1 manufactured by Toagosei Co., Ltd.
The above-mentioned physical properties were evaluated for the curable resin composition obtained by adding 20 parts by weight of 600 and 2 parts by weight of Irgacure 651 manufactured by Ciba Specialty Chemicals Co., Ltd. The results are as follows.・ Curability (pass) 9, ・ Pencil hardness H, ・ Bending resistance △.

[0032]

EFFECT OF THE INVENTION The composition of the present invention is very fast-curing and has a high hardness of the cured product, so that coatings, paints,
Printing inks, adhesives, fillers, molding materials, stereolithography (3D
Modeling) It is useful in various industrial fields such as systems, lens sheets, electronic materials, and resist agents.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Kunihiko Mizutani 1-1-1, Funami-cho, Minato-ku, Nagoya-shi, Aichi F-term (reference) in Nagoya Research Laboratory, Toagosei Co., Ltd. 4J011 AA01 AC04 BA03 QA03 QA08 QA13 QA17 QA23 QA24 QA34 QA39 QB14 QB15 QB19 QB20 QB22 QB23 SA02 SA06 SA07 SA22 SA32 SA36 SA54 SA63 SA64 SA83 SA84 UA01 VA01 VA04 WA01 WA02 WA06 WA07 4J100 AE09P AE09Q AE18P AL08P AL08Q AL08R AL09R AL62R BARR08R BC08 BC66Q BC73R BC79R CA01 CA04 JA01 JA03 JA07 JA33 JA38 JA43

Claims (4)

[Claims] 1. A maleimide group and an ethylenically unsaturated group represented by any of Chemical Formulas 2 to 6 per 100 parts by weight of a compound (A) having a maleimide group and an ethylenically unsaturated group represented by the following Chemical Formula 1. The compound (B) has a content of 0.
An active energy ray-curable resin composition comprising 1 to 20 parts by weight. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image (In the above Chemical Formulas 1 to 6, R ₁ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or an aryl group.) 2. The active energy ray-curable resin composition according to claim 1, wherein the compound (A) is the compound (A-1) represented by the formula (7). Embedded image (Wherein, R ₁ is a hydrogen atom, an alkyl group or an aryl group having 1 to 9 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ is a linear or branched alkylene group having 1 to 6 carbon atoms, And n is an integer from 1 to 6.) 3. The active energy ray-curable resin composition according to claim 1, wherein the compound (A) is a vinyl group-containing maleimide compound (A-2) represented by the following formula (8). Embedded image (Wherein R ₁ is a hydrogen atom, an alkyl or aryl group having 1 to 9 carbon atoms, R ₃ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ₄ , R ₅ and R ₆ are A hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.) 4. An active energy ray-curable resin composition according to claim 1, 2 or 3, and a radical polymerizable compound (C) other than the compound (A) or (B), based on the total amount thereof. An active energy ray-curable resin composition containing 5 to 95% by weight of the active energy ray-curable resin composition and 95 to 5% by weight of the radical polymerizable compound (C).