JP2001064327A - Actinic-radiation-curing resin composition comprising novel maleimide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition being rapid-curing and odorless and giving a cured product having a high hardness simply in good yields by using a compound having both a maleimide group and an ethylenically unsaturated group. SOLUTION: This composition comprises (A) a compound having a maleimide group represented by formula I (wherein R1 is a 1-9C alkyl or aryl) and an ethylenically unsaturated group in the molecule. The ethylenically unsaturated group is desirably (meth)acryloyl or an (un)substituted vinyl. In the former case, compound A is a (meth)acryloyl-containing maleimide compound of formula II (wherein R1 is as defined in formula I; R2 is H or CH3; R3 is a 1-6C linear or branched alkylene; and (n) is an integer of 1-6). In the latter case, compound A is a (substituted)-vinyl-containing maleimide compound of formula III (wherein R1, R3, and (n) are as defined in formula II; and R4, R5, and R6 are each H, a 1-6C alkyl or aryl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a compound having a specific maleimide group and an ethylenically unsaturated group. The resin composition of the present invention can be cured by irradiation with an active energy ray such as an electron beam or an ultraviolet ray, or by heating.

Further, the active energy ray-curable composition of the present invention can be used for coatings, paints, printing inks, adhesives, fillers, molding materials, 3D modeling systems, electronic materials,
It can be used as a resist agent and the like. In the present specification, acrylate and / or methacrylate are represented by (meth) acrylate, acryloyl group and / or methacryloyl group are represented by (meth) acryloyl group, and acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid. .

[0003]

2. Description of the Related Art Active energy ray-curable resins, such as ultraviolet ray-curable resins and electron beam-curable resins, greatly reduce the energy and time required for drying compared to conventional solvent-drying resins due to their rapid curing properties. It has been evaluated for its features of being able to use it, saving space during drying, and using only a small amount of solvent or not using it at all, and being environmentally friendly. Is coming. In recent years, in line assembly products, there is an increasing demand for further increasing the line speed in order to cope with the improvement of productivity and the diversification of small quantities. However, some of the active energy ray-curable resin raw materials have skin irritation or odor, but if the curing becomes insufficient by increasing the line speed, the skin due to uncured components Since irritation and odor become problems, it has been desired to improve curability more than before.

[0004]

SUMMARY OF THE INVENTION The present inventors have made intensive studies in view of such a situation. As a result, the present inventors have found that they are very fast-curing, have high hardness of cured products, have no odor, and are simpler. A novel maleimide compound having both an ethylenically unsaturated group and a maleimide group, which can be produced in good yield by the method, and an active energy ray-curable resin composition containing the novel maleimide compound have been completed, and the present invention has been completed. .

[0005]

That is, the present invention provides an active energy ray-curable resin composition containing, as a main component, a compound (A) having both a maleimide group and an ethylenically unsaturated group represented by the following formula (1). Things.

Embedded image However, in the formula (1), R ₁ is an alkyl group or an aryl group having 1 to 9 carbon atoms. In the present invention, the ethylenically unsaturated group is preferably a (meth) acryloyl group or a (unsubstituted) vinyl group.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (A) in the present invention is
It is a compound having both a maleimide group represented by the formula (1) and an ethylenically unsaturated group in the molecule.

Embedded image However, in the formula (1), R ₁ is an alkyl group or an aryl group having 1 to 9 carbon atoms. In the present invention, the ethylenically unsaturated group is preferably a (meth) acryloyl group or a (unsubstituted) vinyl group.

[0007] In general, the maleimide group undergoes a hydrogen abstraction reaction when irradiated with an active energy ray to generate a radical, as described in "Sony Jonsson et al., Radotech '95 Europe Preliminary Lecture <Academic Day>p.34" and the like. Are known. Further, the maleimide group may cause a cross-linking reaction upon irradiation with an active energy ray, as disclosed in JP-A-52-988 and JP-A-55-988.
As known from Japanese Patent No. -160010 and the like, in the resin composition of the present invention, a cross-linking reaction occurs between molecules by irradiation with active energy rays, and the hardness of the obtained coating film is excellent. In the case of the resin composition of the present invention, in addition to the above-described cross-linking reaction between molecules, the compound having an ethylenically unsaturated group is initiated by radicals generated by a maleimide group, and is cured. The amount of addition can be reduced or eliminated.

In the present invention, the fact that only _one substituent (R ₁ ), which is an alkyl group or an aryl group, is bonded to the alkene moiety constituting the maleimide ring of the formula (1) is extremely difficult to synthesize in the first step. It has been found that the presence of a substituent makes it possible to synthesize a compound having a significantly higher yield than a compound having an unsubstituted maleimide ring. At the same time, the maleimide compound of the present invention having only one substituent on the alkene moiety constituting the maleimide ring has a higher hardness of the cured product than a similar maleimide compound having two substituents on the alkene moiety, and It has also been found that the curability upon irradiation with active energy rays is excellent.

When the ethylenically unsaturated group is a (meth) acryloyl group, the compound (A) in the present invention is substituted with an acid anhydride, an amino alcohol and (meth) acrylic acid, and the ethylenically unsaturated group is substituted. When it is a vinyl group or an unsubstituted vinyl group, it is described in the following documents and patents from an acid anhydride and an aminoalkyl vinyl ether or an ether in which an alkyl group or an aryl group is substituted at the α-position or the β-position of the vinyl group. Can be synthesized by a certain method. Kato Kiyoshi et al., Journal of Synthetic Organic Chemistry, 30 (10), 897,
(1972) Javier de Abajo et al., Polymer, vol 33.
(5), (1992) JP-A-56-53119, JP-A-1-24256
No. 9

As the raw materials in the above synthesis method, examples of the acid anhydride include citraconic anhydride, monoalkylmaleic anhydride and derivatives thereof. Examples of the amino alcohol include alkanolamines such as ethanolamine, propanolamine and hexanolamine, and substituted alkanolamines such as ethoxyethanolamine and propoxypropanolamine. Furthermore, as aminoalkyl vinyl ethers, 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, such as aminoalkylpropenyl ether, aminoalkylisopropenyl ether and aminoalkylstyryl ether. is there.

According to the above method, when the ethylenically unsaturated group is a (meth) acryloyl group, the compound (B)
The synthesis of is divided into two steps. The first step is an addition reaction between an acid anhydride and an amino alcohol and a subsequent dehydration reaction, and the second step is an alcohol having an imide group obtained in the first step and (meth) acrylic acid, This is a condensation reaction with (meth) acrylic acid ester or (meth) acryloyl halide.

Hereinafter, a method for synthesizing the compound (B) will be described in detail. <First process: Addition reaction of acid anhydride and amino alcohol and dehydration ring closure reaction> In the imidation reaction for obtaining a maleimide group-containing alcohol which is a precursor of compound (B), an addition reaction and dehydration ring closure reaction are performed without a catalyst. And a catalyst may be used if necessary. The dehydration ring-closing reaction is carried out without a catalyst or in the presence of sulfonic acids such as sulfuric acid, methanesulfonic acid, and paratoluenesulfonic acid 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. At the time of the dehydration ring closure reaction, it is preferable to use an organic solvent having low solubility in water and promote dehydration while azeotropically evaporating water. Examples of the organic solvent to be used include, but are not limited to, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane and heptane.

<Second Step: (Meth) acryloylation Reaction> After the first step, the esterification reaction for obtaining the compound (B) of the formula (2) may be carried out by transesterification reaction with an alkyl (meth) acrylate or (meth) ) A dehydration esterification reaction in which acrylic acid is dehydrated and a reaction with (meth) acrylic acid halide are not particularly limited.

Next, an example in which a dehydration esterification reaction is employed will be described. This reaction desirably uses a catalyst. The reaction is carried out at 70 ° C to 140 ° C in the presence of sulfonic acids such as sulfuric acid, methanesulfonic acid and paratoluenesulfonic acid.
Is performed under 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 the reaction, it is preferable to use an organic solvent having low solubility in water, and to promote dehydration while azeotropically evaporating water. Examples of the organic solvent to be used include, but are not limited to, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and ketones such as methyl ethyl ketone and cyclohexanone. After the reaction, this solvent may be distilled off under reduced pressure, or may be used as it is for adjusting the viscosity of the composition. Further, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and phenothiazine for suppressing radical polymerization of the (meth) acryloyl group may be used.

In the present invention, when the ethylenically unsaturated group is a substituted or unsubstituted vinyl group, the maleimide compound (C) is obtained by an addition reaction between an acid anhydride and an aminoalkyl (substituted or unsubstituted) vinyl ether, followed by dehydration. Obtained by reaction. These two reactions can be carried out according to the reaction conditions of the first step in the synthesis of compound (B) described above.

In the resin composition of the present invention, an active energy ray-curable resin composition is obtained by using another radically polymerizable compound together with the compound (A). Examples of the radical polymerizable compound 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. (Meth) acrylate monomers include; imide acrylates such as hexahydrophthalimidoethyl acrylate and succinimidoethyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenylpropy Hydroxyalkyl (meth) acrylates such as acrylates; acrylates of alkylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and their halogen nuclei; mono- or di (meth) acrylates of ethylene glycol, methoxyethylene glycol Mono (meth) acrylate, tetraethylene glycol mono or di (meth) acrylate, tripropylene glycol mono or di (meth) acrylate, etc. ,
Glycol mono- or di (meth) acrylates; polyols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate and alkylene oxides thereof ( (Meth) acrylic acid ester, isocyanuric acid EO modified di- or tri (meth) acrylate, and the like.

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.

The polyester (meth) acrylate oligomer includes 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 (meth) acrylate is obtained by subjecting an epoxy resin to an addition reaction with an unsaturated carboxylic acid such as (meth) acrylic acid, and is an epoxy (meth) acrylate of bisphenol A type epoxy resin, phenol or cresol novolac type epoxy resin. Epoxy (meth) acrylate of resin, (meth) acrylic acid addition reactant of diglycidyl ether of polyether and the like can be mentioned. Compound (A) in the curable resin composition of the present invention
The preferable mixing ratio of the above-mentioned radical polymerizable compound is such that the compound (A) is in the range of 5 to 95% by weight based on the total amount thereof. 5% by weight of compound (A)
If it is less than the above, the curing rate by irradiation with active energy rays is too slow to achieve the object of the present invention. On the other hand, when the compounding ratio of the compound (A) is more than 95% by weight, the cured product is brittle and a satisfactory coating film cannot be obtained, which is inconvenient.

When the composition of the present invention is cured by ultraviolet rays, a photoinitiator may be used if necessary. Benzoin and its alkyl ether such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether;
Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexylphenylketone, and 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholino-propane-1-
Acetophenone such as on; 2-methylanthraquinone;
Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
Thioxanthones such as 2-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 initiator. The preferred mixing ratio of these photoinitiators is 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the composition.

[0025]

The present invention will be specifically described below with reference to examples. The chemical formulas of the products obtained in the following Production Examples 1 to 8 were described as Formulas (4) to (11). Production Example 1 Citraconic anhydride 10 was placed in a flask equipped with a stirrer, a condenser, and a Dean-Stark trap (water separator).
0.8 g (0.9 mol) and 156 g of toluene were charged,
Heated to 50 ° C. to dissolve, and ethanolamine 55.0 g
(0.9 mol) was added dropwise over 30 minutes.
After refluxing for 3.5 hours while maintaining the temperature at 5-120 ° C, 15.
0 g of water distilled off in the water separator. After cooling the reaction solution, 64.8 g (0.9 mol) of acrylic acid and hydroquinone 0.
10 g and 8.4 g of concentrated sulfuric acid were added, and the liquid temperature was adjusted to 115-120.
When the mixture was refluxed at 3.0 ° C. for 3.0 hours, 15.0 g of water was distilled off into the water separator. After cooling, the reaction solution was transferred to a separating funnel and extracted once with 30 g of water and once with 60 g of a 20% aqueous NaOH solution. The organic layer was evaporated under reduced pressure to obtain a pale yellow liquid product in a yield of 68%. 1H-NMR confirmed that the desired compound (Formula (4)) was obtained. The obtained compound had no odor at all.

Production Examples 2 to 8 The reaction was carried out under the same conditions except that the acid anhydrides, amino alcohols and unsaturated carboxylic acids used as raw materials were changed as shown in Table 1. In addition, each raw material was charged in the same mole number as in Production Example 1.

[0027]

[Table 1]

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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Production Example 9 Citraconic anhydride 10 was added to a flask equipped with a stirrer, a condenser, and a Dean-Stark trap (water separator).
0.8 g (0.9 mol) and 156 g of toluene were charged,
The mixture was dissolved by heating to 50 ° C., and 91.0 g (0.9 mol) of 3-amino-1 propanol vinyl ether was added dropwise over 30 minutes. Then, the mixture was refluxed for 6 hours while maintaining the liquid temperature at 115 to 120 ° C. 15.0 g of water distilled off in the water separator.
After cooling the reactor, it was transferred to a separating funnel and extracted once with 30 g of water. The organic layer was evaporated under reduced pressure to obtain a pale yellow liquid product in a yield of 65%. 1H-NMR confirmed that a desired compound (formula (12)) was obtained.
The obtained compound had no odor at all.

[0037]

Embedded image

Comparative Production Example 1 Comparative Production Example 1 is different from the maleimide compound of the present invention.
This is an example in which no substituent consisting of an alkyl group or an aryl group is bonded to the alkene portion of the maleimide ring, and was obtained using maleic anhydride as the acid anhydride. The reaction was carried out under the same conditions as in Production Example 1 except that the acid anhydride used as the raw material was changed as shown in the table below. The raw materials were charged in the same mole number as in Production Example 1. Stirring was performed in the same manner, but the amount of dehydration was small, and the reaction rate calculated from the amount of dehydration of the first reaction was about 50%. After the first reaction,
Analysis of the reaction mixture revealed that a large amount of oligomer-like by-products was produced. Further, acrylic acid and a reaction catalyst were charged into the reaction solution, and the second reaction was performed. The reaction rate calculated from the dehydration amount was about 30%. After the completion of the second reaction, the reaction mixture was analyzed. As a result, the desired product (formula (13)) was hardly obtained, and thus the isolation was not performed.

[0039]

Embedded image

Comparative Production Example 2 Comparative Production Example 2 is different from the maleimide compound of the present invention.
The substituent (methyl group) is 2 on the alkene portion of the maleimide ring.
This is an example in which dimethylmaleic anhydride is used as the acid anhydride. The reaction was carried out under the same conditions as in Production Example 1 except that the acid anhydride used as the raw material was changed as shown in [Table 2] to obtain a product of the formula (14). The raw materials were charged in the same mole number as in Production Example 1.

[0041]

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[0042]

[Table 2] Note 1) Almost no desired product was obtained.

Examples and Comparative Examples Curing consisting of various compounds (A) obtained in Production Examples 1 to 11, other radically polymerizable compounds and photoinitiators, having the constitutions shown in [Table 3] and [Table 4]. After coating the mold composition on a substrate and irradiating the coating film with ultraviolet light using a high-pressure mercury lamp, the curability, pencil hardness, and odor of the cured coating film were evaluated by the following methods. 3] and [Table 4]. Further, the curable composition having the constitution shown in [Table 5] consisting of the maleimide compound, other radically polymerizable compound and the photoinitiator obtained in Comparative Production Example was applied and cured in the same manner as in Example. Thereafter, the evaluation results of the coating films are shown in Table 5 as comparative examples. [Evaluation Method of Curability] Bonderite steel plate (PB-144 manufactured by Japan Test Panel Co., Ltd.) was used as a base material, and a curable composition was applied to the base material so as to have a film thickness of 10 μm.
10m / m under 80W / cm focusing high pressure mercury lamp (1 lamp)
The sheet was passed at a conveyor speed of "in" and touched with the hand to evaluate the number of passes until the tack on the surface disappeared. [Pencil hardness] The pencil hardness was measured in accordance with the test method of JIS K-5400. [Odor] The smell of the coating film immediately after curing was directly evaluated. ○: No odor △: Almost none ×: Odor

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

The radical polymerizable compounds other than the compound (A) described in [Table 3], [Table 4] and [Table 5] are as follows. 1) Pentaerythritol triacrylate (Aronix M305 manufactured by Toa Gosei Co., Ltd.) 2) Diacrylate of bisphenol F ethylene oxide 2 mol adduct (Aronix M208 manufactured by Toa Gosei Co., Ltd.) 4) Dipentaerythritol hexaacrylate (Toa Gosei Co., Ltd.) ) Aronix M400) 5) Phenoxyethoxyethyl acrylate (Alonix M101 manufactured by Toagosei Co., Ltd.) 6) Ethoxyethoxyethyl acrylate (Viscoat 190 manufactured by Osaka Organic Co., Ltd.) and photo-start in Tables 3 to 5 Irg651 ³⁾ used as an agent is benzyldimethyl ketal (Irgacure 651 manufactured by Ciba Specialty Chemicals Co., Ltd.).

[0048]

The composition of the present invention is very fast-curing, has a high hardness of the cured product, has no odor, and can be produced in a simple manner with good yield. It is useful in various industrial fields such as adhesives, fillers, molding materials, 3D modeling systems, resist agents, and electronic materials.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J011 QA03 QA07 QA17 QA22 QA23 QA39 QB12 QB19 QB23 SA01 SA31 SA51 SA63 SA64 UA01 UA03 4J100 AL08Q AL09Q AL62Q AL63Q AM21Q AM54P AQ08Q BA02P BA02Q BA05Q BA03 BA04Q JA07 JA37 JA38

Claims (4)

[Claims] 1. An active energy ray-curable resin composition containing a compound (A) having both a maleimide group represented by the formula (1) and an ethylenically unsaturated group in one molecule. Embedded image However, in the formula (1), R ₁ is an alkyl group or an aryl group having 1 to 9 carbon atoms. 2. The active energy ray-curable resin composition according to claim 1, wherein the compound (A) is a (meth) acryloyl group-containing maleimide compound (B) represented by the formula (2). Embedded image Here, R ₁ is an alkyl or aryl group having 1 to 9 carbon atoms, R ₂ is an H or CH ₃ group, R ₃ is a linear or branched alkylene group having 1 to 6 carbon atoms, and n is 1 to 6 Represents an integer up to. 3. A substituted or unsubstituted vinyl group-containing maleimide compound (C) wherein the compound (A) is represented by the formula (3):
The active energy ray-curable resin composition according to claim 1, wherein Embedded image Here, R ₁ is an alkyl group or an 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 H or An alkyl group or an aryl group having 1 to 6 carbon atoms, and n is 1
Is an integer from 1 to 6. 4. An active energy ray-curable resin composition comprising the compound (A) and another radically polymerizable compound and containing the compound (A) in an amount of 5 to 95% by weight based on the total amount thereof.