JP2002060483A - Active energy ray-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an active energy ray-curable resin composition which has good curability by ultraviolet irradiation without using a photocationic polymerization initiator. SOLUTION: This active energy ray-curable resin composition comprises (A) a compound having at least one oxetane ring in the molecule and (B) a maleimide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition which is rapidly cured by irradiation with active energy rays such as ultraviolet rays. More specifically, the present invention relates to an active energy ray-curable resin composition which can be cured without using a cationic photopolymerization initiator such as a sulfonium salt and an iodonium salt.

[0002]

2. Description of the Related Art Active energy ray curing technology has various characteristics such as a high curing speed, good workability due to generally no solvent, and an extremely low energy requirement.
It has become extremely important in various industries such as various coatings, metal painting and printing. While most of the materials used in these fields are polyfunctional acrylates and most of the research has been directed to active energy beam initiated radical polymerization, photoinitiated ionic polymerization is also quite promising in many applications. In particular, photoinitiated cationic polymerization can achieve various chemical and physical properties through the polymerization of a wide variety of materials.

[0003]

In the above-mentioned photo-initiated cationic polymerization, it is conventionally necessary to use a photo-cationic polymerization initiator such as an iodonium salt or a sulfonium salt. It is not preferable because it causes adverse effects depending on the application.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an active energy ray-curable composition containing a compound having one or more oxetane rings in the molecule and a maleimide compound as essential components is practical. The present inventors have found that the composition has excellent curability and good properties and completed the present invention. That is, the present invention provides: 1. An active energy ray-curable resin composition comprising a compound (A) having one or more oxetane rings in the molecule and a maleimide compound (B); 2. The active energy ray-curable resin composition according to item 1, which contains a compound (C) having one or more oxirane rings in the molecule. 3. The active energy ray-curable resin composition according to 1 or 2, which contains a compound (D) having one or more vinyl ether groups in a molecule. Any one of 1 to 3, wherein the maleimide compound (B) is a maleimide compound having a cyclo ring or an aliphatic group
4. The active energy ray-curable resin composition according to the above item, 5. The active energy ray-curable resin composition according to item 3 or 4, wherein the compound (D) having one or more vinyl ether groups in the molecule is cyclohexyl-1,4-dimethanol divinyl ether.

Hereinafter, the present invention will be described in detail. As the compound (A) having one or more oxetane rings in the molecule used in the present invention, various compounds can be used, and preferred compounds include compounds represented by the following formula (1).

[0006]

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(Wherein m is a number from 1 to 30;
Z is an oxygen atom or a sulfur atom. R ¹Is a hydrogen atom,
Nitrogen atom, methyl group, ethyl group, propyl group and butyl
An alkyl group having 1 to 6 carbon atoms such as a group,
Fluoroalkyl group, allyl group, aryl group or furyl
Group. R^TwoIs, for example, a carbon number 1 represented by the formula (2)
Linear or branched alkyl optionally having up to 12 hydroxyl groups
Groups, linear or branched poly (alkyleneoxy) groups
You. )

[0008]

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(In the formula (2), R ³ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group.)

R2 is represented by the following (3), (4), (5),
It may be a polyvalent group selected from the group consisting of (6) and (7).

[0011]

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(In the formula (3), n is an integer of 0 to 2000. R ⁴ and R ⁵ are each an alkyl group having 1 to 10 carbon atoms and a group selected from the group consisting of the following (8). .

[0013]

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(In the formula (8), j is 0 or an integer of 1 to 100, and R ⁶ is an alkyl group having 1 to 10 carbon atoms.)

[0015]

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(In the formula (4), R ⁷ is a hydrogen atom and has 1 carbon atom.
An alkyl group of 10 to 10, an alkoxy group having 1 to 10 carbon atoms,
It is a halogen atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxylate group or a carboxyl group. )

[0017]

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(In the formula (5), R ⁸ is an oxygen atom, a sulfur atom, NH, SO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ or C
(CF ₃ ) ₂ . )

[0019]

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(In the formula (6), R ⁹ is a hydrogen atom and has 1 carbon atom.
10 to 10 alkyl groups or bromine atoms;
~ 30. )

[0021]

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(In the formula (7), X is a number from 0 to 5.)

In the present invention, in formula (1), R ¹ is preferably a lower alkyl group, more preferably an ethyl group. R ² is preferably a group in which R ⁷ is a hydrogen atom in the formula (4), a hexamethylene group, and a group in which R ³ is an ethyl group in the formula (2). Also, R ⁵ , R ⁶ and R ⁹ are preferably methyl. Z is preferably an oxygen atom. Other preferred specific examples of the compound (A) include the compounds of the formulas (9) and (10).

[0024]

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[0025]

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(In the formula (9), y is an integer of 25 to 200, and R ⁹ is an alkyl group having 1 to 4 carbon atoms or a trialkylsilyl group.)

In the present invention, two or more of the above compounds (A) can be used in combination.

As the maleimide compound (B) used in the present invention, various compounds can be used, and preferred compounds include a compound having a maleimide group represented by the following formula (11) or (12). Can be.

[0029]

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(In the formula (11), R ¹¹ and R ¹² are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.)

[0031]

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(In the formula (12), R ¹³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.) Specifically, JP-A-52-988 Gazette, JP-A-55-
No. 160010, JP-A-62-64813,
JP-A-61-250064, JP-A-3-1241
No. 4, JP-A-62-79243, JP-A-57-79243
-205413, JP-A-2-268155, JP-A-58-40374, JP-A-11-12
Maleimide compounds described in JP-A-4404 and JP-A-11-124403 can be used.

More specifically, N-cyclohexylmaleimide, methylenebis (4-N-cyclohexylmaleimide), N- (4-cyclohexyl) dimethylmaleimide, 3- (N-methylmaleimide) -3,5,5- Trimethylcyclohexyl-maleimide, 2,5 (or 6) -bis (N-methylmaleimide) -bicyclo [2,
2,1] heptane 1,3-bis (N-methylmaleimide) cyclohexane and other cyclo-ring-containing maleimide compounds; N-butylmaleimide, 2- (N-ethylmaleimide) -2,6-dimaleimidocaproate, , 2,4
-Trimethylhexamethylene dimaleimide, 2,4,4
-Trimethylhexamethylene dimaleimide, N-methylmaleimide, N-dodecylmaleimide, N-hydroxyethylmaleimide, N-1-methoxymethylpropylmaleimide, N-1-ethoxymethylpropylmaleimide, N-1-methoxymethylbutylmaleimide, Aliphatic maleimide compounds such as bis (3-N-maleimidopropyl) polytetrahydrofuran, N- [6-methyl-4-oxa-5-oxo-heptene 16] -yl] -dimethylmaleimide; {-1-tetrahydronaphthalimide N-phenylmale compounds such as cyclohexyl, △ -1-tetrahydronaphthalimidoethyl, △ -1-tetrahydronaphthalimidopropyl, △ -1-tetrahydronaphthalimidoethyl methacrylate; De, N-(0- chlorophenyl) maleimide, 4,4'-diphenylmethane bismaleimide, N-(P- methoxyphenyl) maleimide,
Aromatic maleimide compounds such as N, N'-m-xylylenebismaleimide and the like can be mentioned.

Particularly preferred maleimide compounds include:
Examples of the above-mentioned cyclo ring-containing maleimide compound and aliphatic maleimide compound can be given.

In the present invention, two or more of the above compounds (B) can be used in combination. In the present invention, the compound (C) having one or more oxirane rings in the molecule can be used. Specific examples of the compound (C) include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. The aromatic epoxy resin is a di- or polyglycidyl ether produced by reacting a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof with epichlorohydrin, for example, bisphenol A or an alkylene oxide thereof. Examples of the adduct include diglycidyl ether as an adduct, hydrogenated bisphenol A or diglycidyl ether or biphenyl diglycidyl ether as an alkylene oxide adduct thereof, a phenol novolak epoxy resin, and a cresol novolac epoxy resin.

The alicyclic epoxy resin is obtained by epoxidizing a compound having at least one cycloalkane ring such as a cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracetic acid.
Cyclohexene oxide or a compound containing cyclopentene oxide is preferred, and specific examples thereof include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, epoxidized polybutadiene, and limonenedi. Oxides and the like can be mentioned.

Preferred examples of the aliphatic epoxy resin include di- or polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, and the like.
Typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol and diglycidyl ether of 1,6-hexanediol, and the like, and di- or tri-alkylene glycol diglycidyl ether, glycerin or an alkylene oxide adduct thereof. And polyglycidyl ethers of polyhydric alcohols such as glycidyl ether. Further, in addition to these compounds, it is also possible to use monoglycidyl ethers of aliphatic higher alcohols, which are monomers having one oxirane ring in the molecule, phenol, cresol or monoglycidyl ethers of these alkylene oxide adducts. it can.

Preferred examples of the compound (C) include the alicyclic epoxy resins described above. In the present invention,
Two or more compounds (C) can be used in combination.

In the present invention, the compound (D) having one or more vinyl ether groups in the molecule can be used.
Monovinyl ether and divinyl ether are preferred as specific examples of compound (D). Examples of monovinyl ethers are alkyl vinyl ethers, typically having from 1 to 22 carbon atoms. As divinyl ether, ethylene glycol, propylene glycol,
Examples include butylene glycol, cyclohexane-1,4-dimethanol, triethylene glycol, divinyl ether of tripropylene glycol, polyester divinyl ether, and polyurethane divinyl ether.

Particularly preferred compound (D) is, for example, divinyl ether of cyclohexane-1,4-dimethanol. In the present invention, two or more of the above compounds (D) can be used in combination. In the present invention, it is particularly preferable to use the compound (B) and the compound (D) in combination from the viewpoint of curability.

As other components, the composition of the present invention comprises:
In addition to the above essential components, inactive components such as an inorganic filler, a dye, a pigment, a viscosity modifier, an organic solvent and an ultraviolet ray blocking agent can be blended.

Further, if necessary, a diaryliodonium salt, a triarylsulfonium salt or various (meth) acrylate compounds which are photocationic polymerization initiators can be used.

As a method for producing the active energy ray-curable resin composition of the present invention, the compounds (A), (B),
(C) and (D) may be mixed according to a conventional method. Here, the compound (A) is preferably compounded in an amount of 5 to 100 parts by weight based on 100 parts by weight of the total amount of the compound (A) and the compound (C) in the composition. Compound (B) and compound (D)
Is preferably 1 to 100 parts by weight, particularly preferably 1 to 50 parts by weight, based on 100 parts by weight of the total amount of compound (A) and compound (C) in the composition. As the compounding ratio of the compound (B) and the compound (D),
When the total amount of the compound (B) and the compound (D) is 100 parts by weight, the compound (B) is preferably 20 to 80 parts by weight.

The resin composition of the present invention is easily cured by irradiation with active energy rays such as ultraviolet rays. When irradiating ultraviolet rays, various light sources can be used, for example, a mercury arc lamp, a xenon arc lamp,
It can be cured by light from fluorescent lamps, carbon arc lamps, tungsten-halogen copy lamps and ambient sunlight. If necessary, curing can be carried out by irradiating ultraviolet rays and using heat in a nitrogen stream.

The composition of the present invention can be applied to substrates such as metals, rubbers, plastics, molded parts, films, paper, wood, glass cloth, concrete and ceramic.

Examples of uses of the composition of the present invention include:
Examples include protective, decorative and insulating coatings, triads, printing inks, sealants, adhesives, photoresists, resin wire insulating materials for stereolithography, textile coatings, laminates, impregnated tapes and printing plates.

[0047]

The present invention will now be described in detail with reference to examples and comparative examples.

Example 1 Xylylene bis octacene 100 was used as compound (A).
g, cyclohexylmaleimide 2 as compound (B)
5 g and 25 g of divinyl ether of cyclohexane-1,4-dimethanol were mixed to prepare an active energy ray-curable resin composition. The composition is placed on a rigid PVC plate for about 2
After application so as to have a thickness of 0 μm, an irradiation amount (mJ / cm ² ) is used in which the tack on the surface of the coating film is eliminated by using a conveyor-type ultraviolet irradiation device provided with a high-pressure mercury lamp of 80 W / cm.
Was measured, and this was regarded as curable. Using this cured coating film, the pencil hardness was measured according to JIS K5400.

Examples 2 to 5, Comparative Examples 1 and 2 Hexamethylene-1,6-dioxetane as compound (A), bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl-3,4 as compound (C) -Epoxycyclohexylcarboxylate,
A composition was prepared in the same manner as in Example 1, using cyclohexylmaleimide as the compound (B) and divinyl ether of cyclohexane-1,4-dimethanol as the compound (D) at the composition ratios shown in Table 1. did. The obtained composition was evaluated in the same manner as in Example 1. Table 1 shows the results.

Example Comparative Example 1 2 3 4 5 12 1 Compound (A) Xylylenebisoxetane 100 100 100 Hexamethylene-1,6-dioxetane 70 70 100 100 Compound (B) Cyclohexylmaleimide 25 50 25 25 Methylene bis (4 -Cyclohexylmaleimide) 15 Compound (C) Bisphenol A diglycidyl ether 30 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate 30 Compound (D) Divinyl ether of cyclohexane-1,4-dimethanol 25 25 25 15 Curability (mJ / cm ² ) 552 1500 828 552 552 Uncured Uncured Pencil hardness H 2B H 2H H − −

Note: In Example 2, the curability was measured by irradiating ultraviolet rays in a nitrogen stream. Comparative Examples 1 and 2 were 2 J / cm ²
Irradiation was performed in air and in a nitrogen gas flow, but it was uncured under any conditions.

[0052]

The active energy ray-curable resin composition of the present invention can be practically cured by irradiating active energy rays such as ultraviolet rays without using a diaryliodonium salt or a triarylsulfonium salt as a cationic photopolymerization initiator. The cured product has good physical properties, protective, decorative and insulating coatings, optical fiber coatings, optical disc coatings, optical disc adhesives, castings, guarants, printing inks, sealants It can be used in various applications such as adhesives, photoresists, wire insulation materials, textile coatings, laminates, impregnated tapes and printing plates.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J005 AA07 AA11 BA00 BB01 4J011 AA05 AC04 BA03 CA00 CC10 QA08 QA19 QA39 QC10 SA73 SA83 UA01 VA01 WA02 WA05 WA06 WA10 4J036 AB01 AB07 AB10 AD08 AD15 AF06 AJ09 EA03 EA03 EA03 EA03 EA03 EA10 FB12 HA02 JA01 JA06 JA09 JA15 KA01

Claims (5)

[Claims] An active energy ray-curable resin composition comprising a compound (A) having at least one oxetane ring in the molecule and a maleimide compound (B). 2. The active energy ray-curable resin composition according to claim 1, comprising a compound (C) having one or more oxirane rings in the molecule. 3. The active energy ray-curable resin composition according to claim 1, which comprises a compound (D) having one or more vinyl ether groups in the molecule. 4. The active energy ray-curable resin composition according to claim 1, wherein the maleimide compound (B) is a maleimide compound having a cyclo ring or an aliphatic group. 5. The active energy ray-curable resin composition according to claim 3, wherein the compound (D) having one or more vinyl ether groups in the molecule is cyclohexyl-1,4-dimethanol divinyl ether.