JP2001106712A - Photopolymerization initiator composition and photocurable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerization initiator composition which can efficiently initiate photopolymerization even in a low quantity of light, and to provide a photocurable composition which has an excellent curing performance even in a low quantity of light. SOLUTION: This photopolymerization initiator composition comprises an organic boron compound having a specific structure, a sensitizer, and a triazine compound. A photocurable composition comprises an organic compound having one or more polymerizable ethylenically unsaturated bonds, and the photopolymerization initiator composition. A method for forming a pattern uses the photocurable composition. A pattern formed on a substrate by the above method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerization initiator composition which efficiently initiates photopolymerization even with low irradiation energy,
The present invention relates to a high-sensitivity photocurable composition which photocurs even at a low light amount, a method of forming a pattern using the composition, and a pattern obtained using the composition.

[0002]

2. Description of the Related Art Photopolymerization initiators are used in various fields as components of photocurable compositions. In particular, in recent years, from the viewpoints of environmental problems, energy saving, work safety, production costs, and the like, the most characteristic features of photocuring, such as room temperature, quick drying, and no solvent, have been attracting attention, and many studies and developments have been made. However, fillers and pigments in the composition, that is, not involved in the photopolymerization reaction, and when the content of additives that greatly inhibit the transmission and penetration of light is high, the light transmitted to the deep part is extremely weak, Since the photoreaction of the photopolymerization initiator cannot sufficiently proceed, photocuring proceeds only with an extremely thin layer on the light irradiation surface.

In such a case, especially in the case of forming a thick film, a method of obtaining a thick cured layer by laminating a photocurable layer by repeating the formation and photocuring of a thin photocurable composition layer conventionally, Method that uses thermal polymerization that does not rely on
A method of obtaining a thick film pattern by chemical removal is used, but the process becomes complicated and the original advantage of photocuring is lost.

As described above, there is an increasing demand for a photocurable composition in forming a thick film, and a photopolymerization initiator that cures with lower energy and that exhibits a deeper curing depth is required.

[0005] On the other hand, there have been reported many applications as photopolymerization initiators obtained by combining a boron complex with a photoacid generator such as a triazine derivative, a diphenylhalogenium salt or a triphenylsulfonium salt. For example, JP
-13140, JP-A-6-329712, JP-A-8
-34808, JP-A-8-217813, JP-A-9
No. -3109 and the like. JP-A-7-292014 and JP-A-9-263604 disclose pigments using a sensitizing dye, a photoacid generator, a photopolymerization initiator composed of a triphenylmonoalkylboron compound derivative or a tetraphenylboron compound derivative, and the like. A photocurable composition containing a large amount of the above filler is described. However, it can not be said that any method has a high filler content and does not have sufficient performance for curing when the cured product is thick, and the sensitive wavelength region is also a narrow part of the ultraviolet to visible light region, Low sensitivity characteristics
Further improvement in performance is required.

[0006]

SUMMARY OF THE INVENTION The present invention provides a highly sensitive photoinitiator composition exhibiting sufficient photopolymerization initiating ability even at a low light amount to solve the above problems, and a photocurable composition using the same. It is to provide a pattern obtained by the photocurable composition. Specifically, stereolithography materials, photocurable inks,
Photocurable solder resist, photocurable printing plate, photoresist for color filter formation, photoresist for black matrix formation, photocurable adhesive, photocurable sealant, rib forming material for PDP, photocurable polyimide precursor , A photopolymerization initiator composition used for road surface display materials and the like,
An object of the present invention is to provide a photocurable composition, a method for forming a pattern using the photocurable composition, and a pattern obtained by curing the photocurable composition.

[0007]

Means for Solving the Problems The present inventors have proposed an organic boron compound (A) in which one or more naphthyl groups represented by the general formula (1) are bonded to a boron atom, and have light absorption in a wavelength region of 300 nm or more. The photopolymerization initiator composition comprising the sensitizer (B) and the triazine compound (C), and the photocurable composition containing the photoinitiator composition and the organic compound having a polymerizable ethylenically unsaturated bond are as described above. The inventors have found that they have solved the problem, and have completed the present invention. That is, the present invention

1) An organic boron compound (A) in which at least one naphthyl group represented by the general formula (1) is bonded to a boron atom, a sensitizer (B) having light absorption in a wavelength region of 300 nm or more, and a triazine compound (C) a photopolymerization initiator composition characterized by the general formula (1);

Embedded image (In the formula, at least one of R _{1 to} R ₄ represents a naphthyl group which may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a heterocyclic group or an alicyclic group, and the remaining R ₁ to R ₄ R ₄ is each independently an alkyl group, an aryl group,
Represents an aralkyl group, an alkenyl group, a heterocyclic group or an alicyclic group. X ⁺ represents an ammonium cation, a sulfonium cation, an oxosulfonium cation, a pyridinium cation, a phosphonium cation, an oxonium cation, or an iodonium cation. )

2) The photopolymerization initiator composition according to 1) above, wherein the triazine compound (C) is represented by the following general formula (2):

[0010]

Embedded image

3) The photopolymerization initiator composition according to any one of 1) and 2), further comprising N-phenylglycine.

4) A composition comprising the photopolymerization initiator composition according to any one of the above 1) to 3) and an organic compound (D) having at least one polymerizable ethylenically unsaturated bond. 5) The photocurable composition according to 4) above, further comprising a polymer (E) soluble in a solvent or an aqueous alkali solution; 6) a filler (F) ) The photocurable composition according to 4) or 5) above,

7) A method for forming a pattern, characterized in that the photocurable composition according to any one of the above 5) to 7) is applied on a substrate and then photocured by exposure. And a pattern formed by the method of (1).

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail.
R ₁ , R ₂ , R ₃ in an organic boron compound having one or more naphthyl groups represented by the above general formula (1) bonded to a boron atom
And the naphthyl group for R ₄ is a substituent (for example, a halogen atom,
An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a dialkylamino group having 2 to 5 carbon atoms, etc.), an α-naphthyl group and a β-
Any of naphthyl groups may be used. Specifically, α-naphthyl group, β-naphthyl group, 4-methyl-α-naphthyl group, 4-methyl-β-naphthyl group, 4-ethyl-α-naphthyl group, 4-n-butyl-α-naphthyl Group, 4-ethyl-β-naphthyl group, 4-methoxy-α-naphthyl group,
4-ethoxy-α-naphthyl group, 6-methyl-α-naphthyl group, 6-methyl-β-naphthyl group, 6-ethyl-α
-Naphthyl group, 6-n-butyl-α-naphthyl group, 6-
Examples thereof include an ethyl-β-naphthyl group, a 6-methoxy-α-naphthyl group, and a 6-ethoxy-α-naphthyl group. Particularly preferred are α-naphthyl, β-naphthyl, 4-methyl-α-naphthyl, 4-ethyl-α-naphthyl, 4-methoxy-α-naphthyl, and 6-methoxy-α-naphthyl. .

In the organic boron compound having one or more naphthyl groups represented by the above general formula (1) bonded to a boron atom,
The alkyl group of ₁ , R ₂ , R ₃ and R ₄ may have a substituent (for example, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a dialkylamino group having 2 to 5 carbon atoms). Well, specifically, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms is preferred, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
-Butyl group, isobutyl group, sec-butyl group, ter
t-butyl group, n-pentyl group, n-hexyl group, n-
Octyl group, cyanomethyl group, 4-chlorobutyl group, 2
-Diethylaminoethyl group, 2-methoxyethyl group and the like.

In the organic boron compound having at least one naphthyl group represented by the above general formula (1) bonded to a boron atom,
The aryl group of ₁ , R ₂ , R ₃ and R ₄ is a substituent (for example, a halogen atom, a halogenated alkyl group having 1 to 5 carbon atoms,
An alkoxy group having 1 to 5 carbon atoms, a cyano group, a nitro group, a dialkylamino group having 2 to 5 carbon atoms, etc., and specifically, a substituted or unsubstituted aryl group,
For example, phenyl, tolyl, xylyl, mesityl, 4-methoxyphenyl, 2-methoxyphenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 1 naphthyl, 2 naphthyl, anthryl Group, phenanthryl group, 4-nitrophenyl group, 4-trifluoromethylphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-dimethylaminophenyl group, and the like.

The aralkyl group of R ₁ , R ₂ , R ₃ and R _{4 in} the general formula (1) is a substituent (for example, halogen atom, carbon atom 1).
To 5 alkoxy groups, cyano groups, dialkylamino groups having 2 to 5 carbon atoms, etc.) and specifically, substituted or unsubstituted aralkyl groups such as benzyl group, phenethyl group, 1- Examples thereof include a naphthylmethyl group, a 2-naphthylmethyl group, and a 4-methoxybenzyl group.

The alkenyl group of R ₁ , R ₂ , R ₃ and R _{4 in} the general formula (1) is a substituent (for example, halogen atom, carbon atom 1).
To 5 alkoxy groups, a cyano group, a dialkylamino group having 2 to 5 carbon atoms, etc.), and specifically, a substituted or unsubstituted alkenyl group such as a vinyl group,
Examples thereof include a propenyl group, a butenyl group, and an octenyl group.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ and R _{4 in} the general formula (1) is a substituent (for example, a halogen atom, having 1 to 5 carbon atoms).
An alkoxy group, a cyano group, a dialkylamino group having 2 to 5 carbon atoms, etc.), specifically, a substituted or unsubstituted heterocyclic group such as a pyridyl group, a 4-methylpyridyl group, Examples include a quinolyl group and an indolyl group.

The alicyclic group represented by R ₁ , R ₂ , R ₃ and R _{4 in} the general formula (1) is a substituent (for example, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a C ₂ to C 5 group). A dialkylamino group, etc.), specifically, a substituted or unsubstituted alicyclic group such as a cyclohexyl group,
Examples thereof include a methylcyclohexyl group, a cyclopentyl group, and a cycloheptyl group.

In the boron compound of the present invention, the substituents R ₁ , R ₂ ,
Of R ₃ and R ₄ , three substituents are preferably aryl groups, particularly preferably 3
One substituent is a substituted or unsubstituted naphthyl group.

Specific examples of the ammonium cation for X ⁺ in the general formula (1) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation, tetra-n-butylammonium cation, and n-butyltriphenyl And quaternary ammonium salts such as ammonium cation, tetraphenylammonium cation, and benzyltriphenylammonium cation.

Specific examples of the sulfonium cation at X ⁺ in the general formula (1) include sulfonium cations such as triphenylsulfonium cation, tri (4-tolyl) sulfonium cation, and 4-tert-butylphenyldiphenylsulfonium cation. No.

Specific examples of the oxosulfonium cation for X ⁺ in the general formula (1) include, for example, triphenyloxosulfonium cation, tri (4-tolyl) oxosulfonium cation, and 4-tert-butylphenyldiphenyloxosulfonium cation. Oxosulfonium cation.

Specific examples of the oxonium cation for X ⁺ in the general formula (1) include, for example, triphenyloxonium cation, tri (4-tolyl) oxonium cation, 4-tert-butylphenyldiphenyloxonium cation and the like. Oxonium cation.

Specific examples of the pyridinium cation for X ⁺ in the general formula (1) include pyridinium cations such as N-methylpyridinium cation and Nn-butylpyridinium cation.

Specific examples of the phosphonium cation for X ⁺ in the general formula (1) include, for example, tetramethylphosphonium cation, tetra-n-butylphosphonium cation, tetra-n-octylphosphonium cation, tetraphenylphosphonium cation, benzyltriphenylphosphonium And a phosphonium cation such as a cation.

Specific examples of the iodonium cation for X ⁺ in the general formula (1) include, for example, an iodonium cation such as a diphenyliodonium cation, a di (4-methylphenyl) iodonium cation, and a di (4-tertbutylphenyl) iodonium cation. Is mentioned. Among these cations, it is particularly preferable to use a quaternary ammonium cation.

Specific examples of the organic boron compound having one or more naphthyl groups represented by the general formula (1) bonded to a boron atom include tetramethylammonium n-butyltri-α.
-Naphthyl borate, tetramethyl ammonium n-butyl tri-β-naphthyl borate, tetraethyl ammonium isobutyl tri-α-naphthyl borate, tetraethyl ammonium n-butyl tri-β-naphthyl borate, tetra n-butyl ammonium n-butyl tri-
α-naphthyl borate, tetra n-butyl ammonium n-butyl tri-β-naphthyl borate, tetra n-butyl ammonium n-butyl tri (4-methyl-α-naphthyl) borate, tetra n-butyl ammonium methyl tri (4- Methylnaphthyl) borate, tetra n-butylammonium n-butyltri (6-methoxy-α-
Naphthyl) borate, triphenylsulfonium n-butyltri-α-naphthylborate, triphenyloxosulfonium n-butyltri-α-naphthylborate,
Triphenyloxonium n-butyltri-α-naphthyl borate, N-methylpyridium n-butyltri-α
-Naphthyl borate, tetraphenylphosphonium n-
Butyl tri-α-naphthyl borate, diphenyl iodonium n-butyl tri-α-naphthyl borate and the like can be mentioned.

Among these organic boron compounds, tetra-n-butylammonium n-butyltri-α-naphthyl borate, tetra-n-butylammonium methyltri (4-methyl-α-naphthyl) borate, tetra-n-butylammonium n-Butyltri (4-methyl-α-naphthyl) borate is particularly preferred.

The organic boron compound used in the present invention can be added to the photopolymerization initiator composition preferably in an amount of 20 to 80% by mass, more preferably 30 to 70% by mass. Below this range, the photopolymerization initiating ability may not be sufficient, and above this range, the ratio of other initiator composition components may be too low, and the photopolymerization initiating ability may be lowered, so neither is preferred. .

The organoboron compound represented by the general formula (1) has almost no light absorption at a wavelength of 300 nm or more, and thus has no sensitivity to the light source of an ordinary ultraviolet lamp. Very high sensitivity can be obtained.

The sensitizer (B) used in the present invention comprises 30
It absorbs light in a wavelength region of 0 nm or more, causes an interaction with an organic boron compound having one or more naphthyl groups represented by the general formula (1) of the present invention bonded to a boron atom, and generates radicals due to decomposition of the boron compound. It is a compound that accelerates, for example, a photoinitiator or a dye that has light absorption in a wavelength region of 300 nm or more. Specific examples of these compounds include cationic dyes such as cyanine, xanthene, oxazine, thiazine, diallylmethane, triallylmethane, and pyrylium, merocyanine, coumarin, indigo, aromatic amine, phthalocyanine, azo, quinone, and thioxanthene-based dyes. There are neutral dyes such as sensitizing dyes, benzophenones, acetophenones, benzoins, thioxanthones, imidazoles, bisimidazoles, coumarins, ketocoumarins, triphenylpyryliums, triazines and the like. Further, compounds such as acylphosphine oxide, methylphenylglyoxylate, a-acyloxime ester, benzyl, camphorquinone, and ethylanthraquinone can also be used. here,
The counter anion in the case of the cationic dye is any anion, for example, a halogen anion such as chlorine, bromine, iodine anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, methanesulfonic acid anion, B
F ₄ anion, PF ₆ anion, perchlorate anion and the like can be mentioned.

Specific examples of the cationic dye include crystal violet (CI. 42555), methyl violet (CI. 42535), malachite green (CI. 42000), and fuchsin (CI. 4251).
0), crystal violet-carbinol base (CI. 42555: 1), parafuchsin (CI.
42500), rhodamine B (CI. 45170),
Victoria Blue B (CI.44045), Victoria Pure Blue BOH (CI.42595), Brilliant Green (CI.42040), Night Blue BX (CI.51185), Neutral Red (CI. .50040), Basic Orange 21
(CI.48035), Basic Yellow 11, Basic Yellow 21, Basic Yellow 22, Basic Red 1 (CI.45160), Basic Red 5 (CI.50040), Basic Red 13
(CI.48015), Basic Violet 7
(CI.48020), Basic Violet 11
(CI. 45175), crystal violet p
-P-toluenesulfonate or perchlorate of Victoria Blue B, such as toluenesulfonate or naphthalenesulfonate, p- of Basic Orange 21
Toluenesulfonate, or BF ₄ salt, a naphthalene sulfonate of basic red 5, or PF ₆ salt and the like.

Examples of the electrically neutral dye include 3-allyl-1
-Carboxymethyl-5- [2- (3-ethyl-2 (3
H) Benzoxazolylidene] -2-thiohydantoin,
4- [2- (3-ethyl-2 (3H) benzothiazolylidene) ethylidene] -3-phenyl-2-isoxazolin-5-one, 3- (2-benzothiazolyl) -7-
(Diethylamino) coumarin, 3- (2-benzimidazolyl) -7- (diethylamino) coumarin, 2,3
6,7-tetrahydro-11-oxo-1H, 5H, 1
1H- [1] benzopyrano [6,7,8-ij] quinaridine-10-carboxylate ethyl, N, N′-diethylindigo, thioxoindigo, 2-dimethylaminoanthraquinone, 4-hydroxyazobenzene, 4-phenylamino -4'-nitroazobenzene and the like.

In addition, benzophenone, 4-methylbenzophenone, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone,
4-diethylthioxanthone, 2-methylthioxanthone, N-methylimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (HABI) , Coumarin,
7-diethylaminocoumarin and the like.

Among these sensitizers, basic orene
Di 21, Basic Yellow 11, Basic Yellow
21, Basic Yellow 22, Basic Red 1
BF _FourSalt, 4,4'-diethylaminobenzophenone,
2,4-diethylthioxanthone and HABI are particularly preferred.
New

These sensitizers can be used alone or in combination of two or more. In particular, a sensitizer whose structure is changed by a reaction with the organic boron compound (A) during light irradiation and whose absorption wavelength range is changed is preferable.

The sensitizer (B) is generally used in the photopolymerization initiator composition in an amount of 0.1 to 30% by mass, preferably 0.5 to 15% by mass. Below this range, the light absorption efficiency may decrease and the photopolymerization initiation ability may decrease, and above this range, light may reach the deep part of the curable composition by light absorption of the sensitizer not involved in the initiation of photopolymerization. However, it is not preferable because the photocurability in the deep part may decrease. The triazine compound (C) used in the present invention is represented by the general formula (2). General formula (2);

Embedded image (Wherein R ₅ is a trihalomethyl group or a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group,
Represents an alkoxy group, a heterocyclic group or an alicyclic group. )

The alkyl group represented by R _{5 in} the general formula (2) has a substituent (eg, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a dialkylamino group having 2 to 5 carbon atoms). And specifically, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms is preferable, for example, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
-Butyl group, tert-butyl group, n-pentyl group, n
-Hexyl group, n-octyl group, cyanomethyl group, 4-
Examples thereof include a chlorobutyl group, a 2-diethylaminoethyl group, and a 2-methoxyethyl group.

In the formula (2), the aryl group represented by R ₅ is a substituent (for example, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, a cyano group, a nitro group, And a substituted or unsubstituted aryl group such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a 4-methoxyphenyl group. , 2-methoxyphenyl group, 4-n-butylphenyl group, 4-t
tert-butylphenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, 4-nitrophenyl group, 4-trifluoromethylphenyl group, 4-
Examples thereof include a fluorophenyl group, a 4-chlorophenyl group, and a 4-dimethylaminophenyl group.

The aralkyl group of R _{5 in} the general formula (2) has a substituent (eg, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a dialkylamino group having 2 to 5 carbon atoms, etc.). And specifically, a substituted or unsubstituted aralkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group,
-Methoxybenzyl group and the like.

The alkenyl group of R _{5 in} the general formula (2) has a substituent (for example, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a dialkylamino group having 2 to 5 carbon atoms). And specific examples thereof include a substituted or unsubstituted alkenyl group such as a vinyl group, a propenyl group, a butenyl group, and an octenyl group.

The alkoxy group of R _{5 in} the general formula (2) has a substituent (for example, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a dialkylamino group having 2 to 5 carbon atoms). Specific examples thereof include a substituted or unsubstituted alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a cyclohexanoxy group, and a phenoxy group.

The heterocyclic group represented by R _{5 in} the general formula (2) has a substituent (eg, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a cyano group, a dialkylamino group having 2 to 5 carbon atoms). And specific examples thereof include a substituted or unsubstituted heterocyclic group such as a pyridyl group, a 4-methylpyridyl group, a quinolyl group, and an indolyl group.

The alicyclic group represented by R _{5 in} the general formula (2) is a substituent (for example, a halogen atom, an alkoxy group having 1 to 5 carbon atoms,
And a substituted or unsubstituted alicyclic group such as a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group, and a cycloalkyl group. A heptyl group and the like can be mentioned.

The triazine compounds of the general formula (2) preferably used in the present invention are 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl)
-S-triazine, 2- (p-methoxyphenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Methoxy-α-naphthyl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(P-tolyl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (m, p-dimethoxyphenyl)
-4,6-bis (trichloromethyl) -s-triazine, 2- [3,4- (methylenedioxy) phenyl]-
4,6-bis (trichloromethyl) -s-triazine and the like, and more preferably, 2-phenyl-4,6-
Bis (trichloromethyl) -s-triazine, 2- (4
-Methoxy-α-naphthyl) -4,6-bis (trichloromethyl) -s-triazine.

In the present invention, the triazine compound can be used in the photopolymerization initiator composition preferably in an amount of 10 to 90% by mass, more preferably 20 to 50% by mass. If the amount is below or above this range, the photopolymerization initiating ability may not be sufficient.

The present invention comprises an organic boron compound (A) having at least one naphthyl group bonded to a boron atom, a sensitizer (B) having light absorption in a wavelength region of 300 nm or more, and a triazine compound (C). The photopolymerization initiator composition can be generally added in an amount of 0.1 to 30% by mass, preferably 1 to 20% by mass, based on the photocurable composition. Below this range, the photopolymerization initiating ability may be insufficient, and above this range, too much light absorption may occur, and the photocurability of the deep part of the photocurable composition may be reduced, so neither is possible. Not preferred.

In the present invention, N-phenylglycine can be further added to the above photopolymerization initiator composition. N
-Phenylglycine acts as a chain transfer agent, increasing the rate of photopolymerization. N-phenylglycine is generally present in the photopolymerization initiator composition in an amount of 5 to 60% by mass, preferably 10 to 4% by mass.
It is used in the range of 0% by mass. Below this range, the effect of adding N-phenylglycine is poor, and above this range, the stability of the photopolymerization initiator composition, the physical properties of the cured product, and the like may be adversely affected.

The organic compound (D) having at least one ethylenically unsaturated bond used in the present invention includes, for example, (meth) acrylic acid and esters thereof, and specific examples thereof include methyl (meth) acrylate, butyl ( (Meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy- 3-phenoxypropyl (meth) acrylate N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, methacryloyloxyisocyanate, and the like.

Also, (meth) acrylamide and its N-substituted product, specifically, N-methyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-
Butoxymethylacrylamide, isobutoxymethylacrylamide, (meth) acrylamide-2-methylpropanesulfonic acid and its sodium salt.

Compounds having an N-vinylamide structure, such as N-vinylacetamide, N-vinylpropioamide, and N-vinylbutylamide, and esterification reaction of unsaturated carboxylic acids or polycarboxylic acids with polyhydroxy compounds And typical examples thereof include phenoxydiethoxy (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2 , 2-bis- [4-
(Meth) acryloyloxypolyethoxyphenyl] propane, neopentylglycol hydroxypivalate di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolethanedi (meth) acrylate, triethylolpropane Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid trierythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acryl , Dipentaerythritol hexa (meth) acrylate, polyhydric alcohol (meth) acrylate, epoxy (meth) acrylates, urethane (meth) acrylates obtained by reaction with (meth) acryloyloxyisocyanate, and the like. be able to.

Among these organic compounds having one or more ethylenically unsaturated bonds, butyl acrylate, 1,3-butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol di (meth) acrylate, pentaerythritol Erythritol tri (meth) acrylate and dipentaerythritol hexaacrylate are used.

The organic compound having at least one ethylenically unsaturated bond of the present invention is generally contained in the photocurable composition in an amount of 2 to 9%.
9.9% by mass, preferably 5 to 99.5% by mass can be used. Below this range, the curability of the photocurable composition decreases, and above this range, the ratio of the photopolymerization initiator becomes too small and the photocurability decreases, which is not preferable.

The polymer (E) soluble in a solvent or an aqueous alkali solution used in the present invention improves the physical properties such as the strength and binding properties of the photocurable composition and the functions such as developability and chemical resistance. Any polymer may be used as long as it is a polymer that can form a uniform film having a thickness of 1 μm or more and is soluble in a solvent or an aqueous alkaline solution.

Examples of the solvent include N-methylpyrrolidone, methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol. Monomethyl ether, propylene glycol monomethyl ether acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, acetonitrile and the like. These include basic substances such as trimethylamine and triethylamine and surfactants. May be added.

As the alkaline aqueous solution, for example, an aqueous solution of an inorganic salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, or an aqueous solution of an organic salt such as hydroxytetramethylammonium or hydroxytetraethylammonium can be used.

The polymer of the present invention includes a thermosetting resin, a thermoplastic resin, a photosensitive resin, and the like. Examples thereof include polyacrylates, poly-α-alkyl acrylates, and the like.
Homopolymers such as polyamides, polyvinyl acetals, polyurethanes, polycarbonates, polystyrenes, polyvinyl esters, phenolic resins, epoxy resins, novolak resins, alkyd resins, and the like, or a mixture of two or more homopolymers are used. Can be These high molecular polymers may have a radically polymerizable ethylenically unsaturated bonding group for the purpose of accelerating the curing reaction of the photocurable composition of the present invention or improving the properties of the cured product. Preferably, polyacrylates and epoxy resins are used.

When the cured product remains as a permanent film or when durability is required in the manufacturing process, for example, in the case of a color filter or a solder resist, a high-temperature treatment or a treatment with various solvents or chemicals is required in a post-production process. Therefore, it is necessary to use a polymer having excellent heat resistance and stability over time as the polymer (E). Meanwhile, PDP
In the case where baking is performed after pattern formation to remove organic components as in the use of a rib forming material or the like, it is desirable to use a high molecular polymer that rapidly decomposes and burns at a certain temperature.

In the present invention, the polymer which is soluble in a solvent or an aqueous alkali solution generally contains 20 to 20
90% by mass, preferably 30 to 70% by mass can be used. Below this range, the effect of adding the high molecular weight polymer is poor, and when added above this range, the ratio of the photo-curable component is reduced and the photo-curability is reduced, so neither is preferred.

The filler (F) used in the present invention is added for the purpose of improving physical properties such as strength and toughness and impact resistance of the cured product.
Silica, titania, alumina, zirconia, zinc oxide,
Examples thereof include powders and particles such as talc, aluminum powder, and glass powder, fibers such as glass fiber, carbon fiber, and metal whiskers, and pigments used for coloring and hiding. The particle size of the powder filler that can be used is not particularly limited. However, in order to obtain dispersibility, dispersion stability, and viscosity characteristics, 0.5
A powder having a size of ５００500 μm, preferably 2-250 μm can be used. One or more of these fillers can be added depending on the purpose, but in particular silica, titania,
Alumina and glass powder are preferably used.

When a filler is added in the present invention, it is generally added to the photocurable composition in an amount of 1 to 90% by mass, preferably 5 to 85% by mass. Below this range, the effect of adding the filler is poor, and when it is more than this range, the ratio of the photocurable component is reduced and the photocurability is reduced, so that both are not preferred.

The pattern formed by the photocurable composition of the present invention means a photocurable product of the photocurable composition formed on a substrate so as to maintain a constant shape. , Photocurable ink, photocurable solder resist, photocurable printing plate, photoresist for color filter formation, photoresist for black matrix formation, photocurable adhesive, photocurable sealant, rib forming material for PDP,
Examples include patterns in application fields such as a photocurable polyimide precursor and a road surface display material, and the photocurable composition of the present invention is particularly suitable as a photocurable material that forms a fine and thick film pattern.

The substrate used for forming the pattern of the present invention includes:
Substrates of silicon, glass, metal, resin film, asphalt, or the like, or those in which a plurality of these are arranged can be used. Here, the surface of the glass is untreated,
A material coated with a metal or a metal oxide can be used. Metals include aluminum, iron, nickel, stainless steel, copper,
A plate of chromium, lead, zinc, gold, platinum, tin or an alloy thereof or a plate obtained by plating these metals on the surface of another material can be used. P for resin film
ET, polyester, polyethylene, polypropylene,
Polystyrene, ABS, polyacrylate resin,
A film or plate of polyimide, epoxy resin, polycarbonate, or the like can be used. These substrate surfaces may be subjected to an acid treatment, an oxidation treatment, a plasma treatment, a rough surface treatment, or a mirror surface treatment in order to control the adhesion to the photocurable composition. Because the photocurable composition is on the surface of the substrate,
The thickness of the substrate can be set arbitrarily. Further, a resin layer or the like which does not participate in the photoreaction may be provided between the photocurable composition and the substrate.

There are roughly two types of the method of forming a fixed pattern using the photocurable composition of the present invention. One is a method in which a photocurable composition is applied in a desired shape in advance and then cured by light irradiation. The other is to apply the photocurable composition uniformly on the substrate, and then irradiate the photocurable composition with light so that the exposed portion has the desired shape. Dissolution, washing, peeling, physical polishing,
This is a method in which a pattern is formed using a photo-cured material that has been removed by means of chemical polishing or the like and remains. After these patterns are formed, pattern formation may be repeated on the same surface using the above-described pattern formation method.

Further, various additives can be added to the photocurable composition of the present invention in order to provide viscosity, operability, and cured product characteristics according to the application. Sufficient dispersion of each component,
A volatile solvent may be added for the purpose of improving operability and adhesion during coating and adjusting viscosity. As the volatile solvent, for example, methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone and the like can be mentioned, and they can be used alone or in combination of two or more.

When it is difficult to use the above volatile solvent depending on the use, a reactive solvent can be used. For example, 2-hydroxy (meth) acrylate, methyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N-acryloyl Examples thereof include morpholine, N-acryloylpiperidine, N, N-dimethyl (meth) acrylamide, N-vinylpyrrolidone, and the like. They can be used alone or as a mixture of two or more kinds. May be mixed.

Further, a thermal polymerization inhibitor can be added to the photocurable composition of the present invention for the purpose of preventing polymerization during storage. Specific examples of the thermal polymerization initiator include p-methoxyphenol, hydroquinone, catechol, tert-
Examples thereof include butyl catechol, phenothiazine, methoquinone, phosphate, phosphite, and phenol derivative.

Further, the photocurable composition of the present invention may be used, if desired, with a fluorescent whitening agent, a surfactant, a plasticizer, a flame retardant, an antioxidant, an ultraviolet absorber, a foaming agent, a fungicide, an antistatic agent. An agent, a magnetic substance, a conductive material, an antibacterial / sterilizing material, a porous adsorbent, a fragrance, a viscosity modifier, and the like may be used.

The production of the photocurable composition is carried out by a three-roll mill, a two-roll mill, a sand mill, an attritor, a ball mill, a kneader, a propeller mixer, an ultrasonic stirrer,
It can be performed using various dispersing and mixing means such as a cutter mill. At the time of dispersion, a dispersing aid can be appropriately added in order to improve the dispersion of the filler. Since the dispersing aid has an effect of assisting dispersion and preventing reaggregation after dispersion, a photocurable composition having a uniform composition and excellent storage stability can be obtained.

The photocurable composition of the present invention is applied to a substrate by a coating method such as spray coating, spinner coating, roll coating, screen coating, spread coating, dip coating, and calendar coating. Here, for the purpose of obtaining appropriate coating characteristics, a small amount of a silicone-based or fluorine-based surfactant may be added to the photocurable composition of the present invention as a leveling agent or a defoaming agent.

The applied photocurable composition may be optionally heated at 60 ° C. to 100 ° C. for 10 minutes to 60 ° C. in a hot air oven, halogen heater, infrared heater, hot plate or the like.
Dry the volatile solvent in minutes. If the temperature at this time is too high or the drying time is too long, partial polymerization or cross-linking occurs, and unexposed portions may cause unintended curing, which may cause so-called burning. Thereafter, depending on the application, an oxygen barrier film may be provided on the coating film.

The dried coating film is exposed. At this time, a photomask having a pattern may be used. Light sources generally include mercury lamps, metal halide lamps, xenon lamps, halogen lamps, semiconductor lasers, He-Ne
A laser, a YAG laser, an Ar laser, or the like is used, and depending on the application or the type of the substrate, a filter having heat ray cutting properties or wavelength selectivity, a reflector or a lens for controlling a light flux or an irradiation area may be used. . After exposure of the coating,
By removing the uncured portion, a pattern can be formed on the substrate.

Specific uses of the photocurable composition according to the present invention include photolithography materials, photocurable inks, photocurable solder resists, photocurable printing plates, photoresists for forming color filters, and black matrix formation. Photoresist, photocurable adhesive, photocurable sealant, PD
Examples thereof include a rib forming material for P, a photocurable polyimide precursor, and a road surface display material, and are particularly suitable for use in forming a fine pattern having a film thickness of 100 μm or more.

[0076]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless departing from the gist thereof. In this example, a photocurable composition containing a large amount of filler and having low light transmittance will be described as an example.

Examples of the resin composition used in the examples are shown.
Parts in the components of the composition represent parts by weight. (Example of Resin Composition) Pentaerythritol triacrylate 50 parts Reactive epoxy resin VR-77 (manufactured by Showa Polymer Co., Ltd.) 15 parts Isobutyl acrylate 30 parts Isobornyl acrylate 5 parts were mixed to prepare resin composition A.

Next, examples of the photocurable composition used in the examples will be shown. (Example of photocurable composition) Resin composition A 25 parts Titanium oxide 13 parts Silicon oxide 30 parts Calcium carbonate 30 parts Dispersant (Floren G-700: manufactured by Kyoeisha Chemical Co., Ltd.) 2 parts are mixed, and the mixture is mixed with a bead mill. After mixing and dispersion for a minute, a white dispersion was obtained.

In each of the examples, the white dispersion 10
To 0 parts, 1.5 parts of the photopolymerization initiator composition of the present invention having the composition shown in Table 1 was added and mixed well to obtain a photocurable composition.
The compound A in Table 1 was a tetraalkylammonium organic boron salt, the compound B was a sensitizing dye, and the compound C was a triazine compound. At the same time, Comparative Examples 1 to 5 were shown as Comparative Examples.

[0080]

[Table 1]

As a measure of photopolymerizability in the examples, comparison was made by the following method. The photocurable composition is applied to a glass plate so as to have a thickness of 300 μm, and irradiated with light using a metal halide lamp, and the lowermost layer of the coating film, that is, the contact surface between the photocurable composition and the glass is touched with a finger. The light irradiation energy required to prevent stickiness was measured. The light irradiation amount at this time is defined as light sensitivity, and the smaller the value, the higher the sensitivity. The upper limit of the light irradiation energy was 2000 mJ / cm ² , which is a realistic value in an actual process. The results are shown in Table 2.

[0082]

[Table 2]

Comparative Examples 1 and 2 lacking each component of the present invention
In Comparative Example 3 and Comparative Example 5 using a conventionally used ultraviolet light polymerization initiator, curing was not possible to the bottom even with irradiation of 2000 mJ / cm ² or more. Further, in Comparative Example 4, a conventional organic boron compound having no naphthyl group as a substituent was used, but the irradiation light amount is required to be two to four times as large as that of the embodiment of the present invention. From these results, the photopolymerization initiator composition according to the present invention and the photocurable composition using the same have significantly improved sensitivity, energy saving and cost saving can be achieved,
It has been clarified that thicker films can be photocured, which was difficult with conventional photopolymerization initiators.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/029 G03F 7/029 7/031 7/031 7/032 7/032 // C09D 11/10 C09D 11/10 C09J 4/00 C09J 4/00 4/06 4/06 F term (reference) 2H025 AA00 AB01 AB13 AB15 AB16 AB17 AB20 AC01 AC08 AD01 BC31 BC51 CA01 CA20 CA28 CA41 CA50 CB52 CC08 FA03 4J011 PA02 PA52 PA63 PA69 PA70 PA83 PA85 PA89 PA95 PB22 PC02 QA03 QA04 QA06 QA07 QA12 QA13 QA17 QA18 QA31 RA03 RA06 RA19 SA01 SA21 SA31 SA64 SA78 SA85 SA87 TA07 UA01 UA06 VA01 WA01 4J026 AA17 AA36 AA37 AA45 AB01 AB32 BA27 BA28 DB09 DB15 DB30 DB36 FA05 GA06 4J040 DF042 EC002 EF341 FA011 FA101 FA141 FA151 FA261 FA291 HA026 HA066 HA136 HA196 HA256 HA306 HA346 HA356 HC25 HD19 HD39 JB08 KA13 KA15 KA42 LA10

Claims (8)

[Claims] An organic boron compound (A) having one or more naphthyl groups bonded to a boron atom represented by the following general formula (1), a sensitizer (B) having light absorption in a wavelength region of 300 nm or more, and a triazine A photopolymerization initiator composition comprising the compound (C). General formula (1); (In the formula, at least one of R _{1 to} R ₄ represents a naphthyl group which may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a heterocyclic group or an alicyclic group, and the remaining R ₁ to R ₄ R ₄ is each independently an alkyl group, an aryl group,
Represents an aralkyl group, an alkenyl group, a heterocyclic group or an alicyclic group. X ⁺ represents an ammonium cation, a sulfonium cation, an oxosulfonium cation, a pyridinium cation, a phosphonium cation, an oxonium cation, or an iodonium cation. ) 2. The photopolymerization initiator composition according to claim 1, wherein the triazine compound (C) is represented by the following general formula (2). General formula (2): (Wherein R ₅ is a trihalomethyl group or a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group,
Represents an alkoxy group, a heterocyclic group or an alicyclic group. ) 3. The photopolymerization initiator composition according to claim 1, further comprising N-phenylglycine. 4. A light comprising the photopolymerization initiator composition according to claim 1, and an organic compound (D) having at least one polymerizable ethylenically unsaturated bond. Curable composition. 5. The photocurable composition according to claim 4, further comprising a polymer (E) soluble in a solvent or an aqueous alkaline solution. 6. The photocurable composition according to claim 4, further comprising a filler (F). 7. A method for forming a pattern, comprising applying the photocurable composition according to any one of claims 4 to 6 onto a substrate, and exposing the photocurable composition to light. 8. A pattern formed by the method according to claim 7.