WO2016058551A9

WO2016058551A9 - Photosensitive resin composition, method for manufacturing colour filter, colour filter and liquid crystal display device

Info

Publication number: WO2016058551A9
Application number: PCT/CN2015/092029
Authority: WO
Inventors: 王端志; 谢栢源; 许荣宾; 许承昌; 何维凯; 郭怡嘉
Original assignee: 奇美实业股份有限公司
Priority date: 2014-10-15
Filing date: 2015-10-15
Publication date: 2017-05-18
Also published as: WO2016058551A1; TW201614373A; TWI620011B; CN107003604A; CN107003604B

Abstract

A photosensitive resin composition, a method for manufacturing a colour filter, a colour filter and a liquid crystal display device. The photosensitive resin composition comprises an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D) and a pigment (E). The alkali-soluble resin (A) comprises an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2). The alkali-soluble resin (A-1) is obtained by reaction of a mixture. The mixture comprises an epoxy compound having at least two epoxy groups (a-1-1), a compound having at least one carboxylic group and at least one ethylenically unsaturated group (a-1-2), a tetracarboxylic acid or a dianhydride thereof (a-1-3) and a dicarboxylic acid or an anhydride thereof (a-1-4). The epoxy compound having at least two epoxy groups (a-1-1) has a structure as shown by the following formula (aI-1) or the following formula (aI-2). The photoinitiator (C) comprises a photoinitiator (C-1) represented by formula (1).

Description

Photosensitive resin composition, method for producing color filter, color filter, and liquid crystal display device

Technical field

The present invention relates to a photosensitive resin composition, a method of producing a color filter, a color filter, and a liquid crystal display device. In particular, it relates to a photosensitive resin composition having high linearity, high outgassing property, and good pattern smoothness, and a color filter and a liquid crystal display device formed using the photosensitive resin composition.

Background technique

At present, color filters have been widely used in the fields of office equipment such as color liquid crystal displays, color facsimile machines, and color cameras. As the market demand is expanding, the production technology of color filters is also diversified. At present, dyeing methods, printing methods, electroplating methods, and dispersion methods have been developed, among which the dispersion method is the mainstream process.

In the dispersion method, the colored pigment is first dispersed in a photosensitive resin, and the photosensitive resin is applied onto a glass substrate, and a specific pattern is obtained by exposure, development, and the like. By repeating the operation three times, a pattern of red (R), green (G), and blue (B) pixel colored layers can be obtained, and then a protective film can be applied on the pattern of the pixel colored layer as needed.

For example, a copolymer obtained by polymerizing (meth)acrylic acid as a monomer component, as disclosed in JP-A-6-95211, and JP-A-H08-183819, This is an alkali-soluble resin as a photosensitive resin.

However, in the manufacturing process of the color filter, it is necessary to undergo a plurality of heat treatment steps, such as red (R), green (G), and blue (B), and the post-bake step after the formation of the pixel colored layer pattern. And a step of forming a transparent conductive film (ITO film), etc., these steps generally need to be operated at a high temperature of 200 ° C or higher, but the above-mentioned known photosensitive resin is heated at 180 ° C for about 1 hour, but in the pixel The generation of pigment agglomerated particles tends to occur in the colored layer (generally, the particle diameter of the pigment agglomerated particles is from 1 to 10 μm), and the heat resistance of the pixel colored layer is also not good.

In order to improve the above-mentioned problems, the photosensitive resin composition disclosed in Japanese Laid-Open Patent Publication No. 2001-075273, A polymer obtained by polymerizing a carboxyl group-containing unsaturated monomer and a glycidyl group-containing monomer is used as an alkali-soluble resin of a photosensitive resin. However, the color filter prepared by the photosensitive resin composition of the prior art has problems such as poor linearity of high-definition pattern, poor pattern smoothness, and high outgassing.

Therefore, how to overcome the problems of poor linearity of the high-definition pattern, poor pattern smoothness, and high outgassing at the same time to meet the requirements of the current industry is an object of diligent research in the technical field to which the present invention pertains.

Summary of the invention

In view of the above, the present invention provides a photosensitive resin composition, a method of producing a color filter, a color filter, and a liquid crystal display device, and the high-definition pattern of the photosensitive resin composition has good linearity and low linearity. Both outgassing and pattern smoothness are good.

The photosensitive resin composition of the present invention includes an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a pigment (E). Wherein the alkali-soluble resin (A) includes an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2), wherein the alkali-soluble resin (A-1) is obtained by reacting a mixture, and The mixture includes an epoxy compound (a-1-1) having at least two epoxy groups, a compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group, and a tetracarboxylic acid Or its acid dianhydride (a-1-3) and dicarboxylic acid or its anhydride (a-1-4);

The epoxy compound (a-1-1) having at least two epoxy groups has a structure represented by the following formula (aI-1) or the following formula (aI-2):

In the formula (aI-1), W ¹ , W ² , W ³ and W ⁴ are each the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5. Alkoxy group, aryl group having 6 to 12 carbon atoms or aralkyl group having 6 to 12 carbon atoms,

In the formula (aI-2), W ⁵ to W ¹⁸ are each the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and s represents An integer from 0 to 10;

The number average molecular weight of the alkali-soluble resin (A-1) is from 1,000 to 8,000;

The alkali-soluble resin (A-2) is an unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1), an alicyclic hydrocarbon group-containing unsaturated compound (a-2-2), and the like. Unsaturated compound (a-2-3) obtained by copolymerization;

The alkali-soluble resin (A-2) has a weight average molecular weight of 3,000 to 30,000;

The weight ratio range (A-1) / (A-2) of the amount of the alkali-soluble resin (A-1) to the alkali-soluble resin (A-2) is 5/95 to 95/5;

The photoinitiator (C) comprises a photoinitiator (C-1) represented by formula (1);

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, COR ₁₆ , OR ₁₇ , halogen, NO ₂ , The group represented by the formula (2) is a group represented by the formula (3),

Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently a group represented by the formula (4). Substituted C ₂ -C ₁₀ alkenyl

Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently taken as —(CH ₂ ) _p —Y— (CH ₂ ) _q —;

Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently a group represented by the formula (5) ;

However, at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ is determined by the formula (5). The group represented,

R _9, R _10, R ₁₁ and R ₁₂ are independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups to one another: halo, Phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, -(CO)OH or -(CO)O-(C ₁ -C ₄ alkyl);

Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted by one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring via a carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ;

Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁ , ₆ NO ₂ or formula (2),

Y represents O, S, NR ₂₆ or a direct bond;

p represents an integer of 0, 1, 2 or 3;

q represents an integer of 1, 2 or 3;

X represents CO or a direct bond;

R ₁₃ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ or a group represented by the formula (6);

Or R ₁₃ represents a C ₂ -C ₂₀ alkyl group, interspersed with one or more of O, S, SO, SO ₂ , NR ₂₆ or CO, or a C ₂ -C ₁₂ alkenyl group which is unintercalated or heterozygous Or a plurality of O, CO or NR ₂₆ , wherein the meta-hetero C ₂ -C ₂₀ alkyl group and the unmeta- or inter-hetero C ₂ -C ₁₂ alkenyl group are unsubstituted or substituted by one or more halogens ;

Or R ₁₃ represents C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl or C ₃ -C ₁₀ cycloalkyl having no or hetero or one or more O, S, CO or NR ₂₆ ;

Or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , CN, NO ₂ , halogen, C ₁ a C ₂ alkyl group, a C ₁ -C ₄ haloalkyl group, a C ₂ -C ₂₀ alkyl group having one or more O, S, CO or NR ₂₆ or a group represented by the formula (7),

Each warp or C ₃ -C ₁₀ cycloalkyl, or interrupted by one or more O, S, CO or NR C ₃ ₂₆ -C ₁₀ cyclic group is unsubstituted;

k represents an integer of 1 to 10;

R ₁₄ represents hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, which is unsubstituted or one or more Substituted by: halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or CN;

Or R ₁₄ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, CN, OR ₁₇ , SR ₁₈ and / or NR ₁₉ R ₂₀ ;

Or R ₁₄ represents a C ₃ -C ₂₀ heteroaryl group, a C ₁ -C ₈ alkoxy group, a benzyloxy group or a phenoxy group, the benzyloxy group and the phenoxy group being unsubstituted or having one or more of the following groups Group substituted: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and/or halogen;

R ₁₅ represents a C ₆ -C ₂₀ aryl group or a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, heterogeneous C ₂ -C ₂₀ alkyl group or a plurality of O, S or NR _26; or a C ₁ -C ₂₀ via respective substituted alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following Group substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ Heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₅ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl having no or hetero or one or more O, CO or NR ₂₆ ; or R ₁₅ represents C ₁ -C ₂₀ alkyl , which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxy a group represented by a carbonyl group, a C ₃ -C ₂₀ heteroaryloxycarbonyl group, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , a phenyl group, and a formula (6) Or a group represented by the formula (8),

Or the C ₁ -C ₂₀ alkyl group is substituted by a phenyl group which is substituted by halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₅ represents a C ₂ -C ₂₀ alkyl group in which one or more O, SO or SO ₂ are heterogeneous, and the inter-hetero C ₂ -C ₂₀ alkyl group is unsubstituted or has one or more of the following groups Substituted: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted by OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₅ represents a C ₂ -C ₂₀ alkanoyl or benzoyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ Or NR ₁₉ R ₂₀ ; or R ₁₅ represents a naphthoyl group which is unsubstituted or substituted with one or more OR ₁₇ or a C ₃ -C ₁₄ heteroarylcarbonyl group;

Or R ₁₅ represents a C ₂ -C ₁₂ alkoxycarbonyl group which is undoped or inter-hetero-doped with one or more O and the inter- or un-doped C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or One or more hydroxyl substitutions;

Or R ₁₅ represents a phenoxycarbonyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m -C ₁ -C ₆ alkyl, unsubstituted or C ₁ -C ₁₂ alkyl or SO _2- C ₁ -C ₆ alkyl-substituted S(O) _m -phenyl;

Or R ₁₅ represents an SO ₂ O-phenyl group which is unsubstituted or substituted by a C ₁ -C ₁₂ alkyl group; or a diphenylphosphono group or a di-(C ₁ -C ₄ alkoxy)-phosphono group ;

m represents 1 or 2;

R' ₁₄ has one of the meanings given for R ₁₄ ;

R' ₁₅ has one of the meanings given for R ₁₅ ;

X ₁ represents O, S, SO or SO ₂ ;

X ₂ represents O, CO, S or a direct bond;

R ₁₆ represents a C ₆ -C ₂₀ aryl group or a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a C ₁ -C ₂₀ alkyl group having one or more O, S or NR ₂₆ ; or each of one or more C ₁ -C ₂₀ alkane Substituted, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₆ represents hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C 3 -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ )alkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO) -phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

Or R ₁₆ represents a C ₂ -C ₁₂ alkyl group in which one or more O, S or NR ₂₆ are heterogeneous; or R ₁₆ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n ( CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl;

Or R ₁₆ represents a phenyl substituted with SR ₁₈ , wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring of the oxazole moiety to which the COR ₁₆ group is attached;

n represents 1 to 20;

R ₁₇ represents hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO) -(C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ - (C _1- C ₄ haloalkyl), O(C ₁ -C ₄ haloalkyl) or a C ₃ -C ₂₀ cycloalkyl having one or more O;

Or R ₁₇ represents C ₂ -C ₂₀ alkyl, in which one or more O, S or NR ₂₆ are heterogeneous;

Or R ₁₇ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkanoyl, C ₂ -C _{a 12} -alkenyl, C ₃ -C ₆ enoyl group or a C ₃ -C ₂₀ cycloalkyl group having no or hetero or one or more O, S, CO or NR ₂₆ ;

Or R ₁₇ represents a C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl group which is undoped or hetero-has one or more O;

Or R ₁₇ represents a benzoyl group which is unsubstituted or substituted by one or more C ₁ -C ₆ alkyl groups, halogen, OH or C ₁ -C ₃ alkoxy groups;

Or R ₁₇ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ An alkyl) ₂ , a diphenyl-amine group or a group represented by the formula (7);

Or R ₁₇ forms a direct bond bonded to one of the carbon atoms of the phenyl or naphthyl ring in which the group represented by the formula (2) or the group represented by the formula (7) is bonded,

R ₁₈ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein the C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ naphthenic Or a phenyl-C ₁ -C ₃ alkyl group which has no or hetero or one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; or R ₁₈ is a C ₁ -C ₂₀ alkyl group which is not Substituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O (C ₁ -C ₄ alkyl) , O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl or (CO)OR ₁₇ ;

Or R ₁₈ represents a C ₂ -C ₂₀ alkyl group with one or more O, S, CO, NR ₂₆ or COOR ₁₇ interspersed therebetween;

Or R ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ olefin Acyl group

Or R ₁₈ represents a benzoyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ Alkylthio group;

Or R ₁₈ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C _4- haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N (C ₁ -C ₈ alkyl) ₂ or a group represented by the formula (7)

R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ - C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl, SO ₂ -(C ₁ - C ₄ haloalkyl) or benzoyl;

Or R ₁₉ and R ₂₀ represent phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₄ haloalkyl, C _1- C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzoyl or C ₁ -C ₁₂ alkoxy;

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR ₁₇ and which is either 5- or 6-membered saturated or unsaturated The ring is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO) R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl, C ₃ -C ₂₀ cycloalkyl having one or more O, S, CO or NR ₁₇ undoped or inter-hetero, or a group represented by the formula (7)

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , halogen, NO ₂ , CN, phenyl or uninter or hetero Or a plurality of C ₃ -C ₂₀ cycloalkyl groups of O, S, CO or NR ₁₇ or a group represented by the formula (7)

R ₂₁ and R ₂₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl;

Or R ₂₁ and R ₂₂ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR ₂₆ and which is either 5- or 6-membered saturated or unsaturated The ring is unfused or the 5- or 6-membered saturated or unsaturated ring is fused to the benzene ring;

R ₂₃ represents hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, intervening one or more O, CO or NR ₂₆ C ₂ -C ₂₀ alkyl, uninter or hetero-O a C ₃ -C ₂₀ cycloalkyl group of S, CO or NR ₂₆ , or R ₂₃ represents phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ;

R ₂₄ represents (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ has one of the meanings given for R ₁₉ and R ₂₀ ;

R ₂₅ represents COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ ;

R ₂₆ represents hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl with one or more O or CO in between; or phenyl-C ₁ -C ₄ alkane a C ₃ -C ₈ cycloalkyl group which is undoped or heterozygous with one or more O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or one or more Substituted by: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a group represented by formula (7)

However, the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule.

In an embodiment of the invention, in the photoinitiator (C-1) represented by the formula (1), R _-1 , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ And R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, COR ₁₆ , NO ₂ or a group represented by formula (2);

However, at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ is determined by the formula (5). a group represented;

X represents CO or a direct bond;

R _-13 represents C _-1 -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups: halogen, OR- ₁₇ , SR ₁₈ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO (OC _k H _2k+1 ) ₂ ;

Or R ₁₃ represents a C ₂ -C ₂₀ alkyl group, interspersed with one or more O, S, NR ₂₆ or CO;

Or R ₁₃ represents a phenyl or naphthyl group, and the two are unsubstituted or substituted by COR ₁₆ or substituted by one or more groups represented by formula (7);

R - ₁₄ represents a C ₁ -C ₂₀ alkyl group, a phenyl group or a C ₁ -C ₈ alkoxy group;

R ₁₅ represents a phenyl group, a naphthyl group, a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ An SR ₁₈ or C ₂ -C ₂₀ alkyl group having one or more O or S hetero; or each of which is substituted by one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group being unsubstituted Substituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxy Alkylcarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ;

Or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl Base, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ;

R' ₁₄ has one of the meanings given for R ₁₄ ;

R' ₁₅ has one of the meanings given for R ₁₅ ;

R ₁₆ represents a phenyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a C ₂ -C ₂₀ having one or more O, S or NR ₂₆ interstitial alkyl;

Or R ₁₆ represents phenyl which is substituted with one or more C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or is substituted with one or more of the following radicals: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₆ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl) or (CO)O(C ₁ -C ₄ alkyl);

R _-17 represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O ( C ₁ -C ₄ alkyl), (CO) O (C 1 -C 4 alkyl), C ₃ -C ₂₀ cycloalkyl interrupted by one or more O or a C ₃ -C ₂₀ cycloalkyl;

Or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, in which one or more O;

R ₁₈ represents a methyl group substituted by COOR ₁₇ ;

R ₁₉ and R ₂₀ are each independently hydrogen, phenyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₈ alkanoyl or C ₁ -C ₈ alkanoyloxy;

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted via a group represented by formula (7);

In one embodiment of the present invention, in the photoinitiator (C-1) represented by the formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 is} independently hydrogen, or R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ are each independently a group represented by the formula (5);

However, at least one of R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ is a group represented by the formula (5);

Or R ₂ represents COR _16, NO ₂ or by formula (2) or a group represented by the formula (3) a group represented by;

Or R ₇ represents COR ₁₆ or a group represented by formula (2);

R ₉ , R ₁₁ and R ₁₂ represent hydrogen;

R- ₁₀ represents hydrogen, OR ₁₇ or COR ₁₆ ;

X represents CO or a direct bond;

R ₁₃ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H _2k+1 ) ₂ ;

Or R ₁₃ represents a C ₂ -C ₂₀ alkyl group, in which one or more O;

Or R ₁₃ represents a phenyl group;

k represents an integer 2;

R ₁₄ represents a C ₁ -C ₂₀ alkyl group or a thienyl group;

R ₁₅ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl groups;

Or R ₁₅ represents a thiophene group, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following _{_{groups: OR 17, SR 18, C}} 3 -C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ;

Or R ₁₅ represents a C ₂ -C ₂₀ alkyl group, interspersed with SO ₂ ;

R ₁₆ represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl;

Or R ₁₆ represents a thienyl group;

R ₁₇ represents hydrogen, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups: halo, O (CO) -(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or a C ₃ -C ₂₀ cycloalkyl group having one or more O;

Or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, in which one or more O;

R ₁₈ represents a C ₃ -C ₂₀ cycloalkyl group, a C ₁ -C ₂₀ alkyl group which is unsubstituted or via one or more OH, O(CO)-(C ₂ -C ₄ alkenyl) or (CO) ) OR ₁₇ replaced;

Or R ₁₈ represents a phenyl group which is unsubstituted or substituted with one or more halogens;

R ₁₉ and R ₂₀ are each independently a C ₁ -C ₈ alkanoyl group or a C ₁ -C ₈ alkanoyloxy group;

Or R ₁₉ and R ₂₀ attached thereto together form a N atoms interrupted by O 5-membered or 6-membered saturated ring;

Provided that at least one group represented by formula (2) is present in the molecule;

In an embodiment of the invention, the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is selected from the group consisting of an unsaturated compound having a biscyclopentyl group and an unsaturated group having a dicyclopentenyl group. a group of compounds and mixtures thereof.

In an embodiment of the invention, the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is selected from the group consisting of dicyclopentanyl (meth)acrylate and dicyclopentenyl (meth)acrylate. a group consisting of dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and mixtures thereof.

In an embodiment of the invention, the compound (B) having an ethylenically unsaturated group includes the first compound (B-1), wherein the first compound (B-1) has a urethane group With at least 7 acryloyl groups.

In an embodiment of the invention, the first compound (B-1) has a urethane group and at least 10 acryl groups.

In an embodiment of the invention, the photosensitive resin composition further includes a dye (F).

In an embodiment of the invention, the dye (F) comprises a dye (F-1) represented by the formula (f-1),

In the formula (f-1),

J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. a substituted cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a substituted phenyl group;

J ⁵ and J ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom;

J ⁷ represents a group having a polymerizable unsaturated group;

a represents an integer from 1 to 5.

In an embodiment of the invention, the compound represented by the formula (f-1) includes a compound represented by the formula (f-2),

In the formula (f-2),

J ⁸ represents a group having a polymerizable unsaturated group.

In an embodiment of the invention, the above J ⁸ is a group represented by the formula (f-3) or a group represented by the formula (f-4),

In the formula (f-3) and the formula (f-4),

J ⁹ and J ¹⁰ each independently represent a hydrogen atom or a methyl group;

V ¹ , V ² , V ³ and V ⁴ each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms;

Q ¹ indicates

Q ² represents a divalent alicyclic hydrocarbon group;

b represents an integer from 0 to 12;

c and d each independently represent an integer from 0 to 6.

In one embodiment of the present invention, the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 20 parts by weight to 200 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). The photoinitiator (C) is used in an amount ranging from 10 parts by weight to 100 parts by weight; the solvent (D) is used in an amount ranging from 500 parts by weight to 5000 parts by weight; the pigment (E) The amount used is in the range of 30 parts by weight to 300 parts by weight.

In an embodiment of the invention, the dye (F) is used in an amount ranging from 5 parts by weight to 90 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).

In an embodiment of the invention, the unsaturated carboxylic acid based on the alkali-soluble resin (A-2) Or the total of the unsaturated carboxylic anhydride compound (a-2-1), the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2), and the other unsaturated compound (a-2-3) The amount of the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is from 10 parts by weight to 50 parts by weight in an amount of 100 parts by weight.

In one embodiment of the present invention, the first compound (B-1) is used in an amount ranging from 5 parts by weight to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).

In one embodiment of the present invention, the photoinitiator (C-1) is used in an amount ranging from 5 parts by weight to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A) used. .

In an embodiment of the invention, the dye (F-1) is used in an amount ranging from 3 parts by weight to 90 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).

A method of producing a color filter according to the present invention is to form a pixel layer using the above-described photosensitive resin composition.

A color filter of the present invention is produced by the above method.

A liquid crystal display device of the present invention includes the above-described color filter.

Based on the above, the photosensitive resin composition of the present invention comprises an alkali-soluble resin (A-1), an alkali-soluble resin (A-2), a first compound (B-1), and a photoinitiator (C-1). Therefore, problems such as poor linearity of the high-definition pattern, poor pattern smoothness, and high outgassing property can be improved, and the color filter and the liquid crystal display device can be applied.

The above described features and advantages of the present invention will be more apparent from the following description.

detailed description

The present invention provides a photosensitive resin composition comprising an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a pigment (E). Further, the photosensitive resin composition may further include a dye (F) and an additive (G). The respective components used in the photosensitive resin composition of the present invention will be described in detail below:

Here, it is explained that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth) acrylate; similarly, (meth) The acryloyl group means an acryloyl group and/or a methacryloyl group.

Alkali soluble resin (A):

The alkali-soluble resin (A) includes an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2).

Alkali soluble resin (A-1)

The alkali-soluble resin (A-1) is obtained by reacting a mixture, and the mixture includes an epoxy compound (a-1-1) having at least two epoxy groups, having at least one carboxylic acid group and at least one ethylene a compound (a-1-2), a tetracarboxylic acid or its acid dianhydride (a-1-3), and a dicarboxylic acid or an anhydride thereof (a-1-4)

Epoxy compound having at least two epoxy groups (a-1-1)

The epoxy compound (a-1-1) having at least two epoxy groups of the present invention may have a structure represented by the following formula (aI-1) or the following formula (aI-2). Here, the description that the "epoxy compound (a-1-1) may have a structure represented by the following formula (aI-1) or the following formula (aI-2)" also encompasses the following formula (aI-1) The compound of the structure shown and the compound which has a structure represented by the following formula (aI-2) exist simultaneously as the epoxy compound (a-1-1). Specifically, the epoxy compound (a-1-1) having at least two epoxy groups described above has, for example, a structure represented by the following formula (aI-1):

In the formula (aI-1), W ¹ , W ² , W ³ and W ⁴ are each the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5. The alkoxy group is an aryl group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

The epoxy compound (a-1-1) having at least two epoxy groups of the above formula (aI-1) may include a reaction of bisphenol fluorene with epihalohydrin. An epoxy group-containing bisphenol quinone type compound, but is not limited thereto.

Specific examples of the above bisphenol quinoid type compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyl group). -3-methylphenyl)fluorene [9,9-bis(4-hydroxy-3-methylphenyl)fluorene], 9,9-bis(4-hydroxy-3-chlorophenyl)indole [9,9-bis(4-hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene [9,9-bis(4-hydroxy-3-bromophenyl) Fluorene], 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3- 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9 -bis(4-hydroxy-3,5-dimethylphenyl)fluorene],9,9-bis(4-hydroxy-3,5-dichlorophenyl)indole [9,9-bis(4-hydroxy-3,5) -dichlorophenyl)fluorene], a compound such as 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene.

The above-mentioned epihalohydrin may include, but is not limited to, 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-propylene oxide (epibromohydrin).

The epoxy group-containing bisphenol quinoid compound obtained by reacting the bisphenol quinoid compound with the halogenated propylene oxide includes, but is not limited to: (1) a product manufactured by Nippon Steel Chemical Co., Ltd. : for example, ESF-300, etc.; (2) goods manufactured by Osaka Gas Co., Ltd.: for example, PG-100, EG-210, etc.; (3) manufactured by SMS Technology Co., Ltd. Goods such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.

Further, the above epoxy compound (a-1-1) having at least two epoxy groups may have a structure represented by the following formula (aI-2):

In the formula (aI-2), W ⁵ to W ¹⁸ are each the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and s represents An integer from 0 to 10.

The epoxy compound (a-1-1) having at least two epoxy groups having the structure represented by the formula (aI-2) may be included in the presence of an alkali metal hydroxide to have the following formula (aI-2- 1) A compound of the structure is obtained by reacting a halogenated propylene oxide.

In the above formula (aI-2-1), and are respectively of formula (aI-2) W ^5, and to the same definition of W, and W ¹⁸ s is defined to ⁵ W ¹⁸ s, and this is not described herein.

Further, the epoxy compound (a-1-1) having at least two epoxy groups of the above formula (aI-2) is, for example, in the presence of an acid catalyst, and has a structure having the following formula (aI-2-2). After the compound is subjected to a condensation reaction with a phenol, a compound having the structure of the formula (aI-2-1) is formed. Next, a dehydrohalogenation reaction is carried out by adding an excess of halogenated propylene oxide to obtain an epoxy compound (a-1-1) having at least two epoxy groups as shown in the formula (aI-2):

In the above formula (aI-2-2), W ¹⁹ and W ²⁰ are the same or different hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; ¹ and M ² are each the same or different halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Preferably, the above halogen atom may be, for example, chlorine or bromine, and the above alkyl group may be, for example, a methyl group, an ethyl group or a third butyl group, and the above alkoxy group may be, for example, a methoxy group or an ethoxy group.

Specific examples of the phenols include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, and t-butyl phenol. (t-butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol (vinylphenol), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The above phenols can be generally used singly or in combination of two or more.

The compound having the structure of the above formula (aI-2-2) is used in an amount of 1 mol, and the phenol is used in an amount of 0.5 mol to 20 mol, preferably 2 mol to 15 mol.

Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, and anhydrous chloride anhydrous. ), zinc chloride or the like, wherein p-toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. The above acid catalysts may be used singly or in combination of two or more.

Further, the amount of the acid catalyst used is not particularly limited, but based on the above formula (aI-2-2) The compound of the structure is used in an amount of 100% by weight (wt%), and the acid catalyst is preferably used in an amount of from 0.1% by weight to 30% by weight.

The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent include toluene, xylene, and methyl isobutyl ketone. The above organic solvents may be used singly or in combination of two or more.

The total amount of the compound and the phenol used based on the structure of the formula (aI-2-2) is 100% by weight, and the above organic solvent is used in an amount of 50% by weight to 300% by weight, preferably 100% by weight to 250% by weight. Further, the above condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the operation time of the condensation reaction is 1 hour to 8 hours.

After completion of the above condensation reaction, a neutralization treatment or a water washing treatment may be carried out. The above neutralization treatment is to adjust the pH of the solution after the reaction to pH 3 to pH 7, preferably pH 5 to pH 7. The water washing treatment may be carried out using a neutralizing agent, and the neutralizing agent is an alkaline substance, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and hydrogen; Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline, phenylenediamine (diethyltetramine) Organic amines such as phenylene diamine; and ammonia, sodium dihydrogen phosphate, and the like. The water washing treatment may be carried out by a known method. For example, an aqueous solution containing a neutralizing agent may be added to the solution after the reaction, and extraction may be repeated. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off by heating under reduced pressure, and concentrated to obtain a compound having the structure of the formula (aI-2-1).

Specific examples of the above halogenated propylene oxide include 3-chloro-1,2-epoxypropane and 3-bromo-1,2-epoxypropane (3). -bromo-1, 2-epoxypropane) or any combination of the above. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added during the reaction before the above dehydrohalogenation reaction. The above dehydrohalogenation reaction has an operating temperature of from 20 ° C to 120 ° C and an operation time ranging from 1 hour to 10 hours.

In a specific example of the present invention, an aqueous solution of the alkali metal hydroxide added to the dehydrohalogenation reaction may be used. In this specific example, while the aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing water. At the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Tetramethyl ammonium may also be added before the above dehydrohalogenation reaction is carried out. a quaternary ammonium salt such as chloride), tetramethyl ammonium bromide or trimethyl benzyl ammonium chloride as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour. After 5 hours, an alkali metal hydroxide or an aqueous solution thereof is further added, and the reaction is carried out at a temperature of from 20 ° C to 120 ° C for 1 hour to 10 hours to carry out a dehydrohalogenation reaction.

The halogenated propylene oxide may be used in an amount of from 1 equivalent to 20 equivalents, preferably from 2 equivalents to 10 equivalents, based on 1 equivalent of the total hydroxyl group in the compound having the structure of the formula (aI-2-1). The alkali metal hydroxide added in the above dehydrohalogenation reaction may be used in an amount of from 0.8 equivalents to 15 equivalents, based on 0.9 equivalents, based on the total equivalent of the hydroxyl group in the compound having the structure of the formula (aI-2-1). Equivalent to 11 equivalents is preferred.

Further, in order to smoothly carry out the above-described dehydrohalogenation reaction, an aprotic such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol. The polar solvent or the like is used to carry out the reaction. In the case of using an alcohol, the alcohol may be used in an amount of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight based on the total amount of the above-mentioned halogenated propylene oxide being 100% by weight. In the example using an aprotic polar solvent, the total amount of the halogenated propylene oxide is 100% by weight, and the aprotic polar solvent may be used in an amount of 5 wt% to 100 wt%, wherein 10 wt% to 90 wt% % is better.

After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, the aprotic polar solvent, and the like are removed by heating and pressure reduction. The heating and depressing is performed, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the dehydrohalogenated reaction solution may be added to a solvent such as toluene or methyl isobutyl ketone, and a base such as sodium hydroxide or potassium hydroxide may be added. The metal hydroxide aqueous solution is again subjected to a dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total equivalent weight of the hydroxyl group in the compound having the structure of the above formula (C-II-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, wherein 0.05 mol is used. It is preferably 0.2 mole. Further, the above dehydrohalogenation reaction has an operating temperature in the range of 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

After the completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, a solvent such as toluene or methyl isobutyl ketone may be distilled off by heating and decompression to obtain, for example, An epoxy compound (i) having at least two epoxy groups represented by the formula (C-II). The epoxy compound (i) having at least two epoxy groups of the above formula (C-II) may include, but is not limited to, a Japanese chemical such as NC-3000, NC-3000H, NC-3000S, and NC-3000P. (Nippon Kayaku Co. Ltd.) manufactured goods.

a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (a-1-2)

The compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is, for example, selected from the group consisting of (1) to (3): (1) acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxybutyl succinic acid, 2-methacryloyloxyethyl adipate, 2-methacryloyloxybutyl adipate, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxypropane Kamalyx, 2-methacryloyloxybutyl maleic acid, 2-methacryloxypropyl succinic acid, 2-methacryloxypropyl adipate, 2-methacryloyl Oxypropyl propyl tetrahydrophthalic acid, 2-methacryloxypropyl phthalic acid, 2-methacryloyloxybutyl phthalic acid, or 2-methacryloyloxybutyl hydrogen phthalate; (2) A compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, ortho-benzene Formic acid; (3) from a half ester compound obtained by reacting a (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group-containing (meth) acrylate includes, but not limited to, 2-hydroxyethyl acrylate; 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate], 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate ], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate. Further, the carboxylic anhydride compound described herein is the same as the tetracarboxylic dianhydride or the dicarboxylic acid anhydride described below, and will not be further described herein.

Tetracarboxylic acid or its acid dianhydride (a-1-3)

The tetracarboxylic acid or its acid dianhydride (a-1-3) includes a tetracarboxylic acid containing a fluorine atom or an acid dianhydride thereof, and a tetracarboxylic acid other than the fluorine atom-containing tetracarboxylic acid or its acid dianhydride. An acid or its acid dianhydride or a combination of the two.

The tetracarboxylic acid containing a fluorine atom or an acid dianhydride thereof is selected from the group consisting of a fluorine atom represented by the formula (K-1) A group consisting of a carboxylic acid compound and a tetracarboxylic dianhydride compound containing a fluorine atom represented by the formula (K-2). Specifically, the fluorine atom-containing tetracarboxylic acid compound represented by the formula (K-1) and the fluorine atom-containing tetracarboxylic dianhydride compound represented by the formula (K-2) are as follows.

In the formula (K-1) and the formula (K-2), L ² is a tetravalent aromatic group having fluorine, and preferably has a benzene ring. Specifically, it is preferably one selected from the group consisting of the formula (L-1) to the formula (L-6).

In the formulae (L-1) to (L-6), E each independently represents a fluorine atom or a trifluoromethyl group, and * represents a position bonded to a carbon atom.

More specifically, specific examples of the tetracarboxylic acid or acid dianhydride containing a fluorine atom include 4,4'-hexafluoroisopropylidene diphthalic acid, 1,4-difluorobenzenetetracarboxylic acid, and 1- a fluorine-containing aromatic tetracarboxylic acid such as monofluorobenzenetetracarboxylic acid or 1,4-bis(trifluoromethyl)benzenetetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid, or the above-mentioned Combination of compounds.

Specific examples of the tetracarboxylic acid or the acid dianhydride containing a fluorine atom further include 3,3'-hexafluoroisopropylidene diphthalic acid, 5,5'-[2,2,2-trifluoro-1 -[3-(Trifluoromethyl)phenyl]ethylidene]diphthalic acid, 5,5'-[2,2,3,3,3-pentafluoro-1-(trifluoromethyl) Propylene]diphthalic acid, 5,5'-oxybis[4,6,7-trifluoro-pyromellitic acid], 3,6-bis(trifluoromethyl)benzenetetracarboxylic acid, a fluorine-containing tetracarboxylic acid such as 4-(trifluoromethyl)benzenetetracarboxylic acid or 1,4-bis(3,4-dicarboxylic acid trifluorophenoxy)tetrafluorobenzene, or a second of the above tetracarboxylic acids An anhydride compound, or a combination of the above compounds.

The other tetracarboxylic acid or acid dianhydride thereof includes a saturated linear hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid, or a combination thereof.

Specific examples of the saturated linear hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or a combination of the above compounds. The saturated linear hydrocarbon tetracarboxylic acid may also have a substituent.

Specific examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, norbornanetetracarboxylic acid, or a combination of the above compounds. The alicyclic tetracarboxylic acid may also have a substituent.

Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylsulfone tetracarboxylic acid, 1,2,3,6 - tetrahydrophthalic acid, or a combination of the above compounds. The aromatic tetracarboxylic acid may also have a substituent.

Dicarboxylic acid or its anhydride (a-1-4)

The dicarboxylic acid or its anhydride (a-1-4) includes a dicarboxylic acid containing a fluorine atom or an anhydride thereof, a dicarboxylic acid other than the fluorine atom-containing dicarboxylic acid or an anhydride thereof, or an anhydride thereof or the above A combination of two.

The dicarboxylic acid containing a fluorine atom or an anhydride thereof is selected from the group consisting of a fluorine atom-containing dicarboxylic acid compound represented by the formula (M-1) and a fluorine atom-containing dicarboxylic anhydride compound represented by the formula (M-2). . Specifically, the fluorine atom-containing dicarboxylic acid compound represented by the formula (M-1) and the fluorine atom-containing dicarboxylic acid anhydride compound represented by the formula (M-2) are as follows.

In the formula (M-1) and the formula (M-2), G ¹ represents an organic group of a fluorine atom having 1 to 100 carbon atoms.

Specific examples of the dicarboxylic acid containing a fluorine atom or an anhydride thereof include 3-fluorophthalic acid and 4-fluoro-o-benzene. Dicarboxylic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, tetrafluorosuccinic acid, or an acid anhydride compound of the above dicarboxylic acid, or a combination of the above compounds.

Specific examples of the other dicarboxylic acid or its anhydride include a saturated linear hydrocarbon dicarboxylic acid, a saturated cyclic hydrocarbon dicarboxylic acid, an unsaturated dicarboxylic acid, or an acid anhydride of the above dicarboxylic acid compound, or a combination of the above compounds.

Specific examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, sebacic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxopentane Acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or a combination of the above compounds. Hydrocarbyl groups in saturated linear hydrocarbon dicarboxylic acids can also be substituted.

Specific examples of the saturated cyclic hydrocarbon dicarboxylic acid include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, or the like combination. The saturated cyclic hydrocarbon dicarboxylic acid may also be a saturated hydrocarbon-substituted alicyclic dicarboxylic acid.

Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl bridgedmethylenetetrahydrophthalic acid, chlorinic acid, and trimellitic acid. , or a combination of the above compounds.

Specific examples of other dicarboxylic acids or anhydrides thereof include trimethoxysilylpropyl succinic anhydride, triethoxysilyl propyl succinic anhydride, methyldimethoxysilyl propyl succinic anhydride, and methyl group. Diethoxysilylpropyl succinic anhydride, trimethoxysilylbutyl succinic anhydride, triethoxysilyl butyl succinic anhydride, methyldiethoxysilyl butyl succinic anhydride, (trimethoxysilyl)phenyl succinic anhydride, p-(triethoxysilyl)phenyl succinic anhydride, p-(methyldimethoxysilyl)phenyl succinic anhydride, p-methyl Ethoxysilyl)phenylsuccinic anhydride, m-(trimethoxysilyl)phenylsuccinic anhydride, m-(triethoxysilyl)phenylsuccinic anhydride, m-(diethoxysilane) A dicarboxylic acid anhydride such as phenyl succinic anhydride or a dicarboxylic acid compound of the above dicarboxylic anhydride or a combination of the above compounds.

The method for synthesizing the alkali-soluble resin (A-1) is not particularly limited as long as the epoxy compound (a-1-1) having at least two epoxy groups, at least one carboxylic acid group, and at least one ethylenic unsaturated group are used. The compound (a-1-2), the tetracarboxylic acid or its acid dianhydride (a-1-3), and the dicarboxylic anhydride or its anhydride (a-1-4) are obtained by reaction.

The number average molecular weight of the alkali-soluble resin (A-1) is usually from 1,000 to 8,000, preferably from 1,500 to 7,500, more preferably from 2,000 to 7,000. The above alkali-soluble resin (A-1) is converted into a number average molecular weight by polystyrene measured by a gel permeation chromatography (GPC).

The alkali-soluble resin (A-1) is used in an amount of 5 to 95 parts by weight, preferably 10 parts by weight to 90 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), and more preferably 15 parts by weight. Parts by weight to 85 parts by weight. When the alkali-soluble resin (A-1) is not used, the photosensitive resin composition has a problem that the outgassing performance is poor.

When the number average molecular weight of the alkali-soluble resin (A-1) is not in the range of from 1,000 to 8,000, the photosensitive resin composition may have a problem that the outgassing performance is poor.

Alkali soluble resin (A-2)

The alkali-soluble resin (A-2) is composed of an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a-2-1), an alicyclic hydrocarbon group-containing unsaturated compound (a-2-2), and other unsaturated groups. The compound (a-2-3) is obtained by copolymerization.

The solvent used to prepare the alkali-soluble resin (A-2) may include, but is not limited to, ethylene glycol methyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol Butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, a (poly)alkylene glycol monoalkyl ether solvent such as tripropylene glycol mono methyl ether or tripropylene glycol mono ethyl ether; ethylene glycol methyl ether acetate; a (poly)alkylene glycol monoalkyl ether acetate solvent such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate or propylene glycol diethyl ether acetate; diglyme, diethylene glycol methyl ether, digan Other ether solvents such as alcohol diethyl ether and tetrahydrofuran; ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate and 2-hydroxypropionic acid Alcoholic acid alkyl ester solvent such as ester; methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyacetic acid Ethyl ester, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropane Acid ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid N-propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate Other ester solvents such as; aromatic hydrocarbon solvents such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide Solvent. The above solvents may be used singly or in combination of plural kinds.

Preferably, the solvent used to prepare the alkali-soluble resin (A-2) is selected from the group consisting of propylene glycol methyl ether acetate Ester, ethyl 3-ethoxypropionate or cyclohexanone.

The initiator for preparing the alkali-soluble resin (A-2) is generally a radical polymerization initiator, and the initiator may include, but is not limited to, 2,2'-azobisisobutyronitrile (2, 2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (2-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methyl An azo compound such as 2,2'-azobis-2-methyl butyronitrile; a peroxy compound such as benzoylperoxide.

Unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1)

The structure of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) is not particularly limited. In a specific example of the present invention, the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) includes acrylic acid (AA), methacrylic acid (MAA), 2-methacryloyloxybutylene Acid ester (HOMS), crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride or The above anhydride or a mixture thereof. Preferably, the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) is acrylic acid, methacrylic acid, 2-methacryloyloxy succinate or the above anhydride or a mixture thereof.

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) based on the alkali-soluble resin (A-2), the alicyclic hydrocarbon group-containing unsaturated compound (a-2- 2) and the total amount of the other unsaturated compound (a-2-3) is 100 parts by weight, and the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) is used in an amount of 20 parts by weight. The portion is 40 parts by weight; preferably 23 parts by weight to 38 parts by weight; more preferably 25 parts by weight to 35 parts by weight.

Alicyclic compound containing an alicyclic hydrocarbon group (a-2-2)

The structure of the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is not particularly limited, and in the specific example of the present invention, an alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) Is a group consisting of an unsaturated compound having a bicyclopentyl group, an unsaturated compound having a dicyclopentenyl group, and a mixture thereof.

In a specific example of the present invention, the unsaturated compound having a bicyclopentyl group has a structure represented by the following formula (aII-1):

among them:

U ¹ represents a hydrogen atom or a methyl group;

u is represented as an integer from 0 to 2.

On the other hand, in a specific example of the present invention, the dicyclopentenyl-containing unsaturated compound has a structure represented by the following formula (aII-2):

among them:

U ² represents a hydrogen atom or a methyl group;

v represents an integer of 0 to 2.

In a preferred embodiment of the present invention, the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is selected from the group consisting of dicyclopentanyl (meth)acrylate and biscyclopentenyl (meth)acrylate. a group consisting of dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and mixtures thereof.

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) based on the alkali-soluble resin (A-2), the alicyclic hydrocarbon group-containing unsaturated compound (a-2- 2) and the total amount of the other unsaturated compound (a-2-3) is 100 parts by weight, and the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is used in an amount of 10 parts. The parts by weight to 50 parts by weight; preferably 15 parts by weight to 45 parts by weight; more preferably 20 parts by weight to 40 parts by weight. .

Other unsaturated compounds (a-2-3)

In a preferred embodiment of the invention, the alkali-soluble resin (A-2) may include other unsaturated compounds (a-2-3). Specific examples of the other unsaturated compound (a-2-3) are styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, divinylbenzene, benzyl methacrylate, benzyl. Acrylate, phenyl methacrylate, phenyl acrylate, 2-nitrophenyl acrylate, 4-nitrophenyl acrylate, 2-nitrophenyl methacrylate, 2-nitrobenzyl Methacrylate, 2-nitrophenyl Acrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, phenoxyethyl methacrylate, Phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol methacrylate, nonyl phenoxy polyethylene glycol acrylate, nonyl phenoxy polyethylene glycol methacrylate, N- Phenyl maleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-ortho -methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenyl Malay Imid, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, o-vinylphenol, m-vinylphenol, p-vinyl Phenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, 2-vinyl- 1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropene 1-naphthol, 3-isopropenyl-1-naphthol, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-methoxymethylstyrene , m-methoxymethylstyrene, p-methoxymethylstyrene, o-(vinylbenzyl)epoxypropyl ether, m-(vinylbenzyl)epoxypropyl ether , p-(vinylbenzyl)epoxypropyl ether, hydrazine, acetylnaphthalene, N-cyclohexylmaleimide, methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, acrylic acid Propyl ester, n-butyl acrylate, isobutyl acrylate, dibutyl acrylate, tert-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy acrylate Butyl ester, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, allyl acrylate, triethylene glycol methacrylate, N,N-dimethylamino acrylate, N,N-diethyl Propyl propyl acrylate, N,N-dibutylamino propyl acrylate, glycidyl acrylate, methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, A Acrylic acid Propyl ester, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, allyl methacrylate, triethylene methacrylate Alcohol methoxy ester, dodecyl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, Tetylene glycol methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, N-iso-butylaminomethyl Ethyl acrylate, glycidyl methacrylate (GMA), vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether, methyl Allyl glycidyl ether, acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, vinyl cyanide, propylene Amide, methacrylamide, α-chloroacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 1,3-butadiene, isoamylene, chlorobutadiene or its Preferably, the third unsaturated single system is methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, acrylic acid Tributyl ester, 2-hydroxyethyl acrylate, C 2-hydroxypropyl enoate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methyl Dibutyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, vinyl acetate, acrylonitrile, methyl Acrylonitrile, 1,3-butadiene, isoamylene or a mixture thereof. Preferably, the third unsaturated single system is styrene, α-methylstyrene, phenyl methacrylate, phenyl acrylate, N-phenylmaleimide (PMI), N-ortho -hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, glycidyl methacrylate, methyl methacrylate Monomer, methyl acrylate monomer, 2-methylglycidyl methacrylate (MGMA), benzyl methacrylate (BzMA) or a mixture thereof.

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) based on the alkali-soluble resin (A-2), the alicyclic hydrocarbon group-containing unsaturated compound (a-2- 2) and the total amount of the other unsaturated compound (a-2-3) is 100 parts by weight, and the other unsaturated compound (a-2-3) is used in an amount ranging from 10 parts by weight to 70 parts by weight; It is preferably from 17 parts by weight to 62 parts by weight; more preferably from 25 parts by weight to 55 parts by weight.

The polystyrene-equivalent weight average molecular weight of the above alkali-soluble resin (A-2) measured by Gel Permeation Chromatography (GPC) is generally from 3,000 to 30,000, preferably from 5,000 to 25,000, more preferably 7000 to 20,000.

The alkali-soluble resin (A-2) is used in an amount of 5 to 95 parts by weight, preferably 10 parts by weight to 90 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), and more preferably 15 parts by weight. Parts by weight to 85 parts by weight. When the alkali-soluble resin (A-2) is not used, the photosensitive resin composition has a problem that the high-definition pattern has poor linearity.

When the weight average molecular weight of the alkali-soluble resin (A-2) is not in the range of 3,000 to 30,000, the photosensitive resin composition has a problem that the pattern linearity of high-definition is poor.

Further, the weight ratio range (A-1) / (A-2) of the amount of the alkali-soluble resin (A-1) to the alkali-soluble resin (A-2) is 5/95 to 95/5. When the weight ratio range (A-1)/(A-2) does not fall within the above range, the photosensitive resin composition has a problem that the outgassing performance is poor and the high definition pattern linearity is poor.

Ethylene unsaturated group compound (B)

The ethylenically unsaturated group-containing compound (B) includes the first compound (B-1) and the second compound (B-2).

First compound (B-1)

The first compound (B-1) may have a urethane group and at least 7 acryloyl groups. Preferably, the first compound (B-1) may have a urethane group and at least 10 acryl groups.

The preparation method of the first compound (B-1) is, for example but not limited to, a condensation reaction of a polyisocyanate compound and a polyol compound, wherein at least one of the polyisocyanate compound and the polyol compound has an acryloyl group, and the polyisocyanate The total number of acryloyl groups contained in the compound and the polyol compound is preferably at least 7, and more preferably at least 10.

When the first compound (B-1) has a urethane group and at least 10 acryl groups, the resulting photosensitive resin composition has better pattern smoothness.

Specific examples of the first compound (B-1) may be commercially available products, for example, those manufactured by Nippon Synthetic Chemical Co., Ltd., and may be of a type of UV1700B (weight average molecular weight of 2000 and having 10 acryloyl groups) ), UV6300B (having 7 acryloyl groups) or UV7640B (having 7 acryloyl groups), etc.; a product manufactured by Nippon Kayaku Co., Ltd., and its model number is DPHA40H (weight average molecular weight is 7000 and it has 10 acryloyl groups) Or UX5001T (with 8 acryloyl groups), etc.; a product manufactured by Gensei Industrial Co., Ltd., and its model can be UN3320HS (weight average molecular weight is 5000 and it has 15 acryloyl groups), UN904 (weight average molecular weight is 4900 and It has 10 acryloyl groups, UN3320HC (weight average molecular weight 1500 and 10 acryloyl groups thereof), etc.; or a product manufactured by Shin-Nakamura Chemical Co., Ltd., and its model may be U15HA (weight average molecular weight is 2000 and it has 15 Acryl), UA-33H (having 9 acryloyl groups) or UA-53H (having 15 acryloyl groups) and the like.

The first compound (B-1) can be used singly or in combination of plural kinds.

Preferably, the aforementioned first compound (B-1) may be any combination of UV6300B, UX5001T, DPHA40H, UN3320HS, U15HA or the above-mentioned commercially available products.

The first compound (B-1) may be used in an amount of 5 parts by weight to 100 parts by weight, preferably 10 parts by weight to 95 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). More preferably, it may be 15 parts by weight to 90 parts by weight.

When the ethylenically unsaturated group-containing compound (B) of the present invention contains the first compound (B-1), the resulting photosensitive resin composition preferably has a pattern smoothness.

Second compound (B-2)

Specific examples of the second compound (B-2) may include diol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, and 1,4-butanediol dimethacrylate. Ester, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, Dicyclopentenyl (meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(a) Acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, three Trimethylolpropyl (meth)acrylate, trimethylolpropyl tris(meth)acrylate modified with ethylene oxide (EO), modified by propylene oxide (PO) Trimethylolpropyl methacrylate, tripropylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate , polyester di(meth) acrylate, polyethylene glycol di(meth) propylene Acid ester, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate modified by caprolactone, di(trimethylolpropyl) tetra(meth)acrylate, EO modified bisphenol A Di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, EO modified hydrogenated bisphenol A di(meth)acrylate, PO modified hydrogenated bisphenol A Di(meth)acrylate, PO modified tris(meth)acrylate, EO modified bisphenol F di(meth)acrylate, novolac polyglycidyl ether (meth)acrylate Or any combination of the above compounds.

The second compound (B-2) can be used singly or in combination of plural kinds.

Preferably, the second compound (B-2) may be caprolactone-modified dipentaerythritol hexa(meth) acrylate, ethylene oxide (EO)-modified tris(meth)acrylic acid III. Hydroxymethyl propyl ester, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate or any combination of the above.

The second compound (B-2) may be used in an amount of 15 parts by weight to 100 parts by weight, preferably 20 parts by weight to 95 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). More preferably, it may be 25 parts by weight to 90 parts by weight.

Further, when the total amount of the alkali-soluble resin (A) used is 100 parts by weight, the compound (B) having an ethylenically unsaturated group may be used in an amount of 20 parts by weight to 200 parts by weight, preferably 30 parts by weight. The portion is 190 parts by weight, and more preferably 40 parts by weight to 180 parts by weight.

Photoinitiator (C)

The photoinitiator (C) includes a photoinitiator (C-1) and other photoinitiators (C-2).

Photoinitiator (C-1)

The photoinitiator (C) includes a photoinitiator (C-1) represented by the formula (1).

Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently a group represented by the formula (4). Substituted C ₂ -C ₁₀ alkenyl,

Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ , NO ₂ or formula (2),

Y represents O, S, NR ₂₆ or a direct bond;

p represents an integer of 0, 1, 2 or 3;

q represents an integer of 1, 2 or 3;

X represents CO or a direct bond;

Or R ₁₃ represents a C ₂ -C ₂₀ alkyl group, interspersed with one or more of O, S, SO, SO ₂ , NR ₂₆ or CO, or a C ₂ -C ₁₂ alkenyl group, which has no inter a plurality of O, CO or NR ₂₆ , wherein the meta-hetero C ₂ -C ₂₀ alkyl group and the unmeta- or inter-hetero C ₂ -C ₁₂ alkenyl group are unsubstituted or substituted with one or more halogens;

k represents an integer from 1 to 10;

Or R ₁₄ represents a C ₃ -C ₂₀ heteroaryl group, a C ₁ -C ₈ alkoxy group, a benzyloxy group or a phenoxy group, the benzyloxy group and the phenoxy group being unsubstituted or having one or more of the following groups Group substituted: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and/or halogen; R ₁₅ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or Substituted by one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, interrupted by one or more O, S or NR C ₂₆ of ₂ -C ₂₀ alkyl; or C ₁ -C ₂₀ each warp Alkyl substituted, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C _3- C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₅ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl having no or hetero or one or more O, CO or NR ₂₆ ; or R ₁₅ is C ₁ -C ₂₀ alkyl , which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxy a group represented by a carbonyl group, a C ₃ -C ₂₀ heteroaryloxycarbonyl group, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , a phenyl group, and a formula (6) Or a group represented by the formula (8),

Or R ₁₅ represents a C ₂ -C ₂₀ alkanoyl or benzoyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ Or NR ₁₉ R ₂₀ ; or R ₁₅ is a naphthoyl group or a C ₃ -C ₁₄ heteroarylcarbonyl group which is unsubstituted or substituted by one or more OR ₁₇ ;

m represents 1 or 2;

R' ₁₄ has one of the meanings given for R ₁₄ ;

R' ₁₅ has one of the meanings given for R ₁₅ ;

X ₁ represents O, S, SO or SO ₂ ;

X ₂ represents O, CO, S or a direct bond;

n represents 1 to 20;

R ₁₇ represents hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO) -(C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ - (C ₁ -C ₄ haloalkyl), O(C ₁ -C ₄ haloalkyl) or a C ₃ -C ₂₀ cycloalkyl group having one or more O;

Or R ₁₈ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C _4- haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N (C ₁ -C ₈ alkyl) ₂ or a group represented by the formula (7),

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR ₁₇ and which is either 5- or 6-membered saturated or unsaturated The ring is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO) R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl, C ₃ -C ₂₀ cycloalkyl having one or more O, S, CO or NR ₁₇ undoped or inter-hetero, or a group represented by the formula (7),

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , halogen, NO ₂ , CN, phenyl or uninter or hetero Or a plurality of C ₃ -C ₂₀ cycloalkyl groups of O, S, CO or NR ₁₇ or a group represented by the formula (7),

R ₂₆ represents hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl with one or more O or CO in between; or phenyl-C ₁ -C ₄ alkane a C ₃ -C ₈ cycloalkyl group which is undoped or heterozygous with one or more O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or one or more Substituted by: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a group represented by formula (7);

The compound of formula (1) is characterized in that it comprises one or more annelated unsaturated rings on the carbazole moiety. In other words, at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ is represented by the formula (5). Group,

C ₁ -C ₂₀ alkyl is straight or branched and is, for example, C ₁ -C ₁₈ -, C ₁ -C ₄ -, C ₁ -C ₁₂ -, C ₁ -C ₈ -, C ₁ -C _8- or C ₁ -C ₄ alkyl or C ₄ -C ₁₂ - or C ₄ -C ₈ alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Amyl, 2-ethylhexyl, octyl, decyl, decyl, dodecyl, tetradecyl, fifteen, hexadecyl, octadecyl and decyl. The C ₁ -C ₆ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms.

An unsubstituted or substituted C ₁ -C ₂₀ alkyl group containing one or more CC multiple bonds means an alkenyl group as explained below.

C ₁ -C ₄ haloalkyl halogen substituted as hereinbefore defined C ₁ -C ₄ alkyl as defined below. The alkyl group is, for example, mono- or polyhalogenated until all H-atoms are replaced by halogen. It is, for example, C _z H _x Hal _y , where x+y=2z+1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. C ₂ -C ₄ hydroxyalkyl means a C ₂ -C ₄ alkyl group substituted with one or two O atoms. The alkyl group is straight or branched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 2,3-dihydroxypropyl or 2,4-dihydroxybutyl. C ₂ -C ₁₀ alkoxyalkyl is interrupted by O atoms, a C ₂ -C ₁₀ alkyl. The C ₂ -C ₁₀ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, Propoxypropyl.

A C ₂ -C ₂₀ alkyl group having one or more O, S, NR ₂₆ or CO intermixed with O, S, NR ₂₆ or CO (for example) 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 Times or 2 times. If more than one meta-group is present, it is the same species or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., exoethyl groups). The alkyl groups are straight or branched. For example, the following structural units will be present: -CH ₂ -CH ₂ -O-CH ₂ CH ₃ , -[CH ₂ CH ₂ O] _y -CH ₃ (where y = 1 to 9), -(CH ₂ - CH ₂ O) ₇ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ ,- CH ₂ -CH ₂ -S-CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-NW ²⁶ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -COO-CH ₂ CH ₃ or -CH ₂ - CH(CH ₃ )-OCO-CH ₂ -CH ₂ CH ₃ .

C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkyl and C ₃ -C ₈ cycloalkyl are understood in the context of the present application to mean an alkyl group containing at least one ring. It is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. C ₃ -C ₁₀ cycloalkyl is intended to encompass a bicyclic ring in the context of the present invention, in other words, a bridging ring, for example

And the corresponding ring. Other examples are such as

(E.g

) or

Such structures, as well as reunion or fused ring systems, for example, the term is intended to cover:

And other structures.

The C ₃ -C ₂₀ cycloalkyl group interspersed with O, S, CO, NR ₂₆ has the meaning given above wherein at least one CH ₂ - group in the alkyl group is replaced by O, S, CO or NR ₂₆ . An example is something like

(E.g

),

And other structures.

C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl is C ₃ -C ₁₀ cycloalkyl as defined above substituted by one or more alkyl groups having up to 8 carbon atoms. An example is:

Wait.

A C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl group interspersed with one or more O is an O-interstitial C ₃ - as defined above substituted with one or more alkyl groups having up to 8 carbon atoms C ₁₀ cycloalkyl. An example is:

Wait.

C ₁ -C ₁₂ alkoxy is O-substituted by a C ₁ -C ₁₂ alkyl. The C ₁ -C ₁₂ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms. C ₁ -C ₄ alkoxy is straight or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy or Tributoxy. The C ₁ -C ₈ alkoxy group and the C ₁ -C ₄ -alkoxy group have the same meanings as described above and have the highest corresponding number of C atoms.

C ₁ -C ₁₂ alkylthio is S atom substituted by a C ₁ -C ₁₂ alkyl. The C ₁ -C ₂₀ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms. C ₁ -C ₄ alkylthio is straight-chain or branched, such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, second butylthio , isobutylthio group, tert-butylthio group.

Phenyl-C ₁ -C ₃ alkyl is, for example, benzyl, phenylethyl, α-methylbenzyl or α,α-dimethyl-benzyl, especially benzyl.

The phenyl-C ₁ -C ₃ alkoxy group is, for example, a benzyloxy group, a phenylethoxy group, an α-methylbenzyloxy group or an α,α-dimethylbenzyloxy group, especially a benzyloxy group.

C ₂ -C ₁₂ alkenyl is mono- or polyunsaturated and is, for example, C ₂ -C ₁₀ -, C ₂ -C ₈ -, C ₂ -C ₅ -alkenyl, such as vinyl, allyl, Methyl allyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-Octyl or dodecenyl, especially allyl. The C ₂ -C ₅ alkenyl group has the same meaning as given above for the C ₂ -C ₁₂ alkenyl group and has the highest corresponding number of C atoms.

a C ₂ -C ₁₂ alkenyl group having one or more O, CO or NR ₂₆ interspersed with O, S, NR ₂₆ or CO, for example 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 time or 2 times. If more than one meta-group is present, it is the same species or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., exoethyl groups). Alkenyl is straight or branched and is as defined above. For example, the following structural units can be formed: -CH=CH-O-CH ₂ CH ₃ , -CH=CH-O-CH=CH ₂ and the like.

The C ₄ -C ₈ cycloalkenyl group has one or more double bonds and is, for example, a C ₄ -C ₆ -cycloalkenyl group or a C ₆ -C ₈ -cycloalkenyl group. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

The C ₃ -C ₆ alkenyloxy group is mono- or polyunsaturated and has one of the meanings given above for an alkenyl group, and the attached oxy group has the highest corresponding number of C atoms. Examples are allyloxy, methylallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.

The C ₂ -C ₁₂ alkynyl group is a mono- or polyunsaturated straight or branched chain and is, for example, a C ₂ -C ₈ -, C ₂ -C ₆ - or C ₂ -C ₄ alkynyl group. Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, Octyl group and the like.

The C ₂ -C ₂₀ alkanoyl group is straight or branched and is, for example, C ₂ -C ₁₈ -, C ₂ -C ₁₄ -, C ₂ -C ₁₂ -, C ₂ -C ₈ -, C ₂ -C _6- or C ₂ -C ₄ alkanoyl or C ₄ -C ₁₂ - or C ₄ -C ₈ alkanoyl. Examples are acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, heptanoyl, octanoyl, decanoyl, decanoyl, dodecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, ten The octayl group, the icosyl group is preferably an acetyl group. The C ₁ -C ₈ alkanoyl group has the same meaning as given above for the C ₂ -C ₂₀ alkanoyl group and has the highest corresponding number of C atoms.

C ₂ -C ₁₂ alkoxycarbonyl is straight-chain or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1,1 - dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially methoxy A carbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a n-butoxycarbonyl group or an isobutoxycarbonyl group is preferably a methoxycarbonyl group.

The C ₂ -C ₁₂ alkoxycarbonyl group having one or more O interstitials is linear or branched. The two O atoms are separated by at least two methylene groups (ie, an extended ethyl group). The meta-heteroalkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups. The C ₆ -C ₂₀ aryloxycarbonyl group is, for example, a phenyloxycarbonyl group [=phenyl-O-(CO)-], a naphthyloxycarbonyl group, a decyloxycarbonyl group or the like. The C ₅ -C ₂₀ heteroaryloxycarbonyl group is a C ₅ -C ₂₀ heteroaryl-O-CO- group.

The C ₃ -C ₁₀ cycloalkylcarbonyl group is a C ₃ -C ₁₀ cycloalkyl-CO- group wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms. The C ₃ -C ₁₀ cycloalkylcarbonyl group having one or more O, S, CO, NR ₂₆ is inter-heterocycloalkyl-CO-, wherein the meta-heterocycloalkyl group is as defined above.

The C ₃ -C ₁₀ cycloalkoxycarbonyl group is C ₃ -C ₁₀ cycloalkyl-O-(CO)-, wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms. The C ₃ -C ₁₀ cycloalkoxycarbonyl group having one or more O, S, CO, NR ₂₆ inter-heterocycloalkyl-O-(CO)-, wherein the inter-heterocycloalkyl group is as described above Defined.

The C ₁ -C ₂₀ alkylphenyl group means a phenyl group substituted by one or more alkyl groups, wherein the sum of the C atoms is at most 20.

C ₆ -C ₂₀ aryl is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, tetracylphenyl, bistriphenyl, etc., especially phenyl or naphthyl, Good is phenyl. The naphthyl group is 1-naphthyl or 2-naphthyl.

In the context of the present invention, C ₃ -C ₂₀ heteroaryl is intended to include monocyclic or polycyclic systems, such as fused ring systems. Examples are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thioxyl, furyl, dibenzofuranyl, xanthenyl, thioxanthyl, phenothiphenyl , pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, mesoindolyl, isodecyl, decyl, oxazolyl, fluorenyl, quinazolyl, isoquinoline , quinolyl, pyridazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, porphyrinyl, acridinyl, oxazolyl, β-carboline, phenanthryl, acridinyl, Naphthalene, diphenylphenyl, phenanthroline, phenazinyl, isothiazolyl, phenothiazine, isoxazolyl, furazinyl, oxo, 7-phenanthryl, indole-2-yl (=9,10-di-oxy-9,10-dihydroindol-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b] Thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-indenyl, 8-methyl-2-indole Base, 3-xanthene, 2-morphothinyl, 2,7-morphothinyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4 -Imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2- Ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4 -pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1 -isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indenyl, 1-methyl-3-indole Azyl, 2,7-dimethyl-8-fluorenyl, 2-methoxy-7-methyl-8-fluorenyl, 2-quinazinyl, 3-isoquinolinyl, 6-isoquinoline , 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolinyl, 2-methoxy-3-quinoline , 2-methoxy-6-quinolyl, 6-pyridazinyl, 7-pyridazinyl, 1-methoxy-6-pyridazinyl, 1,4-dimethoxy-6-indole Zinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy -6-quinoxaline, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-carbolinyl, 6-carbolinyl, 7-carbolinyl, 3-methoxy-7-carbolinyl, 2-acridinyl, 6-acridinyl, 7-acridinyl, 6,7-dimethoxy-2-indolyl 2-咔Azyl, 3-oxazolyl, 9-methyl-2-oxazolyl, 9-methyl-3-oxazolyl, β-carboline-3-yl, 1-methyl-β-carboline- 3-yl, 1-methyl-β-carboline-6-yl, 3-phenantidinyl, 2-acridinyl, 3-acridinyl, 2-naphthyldiazophenyl, 1-methyl 5-5-naphthalene dinitrophenyl, 5-phenanolyl, 6-phenanthroline, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5 -isothiazolyl, 2-phenothiazine, 3-phenothiazine, 10-methyl-3-phenothiazine, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazole Base, 4-methyl-3-furoyl, 2-phenoxy group, 10-methyl-2-phenoxy group, and the like.

The C ₃ -C ₂₀ heteroaryl group is especially thienyl, benzo[b]thienyl, thioxyl, thioxanthyl, 1-methyl-2-indenyl or 1-methyl-3-indolyl Especially tienyl.

A C ₄ -C ₂₀ heteroarylcarbonyl group is a C ₃ -C ₂₀ heteroaryl group as defined above attached to the remainder of the molecule via a CO group.

Substituted aryl (phenyl, naphthyl, C ₆ -C ₂₀ aryl or C ₅ -C ₂₀ heteroaryl) is 1 to 7 times, 1 to 6 times or 1 to 4 times, especially 1 time, respectively , 2 or 3 substitutions. It will be apparent that the defined aryl group cannot have more substituents than the free position at the aryl ring.

The substituent on the phenyl ring is preferably in position 4 on the phenyl ring or in the 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration .

Intermixed with one or more interstitial hetero groups (for example) 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times or 1 or 2 times (obviously, the number of heteroatoms depends on the number of C atoms to be inter-hetero). The substituted group substituted by one or more times has, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.

A group substituted with one or more substituents as defined is intended to have one substituent or a plurality of substituents as defined or differently given. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. When R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ are each independently a group represented by the formula (5) group,

Then, for example, the following (Ia)-(Ii) structure is formed:

Preferred is structure (Ia).

The compound of formula (1) is characterized in that at least one phenyl ring is partially fused to the carbazole to form a "naphthyl" ring. That is, one of the above structures is given by the formula (1).

If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently taken to be -(CH ₂ ) _P -Y- (CH ₂ ) _q -, forming, for example, such as:

And other structures.

If the substituent OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ on the phenyl or naphthyl ring is via the radicals R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ with a naphthyl ring When one carbon atom forms a 5- or 6-membered ring, a structure containing 3 or more rings including a naphthyl ring is obtained. An example is:

And other structures.

If R ₁₇ forms a bond to have a group thereon

a direct bond of a carbon atom of a phenyl or naphthyl ring, for example, such as

structure.

If R ₁₆ represents a phenyl group substituted by SR ₁₈ , wherein the group R ₁₉ represents a direct bond bonded to a phenyl or naphthyl ring to which a carbazole moiety of a COR ₁₆ group is attached, for example, such as

And other structures. That is, if R ₁₆ is a phenyl group substituted by SR ₁₈ , wherein the group R ₁₈ represents a direct bond bonded to a phenyl or naphthyl ring to which a carbazole moiety of a COR ₁₆ group is attached, the thioxanthyl group Part of it is formed together with a phenyl or naphthyl ring of the carbazole moiety.

If R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is optionally interspersed with O, S or NR ₁₇ , a saturated or unsaturated ring, such as aziridine, is formed. Pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine. Preferably, if R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring heterogeneously interspersed with O, S or NR ₁₇ , an inter- or inter-molecular O is formed. Or a 5- or 6-membered saturated ring of NR ₁₇ , especially O.

If R ₂₁ and R ₂₂ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S or NR ₂₆ , and the benzene ring is optionally fused to the saturated or unsaturated ring. , forming a saturated or unsaturated ring, such as aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine or corresponding ring ,E.g

Wait.

If R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, the ring system is intended to contain more than one ring (eg 2 or 3 rings) and one or one from the same species or different species. Above heteroatoms. Suitable heteroatoms are, for example, N, S, O or P, especially N, S or O. Examples are carbazole, anthracene, isoindole, carbazole, anthracene, isoquinoline, quinoline, porphyrin, phenothiazine and the like.

The term "and/or" or "or/and" is intended to mean in the context of the present invention that not only one of the defined substitutes (substituents) may be present, but also a total of several defined substitutes (substituents) may be present, ie different A mixture of substitutes (substituents).

The term "at least" is intended to define one or more than one, for example one or two or three, preferably one or two.

The term "optionally substituted" means that the group to which it is referred to is unsubstituted or substituted.

The term "intervening as appropriate" means that the group to which it is referred is not miscellaneous or interstitial.

Throughout the specification and the claims below, the words "comprise" or variant (eg, "comprises" or "comprising") are understood to include the integer or step, unless the context requires otherwise. Or an integer group or a group of steps, but does not exclude any other integer or step or group of integers or groups of steps. The term "(meth)acrylate" is intended in the context of the present application to mean acrylates and corresponding methacrylates.

The oxime ester of formula (1) is prepared by the methods described in the literature, for example by reacting the corresponding hydrazine with an acid halide, especially a chloride or an acid anhydride, in an inert solvent (for example, tert-butyl methyl ether, tetrahydrofuran (THF) Or dimethylformamide) in the presence of a base such as triethylamine or pyridine or in a basic solvent such as pyridine. The preparation of the compound of the formula Ia is illustrated below as an example, wherein R ₇ represents a oxime ester group and X represents a direct bond [the reaction of the compound (Ib)-(Ih) is carried out starting from an appropriate hydrazine]:

R ₁ , R ₂ , R ₅ , R ₆ , R ₈ , R ₁₃ , R ₁₄ and R ₁₅ are as defined above, and Hal means a halogen atom, especially Cl.

R _{14 is} preferably a methyl group.

Such reactions are well known to those skilled in the art and are typically carried out at a temperature of from -15 ° C to +50 ° C, preferably from 0 to 25 ° C.

When X represents CO, the corresponding hydrazine is nitrosated by using an alkyl nitrite such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite. To synthesize. The esterification is then carried out under the same conditions as described above:

Accordingly, it is an object of the present invention to prepare a compound of formula (1) as defined above by reacting the corresponding hydrazine compound with an acid halide of formula VI or an anhydride of formula VII in the presence of a mixture of bases or bases.

Wherein Hal is halogen, especially C1, and R ₁₄ is as defined above.

The desired hydrazine as a starting material can be passed through standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992) or monographs (eg SRSandler & W. Karo, Organic functional group preparations, Vol. 3, Various methods are described in Academic Press).

One of the most convenient methods is to, for example, react an aldehyde or a ketone with hydroxylamine or a salt thereof in a polar solvent such as dimethylacetamide (DMA), aqueous DMA, ethanol or an aqueous ethanol solution. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and the base can be added continuously at the beginning or during the reaction. Basic solvents such as pyridine can also be used as the base and/or solvent or cosolvent. The reaction temperature is usually from room temperature to the reflux temperature of the mixture, and is usually from about 20 ° C to 120 ° C.

The corresponding ketone intermediates are prepared, for example, by methods described in the literature (e.g., standard chemistry textbooks, e.g., J. March, Advanced Organic Chemistry, 4th Ed., Wiley Interscience, 1992). In addition, the continuous Friedel-Crafts reaction can be effectively used to synthesize intermediates. These reactions are well known to those skilled in the art.

Another convenient synthesis of hydrazine is the nitrosation of "active" methylene groups with nitrous acid or alkyl nitrite. Basic conditions (as described, for example, in Organic Syntheses coll., Volume VI (J. Wiley & Sons, New York, 1988), pages 199 and 840) and acidic conditions (eg, for example, Organic Synthesis coll. V, pages 32 and 373, coll. Volume III, pages 191 and 513, coll. Volume II, pages 202, 204 and 363) A ruthenium used as a starting material in the present invention is prepared. Nitrous acid is generally produced from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.

Another embodiment of the invention is a free (1A) hydrazine compound

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl,

COR ₁₆ , OR ₁₇ , halogen, NO ₂ or a group represented by the formula (3),

Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently

Substituted C ₂ -C ₁₀ alkenyl;

Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently a group represented by the formula (5) ,

But the conditions are R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇

Or at least one of R ₇ and R ₈ is a group represented by the formula (5),

Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other

COR ₁₆ or NO ₂ ;

Y represents O, S, NR ₂₆ or a direct bond;

p represents an integer of 0, 1, 2 or 3;

q represents an integer of 1, 2 or 3;

X represents CO or a direct bond;

R ₁₃ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ or a group represented by the formula (6),

Or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

COR _16, CN, NO _2, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, interrupted by one or more O, S, CO or NR C ₂₆ of ₂ -C ₂₀ alkyl; or each warp C ₃ -C ₁₀ cycloalkyl, or interrupted by one or more O, S, CO or NR C ₃ ₂₆ -C ₁₀ cyclic group is unsubstituted;

k represents an integer from 1 to 10;

Or R ₁₅ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl, which has no or hetero or one or more O, CO or NR ₂₆ ;

Or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ Heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , benzene base,

Or a group represented by the formula (6);

Or R ₁₅ represents a C ₂ -C ₂₀ alkanoyl or benzoyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ Or NR ₁₉ R ₂₀ ;

Or R ₁₅ represents a naphthoyl group or a C ₃ -C ₁₄ heteroarylcarbonyl group which is unsubstituted or substituted with one or more OR ₁₇ ;

m represents 1 or 2;

R' ₁₅ has one of the meanings given for R ₁₅ ;

X ₁ represents O, S, SO or SO ₂ ;

X ₂ represents O, CO, S or a direct bond;

n represents 1 to 20;

Or R ₁₇ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ Alkyl) ₂ , diphenyl-amino group or

Or R ₁₇ forms a bond to have a group thereon,

a direct bond of one of the carbon atoms of the phenyl or naphthyl ring;

Or R ₁₈ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C _4- haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N (C ₁ -C ₈ alkyl) ₂ or

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR ₁₇ and which is either 5- or 6-membered saturated or unsaturated The ring is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO) R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl,

Or a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₁₇ ;

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ ,

Halogen, NO ₂ , CN, phenyl or a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₁₇ without impurity or interstitial;

R ₂₃ represents hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, intervening one or more O, CO or NR ₂₆ C ₂ -C ₂₀ alkyl, uninter or hetero-O a C ₃ -C ₂₀ cycloalkyl group of S, CO or NR ₂₆ ;

Or R ₂₃ represents phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ;

R ₂₆ represents hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl with one or more O or CO in between; or phenyl-C ₁ -C ₄ alkane a C ₃ -C ₈ cycloalkyl group which is undoped or heterozygous with one or more O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or one or more Substituted by the following groups: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

But the condition is that at least one group is present in the molecule

Preferred for the groups defined for the compound of formula (1A) corresponds as given for the compound of formula (1) as given above, except for each of the defined oxime ester groups (eg

Are replaced by corresponding free sulfonium groups

Each oxime ester group can exist in two configurations (Z) or (E). The isomers can be separated by conventional methods, but a mixture of isomers can also be used as, for example, a photoinitiating substance. Accordingly, the present invention is also directed to a mixture of configurational isomers of the compound of formula (1).

Preference is given to compounds of the formula (1) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are, independently of one another, hydrogen, C ₁ -C ₂₀ Alkyl group, COR ₁₆ , NO ₂ or a group represented by formula (2)

Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently a group represented by the formula (5)

However, at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ is determined by the formula (5). Represented group

X represents CO or a direct bond;

R ₁₃ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , PO(OC _k H _{2k+ 1} ) ₂ ;

Or R ₁₃ represents phenyl or naphthyl, the two unsubstituted or via one or more COR ₁₆ or

Replaced

R ₁₄ represents a C ₁ -C ₂₀ alkyl group, a phenyl group or a C ₁ -C ₈ alkoxy group;

R ₁₅ represents a phenyl group, a naphthyl group, a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , a SR ₁₈ or C ₂ -C ₂₀ alkyl group having one or more O or S hetero; or each substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group being unsubstituted or Substituted by one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl , C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ;

Or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl , NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ;

R' ₁₄ has one of the meanings given for R ₁₄ ;

R' ₁₅ has one of the meanings given for R ₁₅ ;

R ₁₆ represents a phenyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a C ₂ -C ₂₀ alkane having one or more O, S or NR ₂₆ base,

Or R ₁₆ represents a phenyl group which -C ₂₀ alkyl substituted by one or more C _1, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following radicals: halogen, COOR _17, CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₆ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted by a halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO) O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl) or (CO)O(C ₁ -C ₄ alkyl);

R ₁₇ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O (C ₁ -C ₄ alkyl), (CO) O (C 1 -C 4 alkyl), C ₃ -C ₂₀ cycloalkyl interrupted by one or more O or a C ₃ -C ₂₀ cycloalkyl;

Or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, in which one or more O;

R ₁₈ represents a methyl group substituted with (CO)OR ₁₇ ;

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or

Substituting; however, the condition is that at least one group represented by the formula (2) or a group represented by the formula (7) is present in the molecule,

It is necessary to pay attention to the compound of the formula (1) as defined above, wherein R ₁ , R ₂ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, COR ₁₆ NO ₂ or a group represented by the formula (2) group,

R ₃ and R ₄ together are a group represented by the formula (5)

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ represent hydrogen

X represents a direct key;

R ₁₃ represents a C ₁ -C ₂₀ alkyl group;

R ₁₄ represents a C ₁ -C ₂₀ alkyl group;

R ₁₅ represents a C ₁ -C ₂₀ alkyl group or a phenyl group which is substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl groups;

R ₁₆ represents a phenyl group which is substituted with one or more C ₁ -C ₂₀ alkyl groups or OR ₁₇ ;

R ₁₇ represents an unsubstituted or substituted by one or more halogen C ₁ -C ₂₀ alkyl interrupted by one or more O or a C ₂ -C ₂₀ alkyl group.

Provided that at least one group represented by formula (2) is present in the molecule

A further object of the invention is a compound of formula (1) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen,

Or R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ are each independently a group represented by the formula (5),

However, the condition is that at least one of R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ is a group represented by the formula (5),

Or R ₂ is a group represented by the formula (2), COR ₁₆ , NO ₂ or a group represented by the formula (3),

Or R ₇ is a group represented by COR ₁₆ or formula (2),

R ₉ , R ₁₁ and R ₁₂ represent hydrogen;

R ₁₀ represents hydrogen, OR ₁₇ or COR ₁₆ ;

X represents CO or a direct bond;

Or R ₁₃ represents a C ₂ -C ₂₀ alkyl group, in which one or more O;

Or R ₁₃ represents a phenyl group;

k represents an integer of 2;

R ₁₄ represents a C ₁ -C ₂₀ alkyl group or a thienyl group;

Or R ₁₅ represents a thiophene group, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following _{_{groups: OR 17, SR 18, C}} 3 -C 8 Cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ;

R ₁₆ represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ represents thienyl ;

R ₁₇ represents hydrogen, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or has one or more of the following groups: halogen, O(CO)-(C ₁ -C ₄ alkyl Or O(CO)-(C ₂ -C ₄ )alkenyl or a C ₃ -C ₂₀ cycloalkyl group having one or more O;

Or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, in which one or more O;

R ₁₈ represents C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl, unsubstituted or via one or more OH, O(CO)-(C ₂ -C ₄ )alkenyl or (CO) Replaced by OR ₁₇ ;

However, the condition is that at least one group represented by the formula (2) is present in the molecule.

An example of a compound of the invention is a compound of formula (Ia)-(Ig) as defined above. Compounds of formula (Ia), (Ib), (Ic), especially formula (Ia) or (Ic), or formula (Ia), (Ic) or (Id), especially formula (Ia) are of interest.

For example, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, COR ₁₆ , a group represented by formula (2), or R ₁ And R ₂ , R ₂ and R ₃ , R ₃ and R ₄ or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ are each independently a group represented by the formula (5),

For example, R ₃ and R ₄ or R ₁ and R ₂ together are a group represented by the formula (5),

Or R ₃ and R ₄ and R ₅ and R ₆ together are a group represented by the formula (5),

R ₃ and R _{4 are in} particular a group represented by the formula (5),

For example, R ₁ , R ₅ , R ₆ and R ₈ represent hydrogen.

R _{7 is} especially a group represented by hydrogen COR ₁₆ or formula (2),

Or R ₇ is a group represented by COR ₁₆ or formula (2), particularly a group represented by formula (2),

R _{2 is} especially a group represented by COR ₁₆ , formula (2) or a group represented by formula (3),

Or R ₂ together with R ₁ is a group represented by the formula (5). R _{2 is} especially COR ₁₆ .

X is preferably a direct bond.

For example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ wherein the substituent OR ₁₇ SR ₁₈ or NR ₁₉ R ₂₀ optionally via a group R _17, R _18, R ₁₉ and / or R ₂₀ and one carbon atom naphthyl ring form a 5-membered or 6-membered ring; or R _9, R _10, R ₁₁ And R ₁₂ are each independently a group represented by COR ₁₆ or formula (2).

Specifically, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ or formula (2).

For example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or substituted by one or more C ₁ -C ₆ alkyl groups. Phenyl group; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ or formula (2),

In another embodiment, for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or one or more of the following groups a substituted phenyl group: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ Wherein the substituent OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring with one carbon atom of the naphthyl ring via the radicals R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ .

Further, for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or COR ₁₆ .

Or by way of example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , COR ₁₆ or NR ₁₉ R ₂₀ .

Preferably, R ₉ , R ₁₁ and R ₁₂ represent hydrogen and R ₁₀ represents hydrogen, OR ₁₇ or COR ₁₆ .

R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ or CONR ₁₉ R ₂₀ ; or R ₁₃ represents C ₂ -C ₂₀ alkyl In between, one or more of O, S, SO, SO2, NR ₂₆ or CO, or a C ₂ -C ₁₂ alkenyl group, optionally having one or more O, CO or NR ₂₆ or R ₁₃ representing C ₃ -C ₁₀ cycloalkyl, which is optionally interrupted by one or more _{O, S, CO, NR 26} , or R ₁₃ represents a phenyl or naphthyl group, which is unsubstituted or substituted with one two or more of the following groups Substitution: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, with one or more Or O, or a group represented by the formula (7),

Or a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k +1} ) ₂ ; or a C ₂ -C ₂₀ alkyl group in which one or more O are heterogeneous.

Further, R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; or a C ₂ -C ₂₀ alkyl group in which one or more O is hetero; or a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₁₀ cycloalkyl group; or R ₁₃ represents a phenyl or naphthyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , NO ₂ , halogen, C ₁ -C ₂₀ alkane a C ₁ -C ₄ haloalkyl group, a C ₂ -C ₂₀ alkyl group, having one or more O or a group represented by the formula (7)

In another embodiment, R ₁₃ represents, for example, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following: halo, R ₁₇ , OR ₁₇ , SR ₁₈ or PO (OC _k H _2k+1 ) ₂ ; or a C ₂ -C ₂₀ alkyl group in which one or more O is hetero; or a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₁₀ cycloalkyl group, a phenyl group or a naphthyl group; .

Or R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H _2k+1 ) ₂ ; or a C ₂ -C ₂₀ alkyl group having one or more O; or a phenyl group, a C ₂ -C ₁₂ alkenyl group or a C ₃ -C ₁₀ cycloalkyl group.

Or R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group, a phenyl group, a C ₂ -C ₁₂ alkenyl group or a C ₃ -C ₁₀ cycloalkyl group.

Or R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₁₂ alkenyl group or a C ₃ -C ₁₀ cycloalkyl group.

Preferably, R ₁₃ represents a C ₁ -C ₂₀ alkyl group, especially a C ₁ -C ₈ alkyl group, such as 2-ethylhexyl.

R ₁₄ represents, for example, hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, which is unsubstituted or subjected to one or Substituted by a plurality of halogens or phenyl groups; or R ₁₄ represents a phenyl or naphthyl group, which are unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl , halogen, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; or R ₁₄ represents a C ₃ -C ₅ heteroaryl group, for example a thienyl group, or a C ₁ -C ₈ alkoxy group, a benzyloxy group or a phenoxy group base.

Or R ₁₄ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more halogen or phenyl groups; or R ₁₄ represents a C ₃ -C ₅ heteroaryl group (e.g., thienyl) or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; R ₁₄ represents a C ₁ -C ₈ alkoxy group, a benzyloxy group or a phenoxy group.

In another embodiment, R ₁₄ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with phenyl; or R ₁₄ represents phenyl, which is unsubstituted or via one or more C ₁ -C ₆ Alkyl substitution.

Preferably, R ₁₄ represents C ₁ -C ₂₀ alkyl, C ₃ -C ₅ heteroaryl (such as thienyl), or phenyl, especially C ₁ -C ₂₀ alkyl or thienyl, especially C _1- C ₈ alkyl.

R ₁₅ represents, for example, a C ₆ -C ₂₀ aryl group or a C ₅ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkane a group, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , C ₁ -C ₂₀ alkyl; or R ₁₅ represents hydrogen, C ₃ -C ₈ cycloalkyl, the C ₃ -C ₈ cycloalkyl Depending on the case, one or more O, CO or NR ₂₆ ; or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , C ₃ -C ₈ -cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₈ -C ₂₀ phenoxycarbonyl, C ₅ -C ₂₀ heteroaryloxy-carbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _2k+1 ) ₂ , a group represented by the formula (6), a phenyl group, or a phenyl group substituted by a halogen group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group , OR ₁₇ or NR ₁₉ R ₂₀ ;

Or R ₁₅ represents a C ₂ -C ₂₀ alkyl group in which one or more O, S or SO ₂ are heterogeneous, or R ₁₅ represents a C ₂ -C ₂₀ alkanoyl group, a benzoyl group, a C ₂ -C ₁₂ alkoxycarbonyl group. , phenoxycarbonyl, CONR ₁₉ R ₂₀ , NO ₂ or C ₁ -C ₄ haloalkyl.

Further, R ₁₅ represents, for example, hydrogen, C ₆ -C ₂₀ aryl, especially phenyl or naphthyl, each unsubstituted or substituted by C ₁ -C ₁₂ alkyl; or C ₃ -C ₅ hetero An aryl group, such as a thienyl group; or a C ₃ -C ₈ cycloalkyl group, a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₇ , C ₃ - C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ represents C ₂ -C ₂₀ alkyl with one or more O or SO ₂ heteromixed therebetween.

Compounds of formula (1) are of interest, wherein R ₁₅ represents, for example, hydrogen, phenyl, naphthyl, each unsubstituted or substituted by C ₁ -C ₈ alkyl; or R ₁₅ represents thienyl, C ₁ - a C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₇ , C ₃ -C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ represents C ₂ a -C ₂₀ alkyl group in which one or more O or SO ₂ are heterogeneous.

R _{15 is} especially, for example, C ₃ -C ₈ cycloalkyl or C ₁ -C ₂₀ alkyl, especially C ₁ -C ₂₀ alkyl, especially C ₁ -C ₁₂ alkyl.

Preferred of R' ₁₄ and R' ₁₅ are as given above for R ₁₄ and R ₁₅ respectively.

X ₁ represents, for example, O, S or SO, such as O or S, especially O.

R ₁₆ represents, for example, a C ₆ -C ₂₀ aryl group (especially phenyl or naphthyl, especially phenyl) or a C ₅ -C ₂₀ heteroaryl (especially thienyl), each unsubstituted or via one or more Substituted for: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a C ₁ -C ₂₀ alkyl group having one or more O; or each with one or more C ₁ -C ₂₀ substituted alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following radicals: _{_{_{halogen, COOR 17, CONR 19 R 20}}} , benzyl , C ₃ -C ₈ cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₅ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R _20; or R ₁₆ represents hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl, (CO) OH or (CO)O(C ₁ -C ₄ alkyl); or R ₁₆ represents a C ₂ -C ₁₂ alkyl group with one or more O in between; or (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C _3- C ₈ cycloalkyl, and n is from 1 to 20, for example from 1 to 12 or from 1 to 8, especially 1 or 2.

Furthermore, R ₁₆ represents, for example, phenyl or naphthyl, especially phenyl, thienyl or oxazole, each unsubstituted or substituted by one or more of the following groups: phenyl, halogen, C ₁ -C _{a 4-} haloalkyl group, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: Halogen, phenyl, OH, SH, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl) , O(CO)-phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkyl); or R ₁₆ represents a C ₂ -C ₁₂ alkyl group, wherein one or more O are heterogeneous; (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl And n is from 1 to 20, such as from 1 to 12 or from 1 to 8, especially 1 or 2.

Further, R ₁₆ represents, for example, phenyl or naphthyl, especially phenyl, each unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ represents a C ₃ -C ₅ heteroaryl group, especially a thienyl group.

R _{16 is} especially, for example, phenyl which is unsubstituted or substituted by one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl, or R ₁₆ represents thienyl .

Preferably, R ₁₆ represents, for example, phenyl or naphthyl, each of which is unsubstituted or substituted with one or more C ₁ -C ₂₀ alkyl groups.

R _{16 is} especially phenyl which is substituted by one or more C ₁ -C ₂₀ alkyl groups.

R ₁₇ represents, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-benzene group, (CO) OH, (CO ) O (C 1 -C 4 alkyl), C ₃ -C ₂₀ cycloalkyl interrupted by one or more O or a C ₃ -C ₂₀ cycloalkyl; or R ₁₇ represents a C ₂ -C ₂₀ alkyl group having one or more O in between; (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl) a C ₁ -C ₈ alkanoyl group, a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₆ enoyl group or a C ₃ -C ₂₀ cycloalkyl group, optionally having one or more O; or R ₁₇ representing a benzene group An acyl group which is unsubstituted or substituted by one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy groups; or R ₁₇ represents phenyl, naphthyl or C ₅ -C ₂₀ Aryl groups each substituted or substituted with one or more of the following groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) _2, diphenyl - group, or of formula (7) table Group

In another embodiment, R ₁₇ represents, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following: halogen , O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or a C ₂ -C ₂₀ alkyl group having one or more O; or C ₁ a C ₈ alkanoyl group, a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₆ alkenoyl group, a C ₂ -C ₂₀ alkyl group having one or more O interstitials, and optionally a C ₃ -C having one or more O _{a 20} cycloalkyl group; or a benzoyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or benzene Or a naphthyl group, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy.

R _{17 is} also, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups : halogen, C ₃ -C ₂₀ cycloalkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or inter-hetero C with one or more O ₂ -C ₂₀ alkyl group, or R ₁₇ represents C ₂ -C ₂₀ alkyl, heteroalkyl having one or more therebetween O.

R _{17 is} especially hydrogen, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by one or more of the following groups: O(CO)-(C ₁ -C ₄ alkyl , O(CO)-(C ₂ -C ₄ alkenyl) or a C ₂ -C ₂₀ alkyl group having one or more O, or R ₁₇ representing a C ₂ -C ₂₀ alkyl group, one or more O.

R ₁₈ represents, for example, a C ₃ -C ₂₀ cycloalkyl group which has no or a hetero or one or more O; or R ₁₈ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or one or more of the following Group substitution: OH, O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ ; or R ₁₈ represents C ₂ -C _{a 20} alkyl group having one or more of O, S, CO, NR ₂₆ or COOR _{17 in between} ; or R ₁₈ represents a C ₂ -C ₈ alkanoyl group or a C ₃ -C ₆ alkenoyl group, a benzoyl group; or R ₁₈ represents Phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted by one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₁₂ alkoxy or NO ₂ .

In another embodiment, R ₁₈ represents, for example, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: OH, O (CO )-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ ; or R ₁₈ represents phenyl or naphthyl, each unsubstituted or via One or more halogen or C ₁ -C ₁₂ alkyl groups, especially halogen.

R ₁₈ represents, for example, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₂₀ cycloalkyl group, a phenyl-C ₁ -C ₃ alkyl group, a C ₂ -C ₈ alkanoyl group, Benzoyl, phenyl or naphthyl.

For example, R ₁₈ represents C ₁ -C ₂₀ alkyl substituted with one or more of the following groups: OH, O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ , or R ₁₈ represents a phenyl group which is substituted by one or more halogens.

Preferably, R ₁₈ represents C ₁ -C ₈ alkyl, which is substituted as defined above.

For example, R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkane a phenyl or naphthyl group, a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkanoyloxy group, a C ₃ -C ₁₂ alkenoyl group or a benzoyl group; or R ₁₉ and R ₂₀ attached thereto The atoms together form a 5- or 6-membered saturated or unsaturated ring heterogeneously interspersed with O, S or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, the ring system is not Substituted or substituted with one or more of the following groups: a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group, or a group represented by the formula (7),

Further, for example, R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C _{a 3-} alkyl group, a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkanoyloxy group, a C ₃ -C ₁₂ alkenoyl group or a benzoyl group; or R ₁₉ and R ₂₀ together with the N atom to which they are attached In the case of a 5- or 6-membered saturated ring of O or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form an indazole ring.

For example, R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkane a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkanoyloxy group, a C ₃ -C ₁₂ alkenoyl group or a benzoyl group; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heterogeneous There is a 5- or 6-membered saturated ring of O or NR ₁₇ .

Preferably, R ₁₉ and R ₂₀ are, independently of each other, a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkanoyloxy group; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a morpholine ring.

For example, R ₂₁ and R ₂₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ₂₁ and R ₂₂ The attached N atoms together form a morpholine ring. R ₂₁ and R _{22 are, in} particular, independently of one another hydrogen or C ₁ -C ₂₀ alkyl.

R ₂₃ represents, for example, hydrogen, OH, phenyl or C ₁ -C ₂₀ alkyl. R _{23 is} especially hydrogen, OH or C ₁ -C ₄ alkyl.

R ₂₄ is preferably as given for R ₁₉ and R ₂₀ . R ₂₅ is preferably as given for R ₁₇ .

R ₂₆ represents, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, heterogeneously having one or more O or CO; or phenyl-C ₁ - a C ₄ alkyl group, a C ₃ -C ₈ cycloalkyl group optionally having one or more O or CO; or (CO)R ₁₉ or a phenyl group which is unsubstituted or has one or more of the following groups Substitution: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ .

Or R ₂₆ represents, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl; phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl, (CO)R ₁₉ or a phenyl group which is unsubstituted or substituted by one or more C ₁ -C ₂₀ alkyl groups. Further, R ₂₆ represents, for example, hydrogen or a C ₁ -C ₂₀ alkyl group, especially a C ₁ -C ₄ alkyl group.

Examples of the compound of the formula (1) of the invention include the following compounds represented by the formula (1-1) to the formula (1-84):

The photoinitiator (C-1) is used in an amount of 5 parts by weight to 100 parts by weight, preferably 10 parts by weight to 90 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), more preferably It is from 15 parts by weight to 80 parts by weight.

When the photosensitive resin composition does not use the photoinitiator (C-1), the pattern smoothness of the photosensitive resin composition is not good.

When the photoinitiator (C-1) is used in an amount of from 5 parts by weight to 100 parts by weight, the high-definition pattern linearity of the obtained photosensitive resin composition is preferable.

Other photoinitiators (C-2)

Specific examples of the other photoinitiator (C-2) include other oxy-acyl steroids (O-acyloxime) or non-oxy-acyl hydrazine-based photoinitiators.

Other oxy-acyl hydrazines

Specific examples of other oxy-acyl hydrazine compounds include 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzoyl group).肟), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoylhydrazine), 1-[4-(phenylthio)phenyl ]-octane-1,2-dione-2-(O-benzoylhydrazine), or a combination of the above compounds. 1-[4-(Phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime) may be manufactured by Ciba Specialty Chemicals Co., Ltd. The model number is IRGACURE OXE-01.

Further, specific examples of other oxy-acyl hydrazine compounds include 1-[4-(benzoyl)phenyl]-heptane-1,2-dione-2-(O-benzoyl hydrazine), 1-[9 -ethyl-6-(2-methylbenzoyl)-9H-indazole-3-substituted]-ethanone-1-(O-acetyl oxime), 1-[9-ethyl-6- (3-methylbenzoyl)-9H-indazole-3-substituted]-ethanone-1-(O-acetylindole), 1-[9-ethyl-6-benzoyl-9H-indole Zyrid-3-yl]-ethane ketone-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)- 9H-carbazole-3-substituted]-1-(O-acetylindole), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl) )-9H-carbazole-3-substituted]-1-(O-acetyl hydrazine), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazole-3-substituted]-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzene) Acyl)-9H-carbazole-3-substituent]-1-(O-acetylhydrazine), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl)-9H-carbazole-3-Substituent]-1-(O-acetylhydrazine), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-4-tetrahydro) Pyranylmethoxybenzoyl)-9H-carbazole-3-take代基]-1-(O-acetyl hydrazine), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoyl)-9H-carbazole- 3-Substituent]-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)- 9H-carbazole-3-substituted]-1-(O-acetyl hydrazine), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl -1,3-dioxolanyl)benzoyl}-9H-indazole-3-substituted]-1-(O-acetylhydrazine), ethane ketone-1-[9-ethyl- 6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-indazole-3-substituted]-1- (O-acetyl hydrazine), or a combination of the above compounds. 1-[9-ethyl-6-(2-methylbenzoyl)-9H-indazole-3-substituted]-ethanone-1-(O-acetylhydrazine) can be refined by Ciba Made by the company, the model is IRGACURE OXE-02.

Other oxy-acyl hydrazine compounds may be used singly or in combination of two or more.

Non-oxy-acyl hydrazine photoinitiator

Specific examples of the non-oxy-acyl hydrazine photoinitiator include a triazabenzene compound, an acetophenone compound, a diimidazole compound, a benzophenone compound, an α-diketone compound, and an alcohol ketone. A compound, an alcohol ketone ether compound, an acylphosphine oxide compound, an anthraquinone compound, a halogen-containing compound, a peroxide, or a combination of the above compounds.

Specific examples of the triazabenzene compound include a vinyl-halomethyl-s-triazabenzene compound, 2-(naphtho-1-substituted)-4,6-di(halomethyl)- An s-triazabenzene compound, a 4-(p-aminophenyl)-2,6-di(halomethyl)-s-triazabenzene compound, or a combination of the above compounds.

Specific examples of the vinyl-halogenomethyl-s-triazabenzene compound include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, 2 ,4-di(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloromethyl- 3-Amino-6-p-methoxystyryl-s-triazabenzene, or a combination of the above compounds.

Specific examples of the 2-(naphtho-1-substituted)-4,6-di(halomethyl)-s-triazabenzene compound include 2-(naphtho-1-substituted)-4,6 - bis(trichloromethyl)-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-di(trichloromethyl)-s-triazole Heterobenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4-butoxy-naphthalene And-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-yl] -4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphthyl-1-substituted]-4,6-di ( Trichloromethyl)-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphthyl-1-substituted]-4,6-di(trichloromethyl)-s -Triazabenzene, 2-(2-methoxy-naphtho-1-substituted)-4,6-di(trichloromethyl)-s-triazabenzene, 2-(6-methoxy 5-methyl-naphtho-2-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(6-methoxy-naphtho-2-substituted -4,6-bis(trichloromethyl)-s-triazabenzene, 2-(5-methoxy-naphtho-1-substituted)-4,6-di(trichloromethyl) )-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-di(trichloromethyl)-s-triaza Benzene, 2-(6-ethoxy-naphtho-2-substituted)-4,6-di(trichloromethyl)-s-triazabenzene, 2-(4,5-dimethoxy -naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, or a combination of the above compounds.

Specific examples of the 4-(p-aminophenyl)-2,6-bis(halomethyl)-s-triazabenzene compound include 4-[p-N,N-di(ethoxycarbonyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(ethoxycarbonylmethyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6- Bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethane) -s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p- N-ethoxycarbonylmethylaminophenyl)-2,6-di (trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(phenyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole Heterobenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-[p-N-(p-a) Oxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-N,N-bis(ethoxycarbonylmethyl)amine Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6- Bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(three Chloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2,6-di(trichloromethyl) -s-triazabenzene, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s- Triazabenzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6 -bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethane) -s-triazabenzene, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-three Azabenzene, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4- [m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-pair -N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxyl) Carbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(three Chloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-three Azabenzene, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(ortho -fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-three Azabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro- p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl) -2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethane) -s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4 -(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 2,4-di(trichloromethyl)- 6-[3-Bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene, or a combination of the above compounds. The triazabenzene compounds may be used singly or in combination of two or more.

The triazabenzene compound preferably includes 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)amino group. Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazole A heterobenzene, or a combination of the above compounds.

Specific examples of the acetophenone compound include p-dimethylacetonone, α,α'-dimethoxy oxy acetophenone, and 2,2'-dimethyl-2-phenylbenzene. Ethyl ketone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, or a combination of the above compounds.

The acetophenone compounds may be used singly or in combination of two or more.

2-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone may be a product of the model IRGACURE 907 manufactured by Ciba Specialty Chemicals Co., Ltd. 2-Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone is commercially available from Ciba Specialty Chemicals, Inc. under the model number IRGACURE 369.

The acetophenone-based compound preferably includes 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-di Methylamine-1-(4-morpholinophenyl)-1-butanone, or a combination of the above compounds.

Specific examples of the diimidazole compound include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2 , 2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4' , 5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-double (2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4 , 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, or the above A combination of compounds.

The diimidazole compounds may be used singly or in combination of two or more.

The diimidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

Specific examples of the benzophenone compound include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamine) II. Benzophenone, 4,4'-bis(diethylamine)benzophenone, or a combination of the above compounds. The benzophenone compounds can be used singly or in combination. The benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone.

Specific examples of the α-diketone compound include benzil, diacetyl, or a combination of the above compounds. The α-diketone compounds may be used singly or in combination of two or more.

Specific examples of the ketol compound include benzoin. The ketol compounds may be used singly or in combination of two or more.

Specific examples of the ketol ether compound include benzophenone methyl ether, benzophenone ether, and diphenyl. Ethanol ketone isopropyl ether, or a combination of the above compounds. The ketol ether compounds may be used singly or in combination of two or more.

Specific examples of the phosphinyl oxide-based compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl A phenylphosphine oxide, or a combination of the above compounds. The acylphosphine oxide compounds may be used singly or in combination of two or more.

Specific examples of the quinone compound include hydrazine, 1,4-naphthoquinone, or a combination of the above compounds. The terpenoids may be used singly or in combination of two or more.

Specific examples of the halogen-containing compound include benzoyl chloride, tribromomethylphenylsulfone, tris(trichloromethyl)-s-triazabenzene, or a combination of the above compounds. The halogen-containing compound may be used singly or in combination of two or more.

Specific examples of the peroxide include di-tert-butyl peroxide and the like. The peroxides may be used singly or in combination of two or more.

The other photoinitiator (C-2) is used in an amount of from 0 part by weight to 95 parts by weight, preferably from 0 part by weight to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), more preferably It is preferably from 0 part by weight to 65 parts by weight.

Further, the photoinitiator (C) is used in an amount of 10 to 100 parts by weight, preferably 15 parts by weight to 90 parts by weight, more preferably 20 based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight to 80 parts by weight.

Solvent (D):

The organic solvent (D) of the present invention is required to dissolve the alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, and the photoinitiator (C), and does not react with the components and has appropriate Volatile.

In a specific embodiment of the present invention, the organic solvent (D) is ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, three Glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol (poly)alkylene glycol monoalkyl ethers such as methyl ether and tripropylene glycol ethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, etc. Poly)alkylene glycol monoalkyl ether acetate; diglyme, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; Ketones such as alkyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropane Methyl ester, ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-B Ethyl oxypropionate (EEP), ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate , 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate , n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate , other esters such as ethyl acetoacetate and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N a solvent such as a carboxylic acid amide such as dimethylacetamide. Preferably, the solvent is selected from the group consisting of propylene glycol methyl ether acetate and 3-ethyl b. Acid ethyl ester, and the mixed solvent may be used alone or plural kinds thereof.

The organic solvent (D) is used in an amount of 500 parts by weight to 5000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably 800 parts by weight to 4,500 parts by weight; more preferably 1,000 to 4,000 parts by weight Parts by weight.

Pigment (E):

The pigment (E) may be an inorganic pigment, an organic pigment or a combination of these.

Specific examples of the above inorganic pigment include barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide red [red iron oxide (III)], cadmium red, ultramarine blue, iron ferricyanide, chromium oxide green, cobalt. Metal oxide powder such as green, amber, titanium black, synthetic iron black, titanium dioxide or triiron tetroxide, metal sulfide powder or metal powder.

Specific examples of the above organic pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 41, 47, 48, 48:1, 48:2, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, Red pigment of 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 or a compound represented by formula (e-1); CI Pigment Yellow 1 , 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37 , 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97 , 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 129, 133, 134, 136, 138, 139, 142, 147, 148 , 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180 , 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206 207 or Yellow pigment of 208 et al; CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61 , orange pigment of 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79; CI pigment violet 1, 14, 19, 23, 29, 32, Purple pigments of 33, 36, 37, 38, 39, 40, 50, etc.; CI pigment blue l, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6 , blue pigments of 16, 21, 22, 60, 61, 64, 66, etc.; green pigments of CI pigment green 7, 36, 37, 42, 58, etc.; brown pigments of CI pigment brown 23, 25, 28; And black pigments such as CI Pigment Black l, 7. The organic pigments may be used singly or in combination of plural kinds.

The compound represented by the formula (e-1) is a brominated diketopyrrolopyrrole pigment which can be passed through a known patent. The synthesis method disclosed in the publication (Publication No. WO 2009/144115) is produced.

The above synthesis method is, for example, a method for synthesizing a brominated diketopyrrolopyrrole pigment using a succinic acid diester as a raw material. Specifically, 2 moles of 4-bromobenzonitrile and 1 mole of succinic acid diester are added to an inert organic solvent (for example, tert-amylalcohol). Next, a condensation reaction is carried out in the presence of an alkali metal or an alkali metal alkoxide and at a high temperature of from 80 ° C to 110 ° C to form an alkali metal salt of a brominated diketopyrrolopyrrole compound. Then, an alkali metal salt of a brominated diketopyrrolopyrrole compound is protonated using water, an alcohol or an acid or the like to obtain a brominated diketopyrrolopyrrole pigment. At the stage of protonation, the size of the primary particle size can be controlled by the temperature of protonation, the water used, the ratio of alcohol to acid, and the amount of addition thereof. The above synthesis method is merely illustrative, and the synthesis method of the brominated diketopyrrolopyrrole pigment is not limited thereto.

The pigment (E) may be used in an amount of 30 parts by weight to 300 parts by weight, preferably 40 parts by weight to 250 parts by weight, and more preferably 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Up to 200 parts by weight.

Dye (F)

The dye (F) includes the dye (F-1) as well as other dyes (F-2).

Dye (F-1)

The dye (F-1) includes a compound represented by the formula (f-1).

In the formula (f-1), J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number. a cycloalkyl group of 3 to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and J ⁵ and J ⁶ each independently represent a hydrogen atom and have a carbon number of 1 to 8. An alkyl group or a chlorine atom; J ⁷ represents a group having a polymerizable unsaturated group; and a represents an integer of 1 to 5.

Specific examples of the alkyl group having 1 to 8 carbon atoms in J ¹ , J ² , J ³ and J ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group and a third butyl group. Base, isobutyl, pentyl, third amyl, hexyl, heptyl, octyl, isooctyl, trioctyl or 2-ethylhexyl, and the like. J ¹ , J ² , J ³ and J ^{4 are} preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the cycloalkyl group having 3 to 8 carbon atoms in J ¹ , J ² , J ³ and J ⁴ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. J ¹ , J ² , J ³ and J ^{4 are} preferably a cycloalkyl group having a carbon number of 5 to 7, and more preferably a cyclohexyl group.

The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, and the phenyl group in J ¹ , J ² , J ³ and J ⁴ may have a substituent, and the substituent is preferably a halogen atom. -J ^a , -OH, -OJ ^a , -SO ₃ H, -SO ₃ T, -CO ₂ H, -CO ₂ J ^a , -SO ₃ J ^a , -SO ₂ NHJ ^b , -SO- ₂ NJ ^b J ^c or -SO ₃ ^- .

Here, J ^a represents a saturated hydrocarbon group having ^a carbon number of 1 to 10. Here, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom, a carbonyl group or -NJ ^a -.

J ^b and J ^c each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having a carbon number of 3 to 30 (preferably 3 to 8) or -D, or A heterocyclic group having 2 to 10 carbon atoms formed by bonding J ^b and J ^{c to} each other. Wherein the hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted by a hydroxyl group, a halogen atom, -D, -CH=CH ₂ or -CH=CHJ ^a , and the methylene group contained in the alkyl group and the cycloalkyl group The group may be substituted with an oxygen atom, a carbonyl group or -NJ ^a -, and the hydrogen atom contained in the heterocyclic group may be substituted with -J ^a , -OH or -D.

T represents a sodium atom or a potassium atom.

D represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. Here, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted with -OH, -J ^a , -OJ ^a , -NO ₂ , -CH=CH ₂ , -CH=CHJ ^a or a halogen atom.

The saturated hydrocarbon group in J ^a may be any of a linear chain, a branched chain, and a cyclic chain as long as the carbon number is from 1 to 10, and may have a bridged structure. Specifically, in addition to the alkyl group similar to the above J ¹ , J ² , J ³ and J ⁴ , specific examples of R ^a may further include an anthracenyl group, a fluorenyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, Cyclooctyl or tricyclic fluorenyl. Further, specific examples of the group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group or a methoxyhexyl group.

Further, specific examples of the alkyl group, the cycloalkyl group and the substituent of the phenyl group -CO ₂ R ^a in J ¹ , J ² , J ³ and J ⁴ include a methyloxycarbonyl group, an ethyloxycarbonyl group, and a methyloxycarbonyl group. Propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, cyclohexyloxycarbonyl or methoxy propyloxycarbonyl. Further, specific examples of -SO ₃ J ^a include a methanesulfonyl group, a ethanesulfonyl group, a hexanesulfonyl group or a decanesulfonyl group.

Specific examples of the heterocyclic group in which J ^b and J ^c are bonded to each other include pyrrole, pyridine, indole, isoindole, quinoline, isoquinoline. (isoquinoline), carbazole, phenanthridine, acridine or phenothiazine.

Specific examples of the aromatic hydrocarbon group in D include a phenyl group, a naphthyl group, an azulenyl group, and the like. Further, specific examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyridyl group, a pyrrolyl group, an oxazolyl group, and an isoxazole. An isothiazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group or a pyrimidyl group.

Specific examples of the alkyl group having 1 to 8 carbon atoms in J ⁵ and J ⁶ are the same as the specific examples of the alkyl group having 1 to 8 carbon atoms in J ¹ , J ² , J ³ and J ⁴ , and Will be described separately.

a represents an integer of 1 to 5, and when a is an integer of 2 or more, a plurality of J ⁷ may be the same or different, and a is preferably 1 or 2, more preferably 1.

The compound represented by the formula (f-1) preferably includes the compound represented by the formula (f-2). Further, the compound represented by the formula (f-2) is preferably a compound in which the -COOJ ⁸ group in the formula (f-2) is substituted at the ortho position on the benzene ring.

In the formula (f-2), J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number. a cycloalkyl group of 3 to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and J ⁵ and J ⁶ each independently represent a hydrogen atom and have a carbon number of 1 to 8. An alkyl group or a chlorine atom; and J ⁸ represents a group having a polymerizable unsaturated group.

The polymerizable unsaturated group in J ⁷ and J ⁸ is preferably an acryloyl group or a methacryloyl group in view of easiness of the crosslinking reaction. Specific examples of J ⁸ are preferably a group represented by the formula (f-3) or a group represented by the formula (f-4).

An integer representing 0 to 6.

J ⁹ and J ^{10 are} preferably a methyl group.

Specific examples of the alkanediyl group having 1 to 12 carbon atoms in V ¹ , V ² , V ³ and V ⁴ include a methylene group, an ethylidene group, an ethane-1,1-diyl group, and a propane-1,1. -diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl Butane-1,4-diyl, pentane-1,2-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-1,5-diyl Hexane-1,5-diyl, hexane-1,6-diyl, octane-1,8-diyl or decane-1,10-diyl. V ¹ , V ² , V ³ and V ^{4 are} preferably an alkanediyl group having a carbon number of 2 to 8, and more preferably an alkanediyl group having a carbon number of 2 to 6.

The substituent of the alkanediyl group includes a hydroxyl group, a halogen atom, a (meth)acryloyloxy group or a phenoxy group, and the like, and is preferably a hydroxyl group.

The divalent alicyclic hydrocarbon group in Q ² is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Further, the alicyclic hydrocarbon group may be a 2 to 4 ring crosslinked cyclic hydrocarbon group.

Specifically, J ^{8 is} preferably a (meth)acryloyloxyalkyl group. Further, the (meth)acryloyloxyalkyl group has a total carbon number of preferably 4 to 16, particularly preferably 4 to 10.

b is preferably an integer representing 0 to 3, and c and d are preferably integers each independently representing 0 to 3.

The compound represented by the formula (f-1) is obtained by reacting a compound having a hydroxyl group and a polymerizable unsaturated group with a compound represented by the formula (f-5), wherein the polymerizable unsaturated group is an acryloyl group or a methyl group. Acryl. A well-known method can be used for this esterification reaction. Further, the -COOH group in the formula (f-5) is preferably substituted with an ortho position on the benzene ring.

In the formula (f-5), J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number. a cycloalkyl group of 3 to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and J ⁵ and J ⁶ each independently represent a hydrogen atom and have a carbon number of 1 to 8. An alkyl or chlorine atom; IN ^- represents an anion.

The compound having a hydroxyl group and a polymerizable unsaturated group may have one or more hydroxyl groups and a (meth)acryloyl group in the compound, and the number of bonds and bonding sites of the hydroxyl group and the (meth)acryloyl group. There are no special restrictions. Further, as the hydroxyl group, any of an alcoholic hydroxyl group and a phenolic hydroxyl group can be used. Further, when other substituents are contained in addition to the hydroxyl group and the (meth)acryloyl group, the kind, the bonding position, and the number of bonds are not limited.

A specific example of the compound having a hydroxyl group and a (meth)acryloyl group is preferably a compound represented by the formula (f-3a) or (f-4a).

In the formulas (f-3a) and (f-4a), J ⁹ , J ¹⁰ , V ¹ , V ² , V ³ , V ⁴ , Q ¹ , Q ² , b, c and d and the formula (f-3) And J ⁹ , J ¹⁰ , V ¹ , V ² , V ³ , V ⁴ , Q ¹ , Q ² , b, c, and d in (f-4) are synonymous, and are not described herein.

Specific examples of the compound having a hydroxyl group and a (meth)acryloyl group preferably include at least one of the compounds represented by the formula (f-2-1) to the formula (f-2-4).

In the formula (f-2-1), J ^d represents a hydrogen atom or a methyl group; and g F are each independently an integer of 0 to 2; H represents an integer of 1 to 6. When at least one of f and g is an integer of 1 or more, the -CH(OH)- group, the -CH(CH ₃ )- group, and the -CH ₂ - group may be bonded in an arbitrary order.

In the formula (f-2-2), J ^e represents a hydrogen atom or a methyl group; and i and j each independently represent an integer of 1 to 12.

In the formula (f-2-3), J ^f represents a hydrogen atom or a methyl group; and k and mx each independently represent an integer of 1 to 12.

In the formula (f-2-4), J ^g represents a hydrogen atom or a methyl group; and A represents a divalent group selected from the group consisting of the groups represented by the following formulas (fI) to (fIV); n and q are each independently An integer representing 0 to 6.

Specific examples of the compound represented by the formula (f-2-1) include 2-hydroxyethyl (meth)acrylate, 1-methyl-2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid 2- Methyl-2-hydroxyethyl ester, 3-hydroxypropyl (meth)acrylate, 1-glycerol (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, (meth)acrylic acid 9 - Hydroxy decyl ester, 10-hydroxydecyl (meth) acrylate, 11-hydroxyundecyl (meth) acrylate or 12-hydroxydodecyl (meth) acrylate.

Further, specific examples of the compound represented by the formula (f-2-2) include 2-(6-hydroxyhexanoyloxy)ethyl (meth)acrylate and 3-(6-hydroxyhexanoyl (meth)acrylate. Oxy)propyl ester, 4-(6-hydroxyhexanoyloxy)butyl (meth)acrylate, 5-(6-hydroxyhexanoyloxy)pentyl (meth)acrylate or (meth)acrylic acid 6 -(6-Hydroxyhexanoyloxy)hexyl ester, etc. (6-hydroxyhexanoyloxy)alkyl (meth)acrylate, etc.; (6-hydroxyhexanoyloxy)alkyl (meth)acrylate Commercial products of the class include the trade names PLACCEL FM1D, PLACCEL FM2D (above, DAICEL Chemical Industry Co., Ltd.) and the like.

Further, specific examples of the compound represented by the formula (f-2-3) include 2-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)ethyl (meth)acrylate, (methyl) ) 3-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)propyl acrylate, 4-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)(meth)acrylate Butyl ester, 5-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)pentyl (meth)acrylate or 6-(3-hydroxy-2,2-(meth)acrylate (3-hydroxy-2,2-dimethylpropoxycarbonyloxy)alkyl (meth)acrylate, etc.; dimethyl oxycarbonyl oxy) hexyl ester; (meth)acrylic acid (3) Commercial products of -hydroxy-2,2-dimethylpropoxycarbonyloxy)alkyl esters include the trade name HEMAC1 (manufactured by DAICEL Chemical Industry Co., Ltd.) and the like.

Further, specific examples of the compound represented by the formula (f-2-4) include 4-hydroxycyclohexyl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and (methyl) ) 2-[4-(2-hydroxyethyl)cyclohexyl acrylate] Ethyl ester, 3-hydroxybicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, (meth)acrylic acid (3-hydroxymethylbicyclo[2.2.1]hept-5-ene 2-yl)methyl ester, 2-[3-(2-hydroxyethyl)bicyclo[2.2.1]hept-5-en-2-yl]ethyl (meth)acrylate, (meth)acrylic acid 8 -Hydroxybicyclo[2.2.1]hept-5-en-2-yl ester, 2-hydroxy octahydro-4,7-methylene fluoren-5-yl (meth) acrylate (meth) -hydroxy octahydro-4,7-methanoindene-5-yl ester), (meth)acrylic acid (2-hydroxymethyl octahydro-4,7-methylene fluoren-5-yl)methyl ester, (methyl) 2-[2-(2-hydroxyethyl) octahydro-4,7-methylene fluoren-5-yl]ethyl acrylate, 3-hydroxyadamantan-1-yl (meth)acrylate, (A) Ethyl (3-hydroxymethyladamantan-1-yl)methyl acrylate or 2-[3-(2-hydroxyethyl)adamantan-1-yl]ethyl (meth)acrylate.

Among these compounds having a hydroxyl group and a (meth)acryloyl group, from the viewpoint of reactivity, the following compounds are preferable: f and g in the formula (f-2-1) are 0, and h is 2 a compound of 6; wherein f in the formula (f-2-1) is 1, g is 0, and h is a compound of 1 to 5; i in the formula (f-2-2) is 2 or 3, and j a compound of 1; a compound of formula (f-2-3) wherein k is 2 or 3 and m is 1; n in formula (f-2-4) is 1 or 2, or q is 1 or 2 And A is a compound of the group represented by the formula (fI) or the formula (fIV).

The compound having a hydroxyl group and a (meth)acryloyl group preferably includes 2-hydroxyethyl (meth)acrylate, 1-glyceryl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (methyl) ) 2-(6-hydroxyhexanoyloxy)ethyl acrylate, 2-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)ethyl (meth)acrylate, (meth)acrylic acid (4-Hydroxymethylcyclohexyl)methyl ester or (3-hydroxymethyladamantan-1-yl)methyl (meth)acrylate.

Specific examples of the compound having a hydroxyl group and a (meth)acryloyl group include 4-hydroxyphenyl (meth) acrylate, in addition to the compound represented by the formula (f-2-1) to the formula (f-2-4). , pentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, a compound represented by formula (f-2-5) or The compound represented by (f-2-6).

In the present invention, the compound having a hydroxyl group and a (meth)acryloyl group may be used singly or in combination of two or more.

Next, IN ^- in the above formula (f-5) will be described.

Specific examples of IN ^- include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion or amethide anion.

Halogen ions include fluoride ions, chloride ions, bromide ions or iodide ions.

Further, specific examples of the boron anion include inorganic boron anions such as BF ₄ ^- ; (CF ₃ ) ₄ B ^- , (CF ₃ ) ₃ BF ^- , (CF ₃ ) ₂ BF ₂ ^- , (CF ₃ ) BF ₃ ^- , ( C ₂ F ₅ ) ₄ B ^- , (C ₂ F ₅ ) ₃ BF-, (C ₂ F ₅ ) BF ₃ ^- , (C ₂ F ₅ ) ₂ BF ₂ ^- , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ^- , (C ₆ F ₅ ) ₄ B ^- , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ^- , (CF ₃ C ₆ H ₄ ) ₄ B ^- , (C ₆ F ₅ ) ₂ BF ₂ ^- , (C ₆ F ₅ )BF ₃ ^- , (C ₆ H ₃ F ₂ ) ₄ B ^- , B(CN) ₄ ^- , B(CN)F ₃ ^- , B(CN) ₂ F ₂ ^- , B( _{^{CN) 3 F -, (CF}} 3) 3 B (CN) -, (CF 3) 2 B (CN) 2 -, (C 2 F 5) 3 B (CN) -, (C 2 F 5) 2 B (CN) ₂ ^- , (nC ₃ F ₇ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₂ B(CN) ₂ ^- , (nC ₆ F ₁₃ ) ₃ B(CN) ^- , (CHF ₂ ) ₃ B(CN) ^- , (CHF ₂ ) ₂ B(CN) ₂ ^- , (CH ₂ CF ₃ ) ₃ B(CN) ^- , (CH ₂ CF ₃ ₂ B(CN) ₂ ^- , (CH ₂ C ₂ F ₅ ) ₃ B(CN) ^- , (CH ₂ C ₂ F ₅ ) ₂ B(CN) ₂ ^- , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B(CN) ₂ ^- , (nC ₃ F ₇ CH ₂ ) ₂ B(CN) ₂ ^- , (C ₆ H ₅ ) ₃ B(CN) ^- , tetraphenyl borate, tetra (monofluorophenyl) Borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)boron Acid salt, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetra (two) Tolyl)borate, (triphenyl, pentafluorophenyl)borate, [paras(pentafluorophenyl), phenyl]borate or tridecahydro-7,8-dicarbonyl undecaborate In addition to the organic boron anions such as the acid salt (tridecahydride-7, 8-dicarbaundecaborate), JP-A-H05-195119, JP-A-2010-094807, and JP-A-2006-243594 The boron anion described in Japanese Laid-Open Patent Publication No. Hei. No. 2002-341533 or Japanese Patent Publication No. Hei 08-015521.

Further, specific examples of the phosphate anion include inorganic phosphate anions such as HPO ₄ ^2- , PO ₄ ^3- , PF ₆ ^- ; (C ₂ F ₅ ) ₂ PF ₄ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , [( CF ₃ ) ₂ CF] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (nC ₃ F ₇ ) ₂ PF ₄ ^- , (nC ₃ F ₇ ) ₃ PF ₃ ^- , (nC ₄ F ₉ ₃ PF ₃ ^- , (C ₂ F ₅ )(CF ₃ ) ₂ PF ₃ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ^- , ( nC ₄ F ₉ ) ₂ PF ₄ ^- , (nC ₄ F ₉ ) ₃ PF ₃ ^- , (C ₂ F ₄ H)(CF ₃ ) ₂ PF ₃ ^- , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ^- , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ^- , an octyl phosphate anion, a dodecyl phosphate anion, an octadecyl phosphate anion, a phenyl phosphate anion or a nonylphenyl phosphate anion.

Further, specific examples of the carboxylic acid anion include CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- and the like, and in addition to Japanese Patent Laid-Open Publication No. 2009-265641 or JP-A-2008- A carboxylic acid anion described in Japanese Patent No. 096680.

Further, specific examples of the sulfate anion include a sulfate anion and a sulfite anion.

Specific examples of the organic sulfonic acid anion include an alkylsulfonic acid anion such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid or nonafluorobutanesulfonic acid; benzenesulfonic acid and benzenedisulfonate An arylsulfonic acid anion such as ion, p-toluenesulfonic acid, p-trifluoromethanesulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid or naphthalene disulfonate ion, in addition to 2-(methyl) Acryloxy-1,1,2,2-tetrafluoroethanesulfonic acid, 2-(4-vinylphenoxy)-1,1,2,2-tetrafluoroethanesulfonic acid, in International Publication No. 2011 An organic sulfonic acid anion described in Japanese Patent No. 3,736,221, or Japanese Patent Application Laid-Open No. 2011-070172.

Further, specific examples of the nitrogen anion include [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ SO ₂ )] ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ^- , [ (FSO ₂ )N{CF ₃ CF ₂ (CF ₃ )CFSO ₂ }] ^- , [(FSO ₂ )N{(CF ₃ ) ₃ CSO ₂ }] ^-, etc., in addition to The nitrogen anions described in JP-A-2010-090341, and JP-A-2010-090341.

Further, specific examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ^- , (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ^- , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ^- , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ^- , (FSO ₂ ) ₃ C ^- and the like, in addition to Japanese Patent Laid-Open No. 2011-145540, No. 5,554,664 The methide anion described in JP-A-2005-309657, JP-A-2004-085657, and JP-A-2010-505787.

The amount of the dye (F-1) used may be 3 based on the amount of the alkali-soluble resin (A) used in an amount of 100 parts by weight. The parts by weight to 90 parts by weight, preferably 5 parts by weight to 85 parts by weight, and more preferably 10 parts by weight to 80 parts by weight.

When the dye (F) of the present invention contains the dye (F-1), the resulting photosensitive resin composition preferably has a gassing property.

Other dyes (F-2)

The dye (F) may include other dyes (F-2). Specific examples of other dyes (F-2) include red dyes such as CI Solvent Red 45 and CI Solvent Red 49; blue solvents such as CI Solvent Blue 35, CI Solvent Blue 37, CI Solvent Blue 59, and CI Solvent Blue 67; Acid red dyes such as red 91, CI acid red 92, CI acid red 97, CI acid red 114, CI acid red 138, CI acid red 151, CI acid red 289; or CI acid blue 80, CI acid blue 83, CI acid Acidic blue dye such as blue 90.

The other dye (F-2) may be used in an amount of from 0 part by weight to 87 parts by weight, preferably from 0 part by weight to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), and more preferably 0 parts by weight to 70 parts by weight.

Further, the dye (F) may be used in an amount of 5 parts by weight to 90 parts by weight, preferably 10 parts by weight to 85 parts by weight, based on the amount of the alkali-soluble resin (A) used in an amount of 100 parts by weight, and more preferably 15 parts by weight. Parts by weight to 80 parts by weight.

Additive (G):

The photosensitive resin composition of the present invention may optionally further be further added with the additive (G) without affecting the efficacy of the present invention.

The additive (G) may include a filler, a polymer (refer to a polymer other than the above-described alkali-soluble resin (A)), an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, a thermal acid generator, and an oxygen-containing agent. a cyclobutane compound, an adamantyl ester compound or a glycoluril derivative or the like.

Specific examples of the filler include glass or aluminum and the like.

Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or a combination of the above polymers.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and N-(2-aminoethyl)-3-amine Propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidylpropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropane Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane or a combination of the above compounds.

Specific examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol or a combination of the above compounds.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxy phenone, and formula (g). -1) A compound represented or a combination of the above compounds.

In the formula (g-1), Gy represents -CH ₂ CH ₂ - or -CH ₂ CH(OH)CH ₂ -, and Gz represents a hydrogen atom or CH ₃ .

Specific examples of the anti-agglomerating agent include sodium polyacrylate and the like.

Specific examples of the thermal acid generator include a thermal acid generator represented by the formula (g-2), Irgacure 250, Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), or a combination of the above compounds.

In the formula (g-2), nx each of Gx ¹ independently represents a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an acyloxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, An aralkoxycarbonyl group having 7 to 10 carbon atoms, preferably an acyloxy group having 1 to 4 carbon atoms (for example, acetoxy (CH ₃ COO ^- )), an alkoxy group having 1 to 4 carbon atoms a carbonyl group (for example, methoxycarbonyl (CH ₃ OC(=O)-O-)) or an aralkoxycarbonyl group having a carbon number of 7 to 10 (for example, benzyloxycarbonyl (PhCH ₂ OC(=O)) -O-)), more preferably an acetoxy group;

Gx ² and Gx ³ each independently represent a benzyl or alkyl having 1 to 4 group, Gx ² is preferably any one or Gx ³ is alkyl having 1 to 4 (especially methyl) is another One is a benzyl group, wherein the benzyl group in Gx ² and Gx ³ is substituted or unsubstituted;

An ^- represents BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , trifluoromethanesulfonate anion or bis(trifluoromethanesulfonyl)amine anion;

Nx represents an integer from 0 to 5.

Preferably, the thermal acid generator represented by the formula (g-2) may be a thermal acid generator represented by the formula (g-2-1).

In the formula (g-2-1), Gx ⁴ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group, preferably an alkyl group having 1 to 4 carbon atoms and preferably a methyl group, and Gx ⁵ represents hydrogen. The atom is preferably an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom, and Gx ⁶ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group, and preferably a benzyl group, and Gx ⁶ represents a benzyl group. When it is substituted or unsubstituted, Gx ⁷ represents an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group.

Preferable specific examples of the thermal acid generator represented by the above formula (g-2) include a 4-acetoxyphenyldimethylhydrazine cation, a 4-hydroxyphenylbenzylmethylphosphonium cation, and a 4-acetoxy group. Phenylbenzylbenzylphosphonium cation, 4-methoxycarbonylphenyl, benzylmethylphosphonium cation, 4-hydroxyphenyldibenzylphosphonium cation or 4-acetoxyphenyldibenzylphosphonium cation Salts formed by PF ₆ ^- , SBF ₆ ^- , trifluoromethanesulfonate anion or bis(trifluoromethanesulfonyl)amine anion; San-aid (registered trademark) SI-60L, SI-80L, SI-100L, SI-110L, SI-145, SI-150, SI160, SI180L, and SI-250 (manufactured by Sanshin Chemical Industry Co., Ltd.), Adeka Optomer SP-170, and SP-172 (manufactured by ADEKA).

Specific examples of the compound having an oxetane group include trade names OXT-121, OXT-213, OXT-221, OXT-101, OXT-212 (manufactured by Toagosei Co., Ltd.) and the like.

The adamantyl ester compound has a structure represented by (g-3).

In the formula (g-3), Ga ¹ represents -O-CO-CH=CH ₂ or -O-CO-C(CH ₃ )=CH ₂ , and Ga ² represents an alkyl group having a carbon number of 1 to 6, gm. An integer of 1 to 3, gn represents an integer of 0 to 4, and one of the carbon atoms in the adamantane skeleton is bonded to Ga ¹ and Ga ² or to two Ga ¹ or two Ga ² .

Preferably, the adamantyl ester compound has 2-adamantyl (meth) acrylate represented by formula (g-3-1) or 1- represented by formula (g-3-2) Adamantyl (meth) acrylate.

In the formula (g-3-1), Ga ³ represents a hydrogen atom or a methyl group, and Ga ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula (g-3-2), Ga ⁵ represents a hydrogen atom or a methyl group.

Specific examples of the adamantyl ester compound include 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl acrylate, 2-butyl-2-adamantyl acrylate, etc. Compound.

The glycoluril derivative has a structure represented by the following formula (g-4).

In the formula (g-4): Gb represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms and an acyl group; Gb may be the same or different; Gc is selected from a hydrogen atom, a substituted or unsubstituted group of hydrocarbon groups having 1 to 15 carbon atoms, an acyl group and a nitro group; Gc may be the same or different; s represents 0, 1 or 2;

Gd ¹ means

Wherein, Gd ² represents a hydrogen atom or a carbon number of 1

An alkyl group to 4.

The above-mentioned glycoluril derivative is characterized in that in the bicyclic system, at least two glycidyl groups are each in a nitrogen-substituted position in the ring system, wherein the substitution positions of the two glycidyl groups are as in the formula (g-4) As shown, the two glycidyl groups are each a nitrogen-substituted position (1,3-position) bonded to the same five-membered ring. Further, the compound having the structure of the formula (g-4) also contains two glycidyl groups each bonded to the nitrogen-substituted position (1,5-position or 1,7-position) of the two five-membered rings. Further, the compound having the structure of the formula (g-4) may also contain 3 glycidyl groups which are each bonded at the nitrogen-substituted position of the two five-membered rings (1, 3, 5- Bit or 1, 3, 7-bit). Further, the compound having the structure of the formula (g-4) may also contain 4 glycidyl groups each bonded to the nitrogen-substituted position of the two five-membered rings (1, 3, 5, 7-bit).

In the formula (g-4), Gb is a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and an acyl group. Preferably, Gb has a carbon number of from 1 to 15; more preferably, the carbon number of Gb is 1 to 12. The carbon number of Gb may be smaller than the above carbon number. For example, the carbon number of Gb is 10, 8, or 4. The above values also apply to unsubstituted Gb. When the above hydrocarbon group is substituted, more carbon number can be introduced to Gb, wherein the above hydrocarbon group is explained below. The description herein for the hydrocarbyl group also applies to the acyl group.

The hydrocarbon group of the above Gb may be a linear or/or branched alkyl group and an alkenyl group having the above carbon number of 1 to 20; and an aryl group may also be used. According to the definition of the invention, the hydrocarbyl group may comprise a narrowly defined aromatic group, i.e. an alkaryl or aralkyl consisting solely of an aromatic ring system. When Gb represents an aryl group, an aralkyl group or an alkylaryl group, preferred examples thereof may include, but are not limited to, a phenyl group, a benzyl group, a tolyl group, a xylyl group or a homologous compound as described above.

Further, the above Gb may also be a cycloalkyl group or a cycloalkenyl group, and the cycloalkyl group or cycloalkenyl group also has a substituted cycloalkyl group or a cycloalkenyl group. On the other hand, when Gb represents a saturated or partially saturated cyclic group, a cyclopentyl group, a cyclohexyl group and a derivative thereof are preferred. In another aspect, when Gb represents a heterocyclic group, a ring compound containing O, N and/or S is preferred. The above ring system preferably has one, two or three heteroatoms or is a saturated, unsaturated or aromatic cyclic group.

The Gb may further have other substituents, preferably a halogen, an alkoxy group, an acyl group or an acyloxy group, wherein the halogen is preferably chlorine or/or bromine.

When Gb further contains a hydrocarbyl substituent, preferably, the substituent has no more than 10 carbon atoms, more preferably no more than 8, more preferably no more than 6, and particularly preferably no more than 4. The hydrocarbyl substituent includes, but is not limited to, an aryl group, an aralkyl group, an alkylaryl group, a cycloalkyl group, and/or an alkyl group having a substituent such as a halogen or an alkoxy group. Further, the above heterocyclic ring system is also contained, for example, a heterocyclic ring system having a hetero atom number of 1 to 3.

In the compound having the structure of the formula (g-4), the total number of carbon atoms of Gb in the presence of the substituent is not more than 12; preferably not more than 10; more preferably not more than 8; Good for no more than 4 or 6. The above numerical values of the number of carbon atoms are also applicable to Gb containing a substituent.

If Gc is not a hydrogen atom, if desired, it may be the same or different hydrocarbon group. Preferably, the respective hydrocarbon groups have no more than 12 carbon atoms; more preferably no more than 10 or 8; more preferably no more than 6 or 4. The description of Gb also applies to Gc.

The hydrocarbon group of Gc may be a linear or/or branched alkyl group and an alkenyl group having the above carbon number of 1 to 15, and the aryl group may be used. The description about Gb also applies to Gc, so the aryl group also contains an alkaryl group or an aralkyl group, and the description about a cycloalkyl group, a cycloalkenyl group and a heterocyclic group in Gb also applies to Gc.

Preferably, the substituent on the Gc is a halogen, a hydroxyl group, an amine group, an N-substituted amine group, a decyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group and/or an acyloxy group. The Gc can have the above one Or multiple substituents. Preferably, Gc has from 1 to 3 substituents; more preferably, Gc has a substituted or unsubstituted alkyl group, and a defined definition of this value in Gb is applicable to Gc.

Preferred specific examples of the glycoluril derivative include N,N'-diglycidylglycolide shown in Table 1.

Table 1:

Wherein - represents a hydrogen atom.

The additive (G) is used in an amount of from 0.1 part by weight to 10 parts by weight, based on the amount of the alkali-soluble resin (A), preferably from 0.3 part by weight to 7 parts by weight, and more preferably from 0.5 part by weight to more preferably 0.5 part by weight. 4 parts by weight.

A method which can be used for preparing a photosensitive resin composition, for example, placing an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), and a pigment (E) The mixture is stirred in a stirrer to be uniformly mixed into a solution state, and if necessary, a dye (F) and an additive (G) may be added and uniformly mixed to obtain a photosensitive resin composition in a solution state.

Further, the method for preparing the photosensitive resin composition is not particularly limited. The photosensitive resin composition is prepared by, for example, dispersing a part of the alkali-soluble resin (A) and the compound (B) having an ethylenically unsaturated group in a part of the solvent (D) to form a dispersion solution; and then mixing The remaining alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the solvent (D), and the pigment (E) are prepared.

Alternatively, the photosensitive resin composition may be obtained by dispersing a part of the pigment (E) in a part of the solvent (D) to form a pigment dispersion liquid; and mixing the remaining pigment (E) and the alkali-soluble resin (A). The compound (B) having an ethylenically unsaturated group, a photoinitiator (C), and a solvent (D) are prepared. Further, the dispersion step of the above pigment (E) can be carried out by mixing with a mixer such as a beads mill or a roll mill.

The color filter is prepared by sequentially pre-baking, exposing, developing, and post-baking the photosensitive composition on the substrate on which the black matrix has been formed, wherein the black matrix is used to isolate each pixel layer. The preparation method of the color filter will be described in detail below.

First, a photosensitive resin composition for a color filter in a solution state is uniformly applied onto a substrate by a coating method such as spin coating or cast coating or roll coating to form a coating film. The substrate is, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyles glass), a quartz glass, and the like to which a transparent conductive film is attached, which is used for a liquid crystal display device; A substrate (for example, a silicon substrate) of a solid-state imaging device; or a substrate having a black matrix for shielding light that can separate pixel layers such as red, green, and blue.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the residual solvent is completely removed by pre-baking to form a pre-baked coating film. It is worth noting that the conditions of drying under reduced pressure and pre-baking vary depending on the type and ratio of each component. In general, the vacuum drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the prebaking is performed at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes. Heat treatment.

Next, the prebaked coating film is exposed by a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet irradiation device may be a (ultra) high-pressure mercury lamp or a metal halide lamp.

Then, the exposed prebaked coating film is immersed in a developing solution at a temperature of 23 ± 2 ° C to remove an unnecessary portion of the prebaked coating film, whereby a specific pattern can be formed on the substrate. Specific examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine, dimethyl Basicity of basic compounds such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo-(5.4.0)-7-undecene Aqueous solution. The concentration of the developer is from 0.001% by weight to 10% by weight, preferably from 0.005% by weight to 5% by weight, and more preferably from 0.01% by weight to 1% by weight.

After the prebaked coating film is developed, the substrate having the specific pattern is washed with water, and the above specific pattern is air-dried with compressed air or compressed nitrogen. Then, post-bake (i.e., heat treatment) is performed by a heating device such as a hot plate or an oven. The post-baking temperature is from 100 ° C to 280 ° C, and the heating time is from 1 minute to 15 minutes to remove volatile components in the coating film and to carry out a thermosetting reaction of the unreacted ethylenically unsaturated double bond. After the above processing steps, a specific map can be fixed on the substrate. Thus, a pixel layer is formed. The above steps are repeated, and pixel layers such as red, green, and blue are sequentially formed on the substrate.

Finally, an ITO (Indium Tin Oxide) protective film (evaporated film) was formed on the surface of the pixel layer by sputtering in a vacuum atmosphere at a temperature of 220 ° C to 250 ° C. When necessary, the ITO protective film is etched and wired, and a liquid crystal alignment film (polyimide for liquid crystal alignment film) is applied onto the surface of the ITO protective film, thereby forming a color filter having a pixel layer.

First, a color filter formed by the above-described method of forming a color filter and a substrate provided with a thin film transistor (TFT) are disposed oppositely, and a gap (cell) is provided between the two Interval, cell gap). Next, the color filter is attached to the peripheral portion of the above substrate with an adhesive and the injection hole is left. Then, liquid crystal is injected from the injection hole in the gap between the surface of the substrate and the adhesive, and the injection hole is sealed to form a liquid crystal layer. Subsequently, a polarizing plate is provided by contacting the other side of the liquid crystal layer in the color filter with the other side of the substrate in contact with the liquid crystal layer to form a liquid crystal display element. Next, a surface light source is provided on one side of the liquid crystal display element to form a liquid crystal display device. The liquid crystal used as the liquid crystal compound or the liquid crystal composition is not particularly limited herein, and any liquid crystal compound or liquid crystal composition can be used.

Further, the liquid crystal alignment film used in the production of the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any of inorganic substances or organic substances may be used, and the present invention is not limited thereto.

Synthesis example of alkali-soluble resin (A-1)

Synthesis Example A-1-1 to Synthesis Example A-1-3 of the alkali-soluble resin (A-1) will be described below:

Synthesis Example A-1-1

First, 100 parts by weight of a ruthenium epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous manner to a 500 ml four-necked flask. The feed rate is controlled at 25 parts by weight/min, and the temperature of the reaction process is maintained at 100 ° C to 110 ° C. After 15 hours of reaction, solidification can be obtained. A pale yellow transparent mixture having a concentration of 50% by weight. Next, the pale yellow transparent mixture is subjected to a step of extraction, filtration, and heat drying to obtain a compound (A-1-1-a) having a solid content of 99.9% by weight.

Next, 1.0 mol of the compound (A-1-1-a), 0.1 mol of biphenyltetracarboxylic acid, 1.4 mol of maleic acid, 1.9 g of benzyltriethylammonium chloride, and 0.6 g of 2, 6-di-t-butyl-p-cresol, 700 g of propylene glycol monomethyl ether acetate, and 100 g of ethyl 3-ethoxypropionate were added to a 500-ml four-necked flask in a simultaneous manner to form a reaction. Solution. Finally, the above reaction solution was heated to 110 ° C, and reacted for 2 hours to obtain an alkali-soluble resin (A-1-1) having an acid value of 125 mg KOH/g and a number average molecular weight of 1,250.

Synthesis Example A-1-2

First, 100 parts by weight of an oxime epoxy compound (Model PG-100, manufactured by Osaka Gas; epoxy equivalent 259), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 135 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous addition to a 500 ml four-necked flask. The feed rate was controlled at 25 parts by weight/min, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid content of 50% by weight was obtained. The pale yellow transparent mixture is subjected to a step of extraction, filtration, and heat drying to obtain a compound (A-1-2-a) having a solid content of 99.9% by weight.

Next, 1.0 mol of the compound (A-1-2-a), 2.9 g of benzyltriethylammonium chloride, and 950 g of propylene glycol methyl ether acetate were placed in a 500 ml four-necked flask to form a reaction. Solution. Next, 0.8 mol of benzophenonetetracarboxylic dianhydride was added and reacted at 90 ° C for 2 hours. Then, 0.8 mol of tetrahydrophthalic anhydride was further added and reacted at 90 ° C for 4 hours. Through the above synthesis step, an alkali-soluble resin (A-1-2) having an acid value of 92 mgKOH/g and a number average molecular weight of 7,860 can be obtained.

Synthesis Example A-1-3

1.0 mol of the compound (A-1-2-a), 2.5 g of benzyltriethylammonium chloride, and 900 g of propylene glycol methyl ether acetate were added to a 500 ml four-necked flask to form a reaction solution. . 0.5 mol of benzophenone tetracarboxylic dianhydride was added and reacted at 90 ° C for 2 hours. Then add 1.0 more The ear was tetrahydrophthalic anhydride and reacted at 90 ° C for 4 hours. Through the above synthesis step, an alkali-soluble resin (A-1-3) having an acid value of 100 mgKOH/g and a number average molecular weight of 4,250 can be obtained.

Synthesis Example and Comparative Synthesis Example of Alkali Soluble Resin (A-2)

Synthesis Example A-2-1 to Synthesis Example A-2-7 and Comparative Synthesis Example A'-2-1 to Comparative Synthesis Example A'-2-3 of the alkali-soluble resin (A-2) will be described below:

Synthesis Example A-2-1

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a 1000-ml four-necked flask and nitrogen was introduced. Then, 20 parts by weight of 2-methacryloyloxy succinate (hereinafter abbreviated as HOMS), 50 parts by weight of dicyclopenteny acrylate (hereinafter abbreviated as FA-511A), 30 parts by weight a portion of benzyl methacrylate (hereinafter abbreviated as BzMA) is dissolved in 100 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as EEP), wherein the monomer mixture is fed in a continuous manner, and After uniformly mixing with stirring, the oil bath temperature of the four-necked flask was simultaneously raised to 100 ° C, and then 10 parts by weight of a polymerization initiator 2,2'-azobis-2-methylbutyronitrile (hereinafter It is abbreviated as AMBN) and dissolved in 100 parts by weight of EEP, and divided into two equal portions, and an aliquot is added to the four-necked flask every one hour. The reaction temperature of the whole polymerization process is maintained at 100 ° C, and the polymerization time is maintained for 3 hours. After the polymerization is completed, the polymerization product is taken out from the four-necked flask, and the solvent is devolatilized to obtain the alkali-soluble resin (A-2). -1).

Synthesis Example A-2-2 to Synthesis Example A-2-7 and Comparative Synthesis Example A'-2-1 to Comparative Synthesis Example A'-2-3

The alkali-soluble resins of Synthesis Example A-2-2 to Synthesis Example A-2-7 and Comparative Synthesis Example A'-2-1 to Comparative Synthesis Example A'-2-3 were the same as Synthesis Example A-2-1. The steps were prepared, and the difference was in the composition types of the respective synthesis examples and comparative synthesis examples, the amounts thereof used, the reaction time, and the reaction temperature, as shown in Table 2.

The compounds corresponding to the abbreviations in Table 2 are as follows.

Synthesis example of dye (F-1)

The synthesis example F-1-1 of the dye (F-1) to the synthesis example F-1-3 will be described below:

Synthesis Example F-1-1

170 parts by mass of anhydrous chloroform, 1.0 part by mass of camphorsulfonic acid, and 1.4 parts by mass of 4-(N,N-dimethylamino)pyridine were added to 18 parts by mass of basic violet 10 (basic violet 10). And 18 parts by mass of 2-hydroxyethyl methacrylate, and stirred for about 30 minutes. Thereafter, 47 parts by mass of anhydrous chloroform was added to 10.5 parts by mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and dissolved in advance. After the solution, it was stirred at room temperature for about 2 hours. After two times of liquid separation operation using 150 parts by mass of 1N aqueous hydrochloric acid solution, the organic layer was washed twice with 150 parts by mass of 10% saline. Then, after adding 43 parts by mass of anhydrous magnesium sulfate and stirring for about 30 minutes, the desiccant was filtered off, and the solvent was distilled off to obtain 20.6 parts by mass of a compound represented by the formula (F-1-1) (hereinafter referred to as dye F). -1-1).

Synthesis Example F-1-2

20 parts by mass of dye F-1-1 and 14.5 parts by mass of lithium bis(trifluoromethanesulfonyl)imide were added to a 500 mL Erlenmeyer flask to which a stir bar was placed, 130 parts by mass of chloroform and 100 masses were added. A portion of the ion-exchanged water was then stirred at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with 200 parts by mass of ion-exchanged water. After concentrating the organic layer under reduced pressure, the residue was dried under reduced pressure at 50 ° C for 12 hours to obtain 26.6 parts by mass of a compound represented by formula (F-1-2) (hereinafter referred to as dye F-1-2). ).

Synthesis Example F-1-3

The dye F- was synthesized in the same manner as in Synthesis Example F-1-2 except that potassium tetracyanoborate was used instead of lithium bis(trifluoromethanesulfonyl)imide in Synthesis Example F-1-2. 1-3.

Example and Comparative Example of Photosensitive Resin Composition

Hereinafter, Examples 1 to 13 and Comparative Examples 1 to 10 of the photosensitive resin composition and film will be described:

Example 1

80 parts by weight of the alkali-soluble resin A-1-1, 20 parts by weight of the alkali-soluble resin A-2-1, 60 parts by weight of dipentaerythritol hexaacrylate (abbreviated as B-2-1), and 15 parts by weight a photoinitiator represented by formula (1-10) (abbreviated as C-1-2), 15 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-indole Zyridin-3-substituted]-ethanone-1-(O-acetylhydrazine) (abbreviated as C-2-1), 50 parts by weight of CI Pigment Red 254 (CIPigment R254) (abbreviated as E-2) And 15 parts by weight of CI Acid Red 91 (abbreviated as F-2-2) are added to 800 parts by weight of propylene glycol methyl ether acetate (abbreviated as D-1), and after being uniformly stirred by a shaker, The photosensitive resin composition of Example 1 was obtained.

Example 2 to Example 13

The photosensitive resin compositions of Examples 2 to 13 were prepared in the same manner as in Example 1, and were different in that the composition of the photosensitive resin composition and the amount thereof were changed (as shown in Table 3). ). The obtained film was evaluated in the following evaluation manners, and the results are shown in Table 3.

Comparative Example 1 to Comparative Example 10

The photosensitive resin compositions of Comparative Example 1 to Comparative Example 10 were the same steps as in Example 1. It was prepared and differed in that the kinds of components of the photosensitive resin composition and the amounts thereof used were changed (as shown in Table 4). The obtained film was evaluated in the following evaluation manners, and the results are shown in Table 4.

The compounds corresponding to the labels in Tables 3 and 4 are as follows.

Evaluation method

a. High definition pattern linearity

The photosensitive resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 10 were applied by spin coating to a glass substrate of 100 mm × 100 mm, and dried under reduced pressure at a pressure of 100 mmHg and time 30. After a second, and then pre-baked at a temperature of 80 ° C for 3 minutes, a pre-baked film having a film thickness of 2.5 μm was formed. The prebaked coating film was exposed through a photomask having a strip pattern of 25 μm width (pitch 50 μm) by using 300 mJ/cm ² of ultraviolet light (exposure model AG500-4N). Thereafter, the developer was immersed in a developing solution at 23° C. for 1 minute and 2 minutes, and then washed with pure water, and then baked at 200° C. for 80 minutes to form a photosensitive resin layer having a film thickness of 2.0 μm on the glass substrate.

The strip pattern formed by the method was observed and evaluated by an optical microscope. The rating of the evaluation is as follows:

◎: Good linearity in 1 minute and good linearity in 2 minutes;

○: The linearity was good in 1 minute, and the linearity was poor in 2 minutes;

△: Partial linearity was poor in 1 minute, and linearity was poor in 2 minutes;

╳: 1 minute of poor linearity and 2 minutes of poor linearity.

b. Pattern smoothness

The pre-baked coating film of the above evaluation method (a) having a film thickness of 2.5 μm was irradiated with ultraviolet light of 100 mJ/cm ² (mJ/cm ² ) using an exposure machine (manufactured by Canon, model: PLA-501F), and then The prebaked coating film was immersed in a developing solution at 23 ° C for 1 minute, and washed with pure water. Then, by baking at 235 ° C for 30 minutes, a pixel layer having a film thickness of 2.0 μm was formed on the glass substrate. The surface roughness of the pixel layer was measured using an Atomic Force Microscope (AFM) (Dimension 3100, manufactured by Veeco Instruments Inc.) to evaluate its pattern smoothness. The measurement area was 10 μm ² . The surface roughness was evaluated based on the following criteria. The smaller the measured surface roughness, the better the surface roughness of the cured product formed of the photosensitive resin composition is. That is, the lower the surface roughness, the better the pattern smoothness. The rating of the evaluation is as follows:

◎: Surface roughness ≤ 6nm

○: 6 nm < surface roughness ≤ 8 nm

△: 8 nm < surface roughness ≤ 10 nm

╳: 10nm<surface roughness

c. outgassing

The photosensitive resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 10 were spin-coated, exposed, and developed in the same manner as described in the above evaluation method (a), and then, in a dust-free oven. Heat treatment was carried out for 1 hour in a clean oven at 230 ° C in a nitrogen atmosphere. After heating, it was heated at 220 ° C for 30 minutes using a thermal desorption spectrum analyzer (manufactured by Electronic Science Co., Ltd., WA1000S/W type), and the amount of outgas was calculated from the amount of the atomic weight 18 (water) which was separated. The rating of the evaluation is as follows:

◎: The amount of degassing is <10 ppm.

○: 10 ppm ≤ degassing amount < 20 ppm.

△: 20 ppm ≤ degassing amount < 30 ppm.

╳: The amount of degassing is ≥30ppm.

table 3

Table 3 (continued)

Table 4

Table 4 (continued)

It is understood from Tables 3 and 4 that the alkali-free resin (A- is used as compared with the film formed of the photosensitive resin composition using the alkali-soluble resin (A-1) (Examples 1 to 13). The film formed of the photosensitive resin composition of 1) (Comparative Examples 4, 8, and 10) had poor gassing properties.

Further, a photosensitive resin containing no alkali-soluble resin (A-2) is used as compared with a film formed of a photosensitive resin composition using an alkali-soluble resin (A-2) (Examples 1 to 13). The high-definition pattern of the film formed by the compositions (Comparative Examples 1 to 3 and 8 to 10) had poor linearity.

Further, a photosensitive film containing no photoinitiator (C-1) was used as compared with a film formed using a photosensitive resin composition containing a photoinitiator (C-1) (Examples 1 to 13). The film formed of the film (Comparative Examples 7, 9, 10) formed of the resin composition had poor pattern smoothness.

Further, when the ratio of the weight ratio of the alkali-soluble resin (A-1) to the alkali-soluble resin (A-2) is (A-1) / (A-2) is 5/95 to 95/5 When the range is outside (Comparative Examples 5 and 6), the formed film has a high-definition pattern with poor linearity and poor gassing properties.

As described above, the photosensitive resin composition of the present invention includes an alkali-soluble resin (A-1), an alkali-soluble resin (A-2), and a photoinitiator (C-1) having a specific structure, and an alkali-soluble resin. The weight ratio range (A-1)/(A-2) of the use amount of (A-1) to the alkali-soluble resin (A-2) is between 5/95 and 95/5, so that high definition can be improved. Problems such as poor pattern linearity, poor pattern smoothness, and high outgassing are applicable to color filters and liquid crystal display devices.

Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, and are not intended to be limiting; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand: The technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features may be equivalently replaced; and the modifications or substitutions do not deviate from the technical solutions of the embodiments of the present invention. The scope.

Claims

A photosensitive resin composition characterized by comprising:

Alkali-soluble resin (A);

a compound (B) having an ethylenically unsaturated group;

Photoinitiator (C);

Solvent (D);

Pigment (E);

Wherein the alkali-soluble resin (A) includes an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2), wherein the alkali-soluble resin (A-1) is obtained by reacting a mixture, and The mixture includes an epoxy compound (a-1-1) having at least two epoxy groups, a compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group, and a tetracarboxylic acid Or its acid dianhydride (a-1-3) and dicarboxylic acid or its anhydride (a-1-4);

The epoxy compound (a-1-1) having at least two epoxy groups has a structure represented by the following formula (aI-1) or the following formula (aI-2):

In the formula (aI-1), W 1 , W 2 , W 3 and W 4 are each the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5. Alkoxy group, aryl group having 6 to 12 carbon atoms or aralkyl group having 6 to 12 carbon atoms,

In the formula (aI-2), W 5 to W 18 are each the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and s represents An integer from 0 to 10;

The number average molecular weight of the alkali-soluble resin (A-1) is from 1,000 to 8,000;

The alkali-soluble resin (A-2) is composed of an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a-2-1), Copolymerization of an alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) and other unsaturated compound (a-2-3);

The alkali-soluble resin (A-2) has a weight average molecular weight of 3,000 to 30,000;

The weight ratio range (A-1) / (A-2) of the amount of the alkali-soluble resin (A-1) to the alkali-soluble resin (A-2) is 5/95 to 95/5;

The photoinitiator (C) comprises a photoinitiator (C-1) represented by formula (1);

Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 20 alkyl, COR 16 , OR 17 , halogen, NO 2 , The group represented by the formula (2) is a group represented by the formula (3),

Or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (4). Substituted C 2 -C 10 alkenyl

Or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently taken as —(CH 2 ) p —Y— (CH 2 ) q —;

Or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (5) ;

However, at least one of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is determined by the formula (5). The group represented,

R 9, R 10, R 11 and R 12 are independently hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups to one another: halo, Phenyl, CN, OH, SH, C 1 -C 4 -alkoxy, -(CO)OH or -(CO)O-(C 1 -C 4 alkyl);

Or R 9 , R 10 , R 11 and R 12 are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted by one or more of the following groups: C 1 -C 6 alkyl, halogen, CN, OR 17 , SR 18 or NR 19 R 20 ;

Or R 9 , R 10 , R 11 and R 12 are, independently of each other, halogen, CN, OR 17 , SR 18 , SOR 18 , SO 2 R 18 or NR 19 R 20 , wherein the substituents OR 17 , SR 18 or NR 19 R 20 optionally forms a 5- or 6-membered ring via a carbon atom in the naphthyl ring via the groups R 17 , R 18 , R 19 and/or R 20 ;

Or R 9 , R 10 , R 11 and R 12 are each independently a group represented by COR 16 , NO 2 or formula (2),

Y represents O, S, NR 26 or a direct bond;

p represents an integer of 0, 1, 2 or 3;

q represents an integer of 1, 2 or 3;

X represents CO or a direct bond;

R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 or a group represented by the formula (6);

Or R 13 represents a C 2 -C 20 alkyl group, interspersed with one or more of O, S, SO, SO 2 , NR 26 or CO, or a C 2 -C 12 alkenyl group which is unintercalated or heterozygous Or a plurality of O, CO or NR 26 , wherein the meta-hetero C 2 -C 20 alkyl group and the unmeta- or inter-hetero C 2 -C 12 alkenyl group are unsubstituted or substituted by one or more halogens ;

Or R 13 represents C 4 -C 8 cycloalkenyl, C 2 -C 12 alkynyl or C 3 -C 10 cycloalkyl having no or hetero or one or more O, S, CO or NR 26 ;

Or R 13 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 , COR 16 , CN, NO 2 , halogen, C 1 a C 2 alkyl group, a C 1 -C 4 haloalkyl group, a C 2 -C 20 alkyl group having one or more O, S, CO or NR 26 or a group represented by the formula (7),

Each warp or C 3 -C 10 cycloalkyl, or interrupted by one or more O, S, CO or NR C 3 26 -C 10 cyclic group is unsubstituted;

k represents an integer of 1 to 10;

R 14 represents hydrogen, C 3 -C 8 cycloalkyl, C 2 -C 5 alkenyl, C 1 -C 20 alkoxy or C 1 -C 20 alkyl, which is unsubstituted or one or more Substituted by: halogen, phenyl, C 1 -C 20 alkylphenyl or CN;

Or R 14 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, halogen, CN, OR 17 , SR 18 and / or NR 19 R 20 ;

Or R 14 represents a C 3 -C 20 heteroaryl group, a C 1 -C 8 alkoxy group, a benzyloxy group or a phenoxy group, the benzyloxy group and the phenoxy group being unsubstituted or having one or more of the following groups Group substituted: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl and/or halogen;

R 15 represents a C 6 -C 20 aryl group or a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 , SO-C 1 -C 10 alkyl, SO 2 -C 1 -C 10 alkyl, heterogeneous C 2 -C 20 alkyl group or a plurality of O, S or NR 26; or a C 1 -C 20 via respective substituted alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following Group substitution: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 Heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ;

Or R 15 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 8 cycloalkyl having no or hetero or one or more O, CO or NR 26 ; or R 15 represents C 1 -C 20 alkyl , which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxy a group represented by a carbonyl group, a C 3 -C 20 heteroaryloxycarbonyl group, NR 19 R 20 , COOR 17 , CONR 19 R 20 , PO(OC k H 2k+1 ) 2 , a phenyl group, and a formula (6) Or a group represented by the formula (8),

Or the C 1 -C 20 alkyl group is substituted by a phenyl group which is substituted by halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, OR 17 , SR 18 or NR 19 R 20 ;

Or R 15 represents a C 2 -C 20 alkyl group in which one or more O, SO or SO 2 are heterogeneous, and the inter-hetero C 2 -C 20 alkyl group is unsubstituted or has one or more of the following groups Substituted: halogen, OR 17 , COOR 17 , CONR 19 R 20 , phenyl or phenyl substituted by OR 17 , SR 18 or NR 19 R 20 ;

Or R 15 represents a C 2 -C 20 alkanoyl or benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, phenyl, OR 17 , SR 18 Or NR 19 R 20 ; or R 15 represents a naphthoyl group which is unsubstituted or substituted with one or more OR 17 or a C 3 -C 14 heteroarylcarbonyl group;

Or R 15 represents a C 2 -C 12 alkoxycarbonyl group which is undoped or inter-hetero-doped with one or more O and the inter- or un-doped C 2 -C 12 alkoxycarbonyl group is unsubstituted or One or more hydroxyl substitutions;

Or R 15 represents a phenoxycarbonyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, C 1 -C 4 haloalkyl, phenyl, OR 17 , SR 18 or NR 19 R 20 ;

Or R 15 represents CN, CONR 19 R 20 , NO 2 , C 1 -C 4 haloalkyl, S(O) m -C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl or SO 2- C 1 -C 6 alkyl-substituted S(O) m -phenyl;

Or R 15 represents an SO 2 O-phenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl group; or a diphenylphosphono group or a di-(C 1 -C 4 alkoxy)-phosphono group ;

m represents 1 or 2;

R' 14 has one of the meanings given for R 14 ;

R' 15 has one of the meanings given for R 15 ;

X 1 represents O, S, SO or SO 2 ;

X 2 represents O, CO, S or a direct bond;

R 16 represents a C 6 -C 20 aryl group or a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or a C 1 -C 20 alkyl group having one or more O, S or NR 26 ; or each of one or more C 1 -C 20 alkane Substituted, the C 1 -C 20 alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ;

Or R 16 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 )alkyl, O(CO)-(C 1 -C 4 alkyl), O(CO) -phenyl, (CO)OH or (CO)O(C 1 -C 4 alkyl);

Or R 16 represents a C 2 -C 12 alkyl group in which one or more O, S or NR 26 are heterogeneous; or R 16 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n ( CO)-(C 1 -C 8 alkyl), C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl;

Or R 16 represents a phenyl substituted with SR 18 , wherein the group R 18 represents a direct bond to the phenyl or naphthyl ring of the oxazole moiety to which the COR 16 group is attached;

n represents 1 to 20;

R 17 represents hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl), O(CO) -(C 2 -C 4 )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl, SO 2 - (C 1 -C 4 haloalkyl), O(C 1 -C 4 haloalkyl) or a C 3 -C 20 cycloalkyl group having one or more O;

Or R 17 represents C 2 -C 20 alkyl, in which one or more O, S or NR 26 are heterogeneous;

Or R 17 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 1 -C 8 alkanoyl, C 2 -C a 12 -alkenyl, C 3 -C 6 enoyl group or a C 3 -C 20 cycloalkyl group having no or hetero or one or more O, S, CO or NR 26 ;

Or R 17 represents a C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl group which is undoped or hetero-has one or more O;

Or R 17 represents a benzoyl group which is unsubstituted or substituted by one or more C 1 -C 6 alkyl groups, halogen, OH or C 1 -C 3 alkoxy groups;

Or R 17 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 An alkyl) 2 , a diphenyl-amine group or a group represented by the formula (7);

Or R 17 forms a direct bond bonded to one of the carbon atoms of the phenyl or naphthyl ring in which the group represented by the formula (2) or the group represented by the formula (7) is bonded,

R 18 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl, wherein the C 2 -C 12 alkenyl, C 3 -C 20 naphthenic Or a phenyl-C 1 -C 3 alkyl group which has no or hetero or one or more O, S, CO, NR 26 or COOR 17 ; or R 18 is a C 1 -C 20 alkyl group which is not Substituted or substituted with one or more of the following groups: OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O (C 1 -C 4 alkyl) , O(CO)-(C 2 -C 4 )alkenyl, O(CO)-(C 1 -C 4 alkyl), O(CO)-phenyl or (CO)OR 17 ;

Or R 18 represents a C 2 -C 20 alkyl group with one or more O, S, CO, NR 26 or COOR 17 interspersed therebetween;

Or R 18 represents (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 8 alkanoyl or C 3 -C 6 olefin Acyl group

Or R 18 represents a benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH, C 1 -C 4 alkoxy or C 1 -C 4 Alkylthio group;

Or R 18 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 12 alkyl, C 1 -C 4- haloalkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenylamino, (CO)O(C 1 -C 8 alkyl), (CO)-C 1 -C 8 alkyl, (CO)N (C 1 -C 8 alkyl) 2 or a group represented by the formula (7)

R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 3 - C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkanoyl, C 1 -C 8 alkanoyloxy, C 3 -C 12 alkenoyl, SO 2 -(C 1 - C 4 haloalkyl) or benzoyl;

Or R 19 and R 20 represent phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 4 haloalkyl, C 1- C 20 alkoxy, C 1 -C 12 alkyl, benzoyl or C 1 -C 12 alkoxy;

Or R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR 17 and which is either 5- or 6-membered saturated or unsaturated The ring is unsubstituted or substituted with one or more of the following groups: C 1 -C 20 alkyl, C 1 -C 20 alkoxy, =0, OR 17 , SR 18 , NR 21 R 22 , (CO) R 23 , NO 2 , halogen, C 1 -C 4 -haloalkyl, CN, phenyl, C 3 -C 20 cycloalkyl having one or more O, S, CO or NR 17 undoped or inter-hetero, or a group represented by the formula (7)

Or R 19 and R 20 together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C 1 -C 20 alkyl, C 1 - C 4 haloalkyl, C 1 -C 20 alkoxy, =0, OR 17 , SR 18 , NR 21 R 22 , (CO)R 23 , halogen, NO 2 , CN, phenyl or uninter or hetero Or a plurality of C 3 -C 20 cycloalkyl groups of O, S, CO or NR 17 or a group represented by the formula (7)

R 21 and R 22 are each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl;

Or R 21 and R 22 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR 26 and which is either 5- or 6-membered saturated or unsaturated The ring is unfused or the 5- or 6-membered saturated or unsaturated ring is fused to the benzene ring;

R 23 represents hydrogen, OH, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, intervening one or more O, CO or NR 26 C 2 -C 20 alkyl, uninter or hetero-O a C 3 -C 20 cycloalkyl group of S, CO or NR 26 , or R 23 represents phenyl, naphthyl, phenyl-C 1 -C 4 alkyl, OR 17 , SR 18 or NR 21 R 22 ;

R 24 represents (CO)OR 17 , CONR 19 R 20 , (CO)R 17 ; or R 24 has one of the meanings given for R 19 and R 20 ;

R 25 represents COOR 17 , CONR 19 R 20 , (CO)R 17 ; or R 25 has one of the meanings given for R 17 ;

R 26 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl with one or more O or CO in between; or phenyl-C 1 -C 4 alkane a C 3 -C 8 cycloalkyl group which is undoped or heterozygous with one or more O or CO; or (CO)R 19 ; or a phenyl group which is unsubstituted or one or more Substituted by: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 or a group represented by formula (7)

However, the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule.
The photosensitive resin composition according to claim 1, wherein the photoinitiator (C-1) represented by the formula (1), the R 1 , R 2 , R 3 , R 4 And R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 20 alkyl, COR 16 , NO 2 or a group represented by the formula (2);

Or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (5) ;

However, at least one of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is determined by the formula (5). a group represented;

X represents CO or a direct bond;

R -13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , SR 18 , COOR 17 , CONR 19 R 20 or PO (OC k H 2k +1 ) 2 ;

Or R 13 represents a C 2 -C 20 alkyl group, interspersed with one or more O, S, NR 26 or CO;

Or R 13 represents a phenyl or naphthyl group, and the two are unsubstituted or substituted by one or more groups represented by COR 16 or formula (7);

R - 14 represents a C 1 -C 20 alkyl group, a phenyl group or a C 1 -C 8 alkoxy group;

R 15 represents a phenyl group, a naphthyl group, a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, OR 17 An SR 18 or C 2 -C 20 alkyl group having one or more O or S hetero; or each of which is substituted by one or more C 1 -C 20 alkyl groups, the C 1 -C 20 alkyl group being unsubstituted Substituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxy Alkylcarbonyl, C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 , NR 19 R 20 or PO(OC k H 2k+1 ) 2 ;

Or R 15 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl Base, NR 19 R 20 , COOR 17 , CONR 19 R 20 or PO(OC k H 2k+1 ) 2 ;

R' 14 has one of the meanings given for R 14 ;

R' 15 has one of the meanings given for R 15 ;

R 16 represents a phenyl group which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or a C 2 -C 20 having one or more O, S or NR 26 interstitial alkyl;

Or R 16 represents phenyl which is substituted with one or more C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or is substituted with one or more of the following radicals: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ;

Or R 16 represents C 1 -C 20 alkyl, which is unsubstituted or substituted by halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 (CO O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl) or (CO)O(C 1 -C 4 alkyl);

R -17 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O ( C 1 -C 4 alkyl), (CO) O (C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl interrupted by one or more O or a C 3 -C 20 cycloalkyl;

Or R 17 represents a C 2 -C 20 alkyl group, in which one or more O;

R 18 represents a methyl group substituted with (CO)OR 17 ;

R 19 and R 20 are each independently hydrogen, phenyl, C 1 -C 20 alkyl, C 1 -C 8 alkanoyl or C 1 -C 8 alkanoyloxy;

Or R 19 and R 20 together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted via a group represented by formula (7);

However, the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule.
The photosensitive resin composition according to claim 1, wherein the photoinitiator (C-1) represented by the formula (1), the R 1 , R 2 , R 3 , R 4 R 5 , R 6 , R 7 and R 8 are each independently hydrogen, or R 1 and R 2 , R 3 and R 4 or R 5 and R 6 are independently of each other and are a group represented by the formula (5). ;

However, at least one of R 1 and R 2 , R 3 and R 4 or R 5 and R 6 is a group represented by the formula (5);

Or R 2 represents COR 16, NO 2 or by formula (2) or a group represented by the formula (3) a group represented by;

Or R 7 represents COR 16 or a group represented by formula (2);

R 9 , R 11 and R 12 represent hydrogen;

R 10 represents hydrogen, OR 17 or COR 16 ;

X represents CO or a direct bond;

R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , OR 17 , SR 18 or PO(OC k H 2k+1 ) 2 ;

Or R 13 represents a C 2 -C 20 alkyl group, in which one or more O;

Or R 13 represents a phenyl group;

k represents an integer 2;

R 14 represents a C 1 -C 20 alkyl group or a thienyl group;

R 15 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more OR 17 or C 1 -C 20 alkyl groups;

Or R 15 represents a thiophene group, hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: OR 17, SR 18, C 3 -C 8 -cycloalkyl, NR 19 R 20 or COOR 17 ;

Or R 15 represents a C 2 -C 20 alkyl group, interspersed with SO 2 ;

R 16 represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl;

Or R 16 represents a thienyl group;

R 17 represents hydrogen, C 1 -C 8 alkanoyl, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: halo, O (CO) a (C 1 -C 4 alkyl), O(CO)-(C 2 -C 4 )alkenyl group or a C 3 -C 20 cycloalkyl group having one or more O;

Or R 17 represents a C 2 -C 20 alkyl group, in which one or more O;

R 18 represents C 3 -C 20 cycloalkyl, C 1 -C 20 alkyl, which is unsubstituted or via one or more OH, O(CO)-(C 2 -C 4 )alkenyl or (CO) ) OR 17 replaced;

Or R 18 represents a phenyl group which is unsubstituted or substituted with one or more halogens;

R 19 and R 20 are each independently a C 1 -C 8 alkanoyl group or a C 1 -C 8 alkanoyloxy group;

Or R 19 and R 20 attached thereto together form a N atoms interrupted by O 5-membered or 6-membered saturated ring;

Provided that at least one group represented by formula (2) is present in the molecule;
The photosensitive resin composition according to claim 1, wherein the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is selected from the group consisting of unsaturated compounds having a bicyclopentyl group, A group consisting of unsaturated compounds having a dicyclopentenyl group and mixtures thereof.
The photosensitive resin composition according to claim 4, wherein the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is selected from the group consisting of dicyclopentanyl (meth)acrylate, Methyl) propylene A group consisting of dicyclopentenyl acid ester, dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and mixtures thereof.
The photosensitive resin composition according to claim 1, wherein the compound (B) having an ethylenically unsaturated group comprises a first compound (B-1), wherein the first compound (B-1) ) having a urethane group and at least 7 acryl groups.
The photosensitive resin composition according to claim 6, wherein the first compound (B-1) has a urethane group and at least 10 acryl groups.
The photosensitive resin composition according to claim 1, further comprising a dye (F).
The photosensitive resin composition according to claim 8, wherein the dye (F) comprises a dye (F-1) represented by the formula (f-1),

In the formula (f-1),

J 1 , J 2 , J 3 and J 4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. a substituted cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a substituted phenyl group;

J 5 and J 6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom;

J 7 represents a group having a polymerizable unsaturated group;

a represents an integer from 1 to 5.
The photosensitive resin composition according to claim 9, wherein the compound represented by the formula (f-1) includes a compound represented by the formula (f-2).

In the formula (f-2),

J 1 , J 2 , J 3 and J 4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. a substituted cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a substituted phenyl group;

J 5 and J 6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom;

J 8 represents a group having a polymerizable unsaturated group.
The photosensitive resin composition according to claim 10, wherein J 8 is a group represented by the formula (f-3) or a group represented by the formula (f-4).

In the formula (f-3) and the formula (f-4),

J 9 and J 10 each independently represent a hydrogen atom or a methyl group;

V 1 , V 2 , V 3 and V 4 each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms;

Q 1 indicates

Q 2 represents a divalent alicyclic hydrocarbon group;

b represents an integer from 0 to 12;

c and d each independently represent an integer from 0 to 6.
The photosensitive resin composition according to claim 1, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the ethylenically unsaturated group-containing compound (B) is used. The amount ranges from 20 parts by weight to 200 parts by weight; the photoinitiator (C) is used in an amount ranging from 10 parts by weight to 100 parts by weight; the solvent (D) is used in an amount ranging from 500 parts by weight to 5000 parts by weight. The pigment (E) is used in an amount ranging from 30 parts by weight to 300 parts by weight.
The photosensitive resin composition according to claim 8, wherein the dye (F) is used in an amount of 5 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A) used. 90 parts by weight.
The photosensitive resin composition according to claim 1, wherein the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1) based on the alkali-soluble resin (A-2) The total amount of the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) and the other unsaturated compound (a-2-3) is 100 parts by weight, and the alicyclic hydrocarbon group is contained. The unsaturated compound (a-2-2) is used in an amount ranging from 10 parts by weight to 50 parts by weight.
The photosensitive resin composition according to claim 6, wherein the first compound (B-1) is used in an amount ranging from 100 parts by weight based on the total amount of the alkali-soluble resin (A) used. 5 parts by weight to 100 parts by weight.
The photosensitive resin composition according to claim 1, wherein the photoinitiator (C-1) is used in an amount of 100 parts by weight based on the total amount of the alkali-soluble resin (A) used. It is 5 parts by weight to 100 parts by weight.
The photosensitive resin composition according to claim 9, wherein the dye (F-1) is used in an amount of 3 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). Parts to 90 parts by weight.
A method of producing a color filter, comprising forming a pixel layer using the photosensitive resin composition according to any one of claims 1 to 17.
A color filter produced by the method of claim 18.
A liquid crystal display device comprising the color filter of claim 19.