TWI620011B - Photosensitive resin composition, manufacturing method for color filter, color filter and liquid crystal display element using the same - Google Patents

Abstract

A photosensitive resin composition comprising an alkali-soluble resin (A) having The ethylenically unsaturated group compound (B), the photoinitiator (C), the solvent (D), and the pigment (E). The alkali-soluble resin (A) includes an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2). The alkali-soluble resin (A-1) is obtained by reacting a mixture comprising an epoxy compound (a-1-1) having at least two epoxy groups, having at least one carboxylic acid group and at least one ethylene The compound (a-1-2), the tetracarboxylic acid or its acid dianhydride (a-1-3), and the 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). The photoinitiator (C) includes a photoinitiator (C-1) represented by the formula (1).

Description

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

The present invention relates to a photosensitive resin composition and a color filter and a liquid crystal display device formed using the photosensitive resin composition. In particular, there is 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.

At present, color filters have been widely used in the fields of color liquid crystal displays, color facsimile machines, color cameras and the like. 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.

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

For example, as disclosed in Japanese Laid-Open Patent Publication No. Hei. It is used as an alkali-soluble resin of a photosensitive resin.

However, in the manufacturing process of the color filter, it is necessary to undergo multiple heat treatment steps, such as red (R), green (G) and blue (B), and the like, after the formation of the colored layer pattern, post-bake step And a transparent conductive film (ITO film) forming step, etc., these steps generally need to be operated at a high temperature of 200 ° C or higher, but the above-mentioned photosensitive resin is heated at 180 ° C for about 1 hour, but painted The generation of pigment agglomerated particles tends to occur in the pigmented layer (generally, the pigment agglomerated particles have a particle diameter of 1 to 10 μm), and the heat resistance of the pixel colored layer is also poor.

In order to improve the above-mentioned problem, the photosensitive resin composition disclosed in Japanese Laid-Open Patent Publication No. 2001-075273, which comprises a polymer obtained by polymerizing an unsaturated monomer having a carboxyl group and a monomer containing a glycidyl group, is used as a photosensitive resin. Alkali soluble 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 high-definition pattern at the same time, the linearity is poor, the pattern Problems such as poor smoothness and high outgassing to meet the requirements of the current industry are the goals of the research in the technical field to which the present invention pertains.

In view of the above, the present invention provides a photosensitive resin composition, and the high-precision pattern of the photosensitive resin composition has good linearity, low outgassing property, and pattern smoothness.

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 an acid dianhydride (a-1-3) and a dicarboxylic acid or an anhydride thereof (a-1-4); the epoxy compound (a-1-1) having at least two epoxy groups having the following formula (aI-1) or the structure shown in 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 of 0 to 10; the number average molecular weight of the alkali-soluble resin (A-1) is from 1,000 to 8,000; and the alkali-soluble resin (A-2) is an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a- 2-1) an alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) and another unsaturated compound (a-2-3) obtained by copolymerization; the alkali-soluble resin (A-2) The weight average molecular weight is 3,000 to 30,000; the weight ratio range (A-1)/(A-2) 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 the 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 independently of the formula ( 5) the group represented; However, the condition is that 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) The group represented, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl group being unsubstituted or having one or more of the following groups Group substitution: halogen, 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 with 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 each independently 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 with one of the carbon atoms 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 1, 2 or 3; X represents CO or a direct bond; R ₁₃ represents a C ₁ - C ₂₀ alkyl group, It 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 inter-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 a C ₄ -C ₈ cycloalkenyl group, a C ₂ -C ₁₂ alkynyl group or a C ₃ -C ₁₀ cycloalkyl group having one or more O, S, CO or NR ₂₆ without inter or hetero-hetero; or R ₁₃ 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 , COR ₁₆ , CN, NO ₂ , halogen, C ₁ - a C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group, a hetero group having one or more C ₂ -C ₂₀ alkyl groups of 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 ₂₆ of the C ₃ -C ₁₀ cycloalkyl; K represents 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 substituted with one or more of the following groups: halogen , phenyl, C ₁ -C ₂₀ alkylphenyl or CN; or R ₁₄ represents phenyl or naphthyl, each unsubstituted or substituted by 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 C ₃ -C ₂₀ heteroaryl, C ₁ -C ₈ alkoxy, decyloxy Or phenoxy, the benzyloxy and phenoxy are unsubstituted or substituted by one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and/or halogen; R ₁₅ Represents a C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halo, 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, one or more O, S or NR The ₂ -C ₂₀ C ₂₆ alkyl group; or each warp substituted C ₁ -C ₂₀ 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 , 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 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 a C ₆ -C ₂₀ aryloxycarbonyl 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 , phenyl, a group represented by the 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 interstitial C ₂ -C ₂₀ alkyl group is unsubstituted or has one or more of the following groups Substitution: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents C ₂ -C ₂₀ alkanoyl or benzamidine a 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 unsubstituted or a naphthylmethyl group 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 one or more of unintermixed or heterozygous O and the interstitial or unintercalated C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted by one or more hydroxy groups; or R ₁₅ represents a phenoxycarbonyl group which is unsubstituted or subjected to one or Substituted by a plurality of 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 , S(O) _m -phenyl which is unsubstituted or substituted by C ₁ -C ₁₂ alkyl or SO ₂ -C ₁ -C ₆ alkyl; or R ₁₅ represents SO ₂ O-phenyl, which is not Substituted or substituted by C ₁ -C ₁₂ alkyl; or diphenylphosphonium or di-(C ₁ -C ₄ alkoxy)-phosphonium; m represents 1 or 2; R' ₁₄ has One of the meanings given by 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 heterocyclic one or more C ₁ -C ₂₀ alkyl groups of O, S or NR ₂₆ ; or each of one or more C ₁ -C ₂₀ alkanes 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 _{2 0} 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, the C ₁ -C ₂₀ alkyl group Is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenoxy, 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 with one or more O, S or NR _{26 in between} ; 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 Bonding to the direct bond of 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, (C O) 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 a C ₂ -C ₂₀ alkyl group, wherein 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 ₁₂ alkenyl, C ₃ - acyl or C ₆ alkenyl interrupted or not interrupted with one or more O, S, CO or NR ₂₆ of the C ₃ -C ₂₀ cycloalkyl; or R ₁₇ represents C ₁ -C ₈ alkyl -C ₃ -C ₁₀ a cycloalkyl group which has no or hetero or one or more O; or R ₁₇ represents a benzhydryl group which is unsubstituted or has one or more C ₁ -C ₆ alkyl groups, halogen, OH or C ₁ -C ₃ alkoxy substituted; 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, phenyl sulfide a group, N(C ₁ -C ₁₂ 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 C _2- C ₂₀ alkyl group with one or more O, S, CO, NR ₂₆ or COOR _{17 in between} ; 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 alkenyl; or R ₁₈ represents a benzinyl group which is unsubstituted or one or more of the following Group substitution: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio; 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 radicals: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₁₂ Group, 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 formula ( 7) the indicated group 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 alkenyloxy, C ₃ -C ₁₂ alkenyl, SO ₂ -( a C ₁ -C ₄ haloalkyl group or a benzylidene group; or R ₁₉ and R ₂₀ represent a phenyl group, a naphthyl group or a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or has one or more of the following groups; Group substitution: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzhydryl or C ₁ -C ₁₂ alkoxy; or R ₁₉ and R ₂₀ Together with the N atom to which it is attached, it forms a 5- or 6-membered saturated or unsaturated ring which is not intermixed or intermixed with O, S or NR ₁₇ , and the 5 or 6 member saturated or unsaturated ring is unsubstituted or Substituted by 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 unintercalated or heterozygous, or represented by formula (7) Group 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 are attached thereto The N atoms together form a 5- or 6-membered saturated or unsaturated ring without inter- or inter-organic O, S or NR ₂₆ , and the 5- or 6-membered saturated or unsaturated ring is unfused or the 5 or 6 a saturated or unsaturated ring fused to a benzene ring; R ₂₃ represents hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, hetero or one or more O, CO or C _{2 of} NR ₂₆ a C ₂₀ alkyl group, a C ₃ -C ₂₀ cycloalkyl group which is undoped or intermixed with O, S, CO or NR ₂₆ or R ₂₃ represents a phenyl group, a naphthyl group, a phenyl-C ₁ -C ₄ alkyl group, 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 _{a 4-} haloalkyl group, a C ₂ -C ₂₀ alkyl group, optionally having one or more O or CO; or a phenyl-C ₁ -C ₄ alkyl group, a C ₃ -C ₈ cycloalkyl group, which is unintercalated or Miscellaneous with one or more O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a group represented by the formula (7) However, the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule.

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 of each other 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, the condition is that 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) a group represented by X; 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 with one or more O, S, NR ₂₆ or CO in between; or R ₁₃ represents a phenyl group or Naphthyl, both of which 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 subjected to a Or substituted with a plurality of groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or C ₂ -C ₂₀ alkyl, interspersed with one or more O or S; or more C ₁ -C ₂₀ 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} , 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 naphthenic a group, a C ₃ -C ₂₀ heteroaryl group, 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 the meanings for R ₁₅ Suo one of those given; R ₁₆ represents phenyl, which is unsubstituted or substituted with one or more of the following _{groups: oR 17, SR 18, NR} 1 ₉ R ₂₀ or a heterocyclic one or more C ₂ -C ₂₀ alkyl groups of O, S or NR ₂₆ ; or R ₁₆ represents a phenyl group which is substituted by one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl 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 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 the following groups: 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 C ₁ -C ₂₀ alkyl, 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 or interrupted by one or more O of C ₃ -C ₂₀ cycloalkyl; or R ₁₇ represents C ₂ -C ₂₀ alkyl, heteroalkyl having one or more therebetween O; R ₁₈ represents a substituted by COOR ₁₇ a of R ₁₉ and R ₂₀ are each independently hydrogen, phenyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₈ alkane An indenyl or C ₁ -C ₈ alkanoyloxy group; 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 represented by formula (7) Group substitution However, the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule.

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, 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 represents COR ₁₆ , NO ₂ or (2) the group represented by the group represented by the formula (3); 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 with one or more O in between; 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; and R ₁₅ represents a phenyl group or a naphthalene group. a group, 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 thienyl group, hydrogen, C ₁ -C ₂₀ alkyl group, the C ₁ -C ₂₀ alkane The group 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 C ₂ -C ₂₀ alkyl therebetween contaminated 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 group; or R ₁₆ represents a thienyl group; R ₁₇ represents hydrogen, C ₁ -C ₈ alkanoyl group, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group which is not A substituted or by one or more of the following groups: halo, O (CO) - (C 1 -C 4 alkyl), O (CO) - ( C 2 -C 4 alkenyl) or interrupted by one or more O the C ₃ -C ₂₀ cycloalkyl; or R ₁₇ represents C ₂ -C ₂₀ alkyl, heteroalkyl having one or more therebetween O; R ₁₈ represents a C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl, It is unsubstituted or substituted by one or more OH, O(CO)-(C ₂ -C ₄ alkenyl) or (CO)OR ₁₇ ; or R ₁₈ represents a phenyl group which is unsubstituted or Or a plurality of halogen substitutions; R ₁₉ and R ₂₀ are each independently C ₁ -C ₈ alkanoyl or C ₁ -C ₈ alkenyloxy; or R ₁₉ and R ₂₀ are taken together with the N atom to which they are attached a 5- or 6-membered saturated ring of O; however, the condition is 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 unsaturated compounds having a bicyclopentyl group and having a double ring. A group consisting of an unsaturated compound of a pentenyl group and a mixture 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 biscyclopentenyl (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 propylene sulfhydryl 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 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.

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 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.

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 formulae (f-3) and (f-4), J ⁹ and J ¹⁰ each independently represent a hydrogen atom or a methyl group; and V ¹ , V ² , V ³ and V ⁴ each independently represent substituted or unsubstituted. An alkanediyl group having a carbon number of 1 to 12; Q ¹ represents or ; Q ² represents a divalent alicyclic hydrocarbon group; b represents an integer of 0 to 12; and c and d each independently represent an integer of 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 one embodiment of the present invention, the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1), the alicyclic carbon-containing carbon based on the alkali-soluble resin (A-2) The total amount of the hydrogen 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-containing unsaturated compound (a) -2-2) is used in an amount ranging from 10 parts by weight to 50 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). .

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.

In order to make the above features and advantages of the present invention more apparent, the following is a special The embodiments are described in detail below in conjunction with the drawings.

<Photosensitive resin composition>

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). Hereinafter, each component of the photosensitive resin composition used in the present invention will be described in detail. Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and is represented by (meth) acrylate. Acrylate and/or methacrylate; similarly, the (meth)acrylonitrile group represents an acryloyl group and/or a methacryl 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 mixing The compound 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, a tetracarboxylic acid or Its acid dianhydride (a-1-3) and dicarboxylic acid or its anhydride (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 having the structure shown and the compound having the 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 as 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 bisphenol fluorene and a halogenated propylene oxide. (epihalohydrin) The epoxy group-containing bisphenol quinone type compound obtained by the reaction, 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)fluorene [9,9-bis (4-hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9 - bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl) [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)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 quinone type 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: for example SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.

Further, the 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 of the following formula (aI-2-2). The compound is subjected to a condensation reaction with a phenol to form a compound having the structure of the formula (aI-2-1). Next, an 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, and boron trifluoride (boron). Trifluoride), aluminum chloride anhydrous, zinc chloride, etc., of which 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, although the amount of the acid catalyst used is not particularly limited, the amount of the acid catalyst used is preferably based on 100 parts by weight (wt%) of the compound having the structure of the formula (aI-2-2). It is from 0.1 wt% to 30 wt%.

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 above organic solvent is used in an amount of from 50% by weight to 300% by weight based on the total amount of the compound having the structure of the formula (aI-2-2) and the phenol, and is preferably from 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) Phenylene diamine) Such as organic amines; and ammonia, sodium dihydrogen phosphate and the like. The above washing treatment can be carried out by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be carried out repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off by heat treatment 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 to the reaction before the 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.

Before the dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or the like may be added. The ammonium salt is used as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is carried out at a temperature of 20 ° C to 120 ° C for 1 hour. 10 hours to take off Hydrogen halide 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. A 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 case of using an aprotic polar solvent, the total amount of the aprotic polar solvent may be from 5 wt% to 100 wt%, wherein 10 wt% to 90 wt%, based on the total amount of the halogenated propylene oxide, is 100 wt%. good.

After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and decompression. 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 solution after the dehydrohalogenation reaction 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. Metal hydroxide water The 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 moles to 0.2 moles are preferred. 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 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 pressure reduction to obtain an epoxy compound having at least two epoxy groups as shown in the formula (C-II). (i). 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-methylpropenyl ethoxide, adipic acid 2-methylpropenyloxybutyl adipate, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropane Kamalyx, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene oxime Oxypropyl propyl tetrahydrophthalic acid, 2-methyl propylene oxypropyl phthalic acid, 2-methyl propylene oxybutyl butyl Terephthalic acid, or 2-methylpropenyloxybutyl phthalic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid The compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, phthalic acid; (3) a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group The (meth) acrylate includes, but is not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Acrylate [(2-hydroxypropyl)acrylate], 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutylmethyl Acrylate [(4-hydroxybutyl)methacrylate], pentaerythritol trimethacrylate, and the like. 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-containing tetracarboxylic acid compound represented by formula (K-1) and a fluorine atom-containing tetracarboxylic dianhydride compound represented by formula (K-2). The group of people formed. Specifically, a fluorine-containing tetracarboxylic acid compound represented by formula (K-1) and a fluorine atom-containing tetracarboxylic acid represented by formula (K-2) The anhydride compound is 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- Monofluorocarbon A fluorine-containing aromatic tetracarboxylic acid such as pyromellitic acid or 1,4-bis(trifluoromethyl)benzenetetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid, or a combination of the above 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)benzenedicarboxylic acid or 1,4-bis(3,4-dicarboxylic acid trifluorophenoxy)tetrafluorobenzene, or the above tetracarboxylic acid 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, diphenylphosphonium 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 the 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 fluorine-containing dicarboxylic acid or its anhydride include 3-fluorophthalic acid, 4-fluorophthalic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, and tetrafluoroethylene. Succinic 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, and tartar. Acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or a combination of the above compounds. The hydrocarbon group in the saturated linear hydrocarbon dicarboxylic acid may 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 trimethoxydecyl propyl succinic anhydride, triethoxy decyl propyl succinic anhydride, methyl dimethoxy decyl succinic anhydride, and methyl group. Diethoxydecyl propyl succinic anhydride, trimethoxy decyl butyl succinic anhydride, triethoxy decyl butyl succinic anhydride, methyl diethoxy decyl butyl succinic anhydride, (trimethoxydecyl)phenyl succinic anhydride, p-(triethoxydecyl)phenyl succinic anhydride, p-(methyldimethoxydecyl)phenyl succinic anhydride, p-methyl Ethoxy decyl)phenyl succinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, m-(dimethoxy decane) 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. Compound (a-1-2), tetracarboxylic acid or acid dianhydride thereof (a-1-3) and a dicarboxylic anhydride or its anhydride (a-1-4) can be 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) was 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 an unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1), an alicyclic hydrocarbon-containing unsaturated compound (a-2-2), and other unsaturated 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 ethyl 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, Tripropylene glycol mono methyl ether, tripropylene glycol Monoethyl ether) (poly)alkylene glycol monoalkyl ether solvent; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, etc. Alkylene glycol monoalkyl ether acetate solvent; diglyme, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ether solvents; methyl ethyl ketone, cyclohexanone, 2 a ketone solvent such as heptanone or 3-heptanone; an alkyl lactate solvent such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate; Ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ester, 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, Other ester solvents such as methyl ketone, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate; aromatics such as toluene and xylene Group hydrocarbon solvent; carboxylic acid guanamine solvent such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide. 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, ethyl 3-ethoxypropionate or cyclohexanone.

The initiator for preparing the alkali-soluble resin (A-2) is generally a radical type 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-(2,4-dimethylvaleronitrile)], 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) [2,2'-azobis- (4-methoxy-2,4-dimethylvalero nitrile)], 2,2'-azobis-2-methylbutyronitrile (2,2'-azobis-2-methyl butyro nitrile), etc. a compound; 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) comprises acrylic acid (AA), methacrylic acid (MAA), 2-methylpropenyl ethoxylated butyl 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-methylpropenyl ethoxy succinate or the above anhydride or a mixture thereof.

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1), the alicyclic hydrocarbon group-containing unsaturated compound (a-2-) based on the alkali-soluble resin (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) It is selected from the group consisting of unsaturated compounds having a bicyclopentyl group, unsaturated compounds having a dicyclopentenyl group, and mixtures thereof.

In one embodiment of the present invention, the dicyclopentyl group-unsaturated compound has a structure represented by the following formula (aII-1): Wherein: U ¹ represents a hydrogen atom or a methyl group; and u represents an integer of 0 to 2.

On the other hand, in one embodiment of the present invention, the dicyclopentenyl unsaturated compound has a structure represented by the following formula (aII-2): Wherein: U ² represents a hydrogen atom or a methyl group; and 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 (meth)acrylic acid. A group consisting of cyclopentenyl ester, dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and mixtures thereof.

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1), the alicyclic hydrocarbon group-containing unsaturated compound (a-2-) based on the alkali-soluble resin (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 by weight. 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 methacrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate Ester, phenoxyethyl methacrylate, phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol methacrylate, nonylphenoxy polyethylene glycol acrylate, nonyl phenoxy Polyethylene glycol methacrylate, N-phenyl maleimide, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl maleimide, N-pair Hydroxyphenyl maleimide, N-o-methylphenyl maleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxy Phenylmaleimide, N-p-methoxyphenylmaleimide, o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinyl Phenol, 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-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, o-methoxy Styrene, m-methoxystyrene, p-methoxystyrene, o-methoxymethylstyrene, m-methoxymethylstyrene, p-methoxymethylstyrene, O-(Vinylbenzyl)epoxypropyl ether, m-(vinylbenzyl)epoxypropyl ether, p-(vinylbenzyl)epoxypropyl ether, hydrazine, ethyl hydrazino Naphthalene, N-cyclohexylmaleimide, methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, Second butyl acrylate, tert-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, acrylic acid 4- Hydroxybutyl ester, allyl acrylate, triethylene glycol methacrylate, ethyl N,N-dimethylaminoacrylate, N,N-diethyl propyl acrylate, N,N-dibutyl Propyl propyl acrylate, glycidyl acrylate, methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Isobutyl methacrylate, second butyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, methyl propyl Allyl olefinate, triethylene glycol methacrylate methacrylate, dodecyl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate Base ester, eicosyl methacrylate, behenyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylamino methacrylate Ester, N-iso-butylaminoethyl methacrylate, glycidyl methacrylate (GMA), vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ether , allylepoxypropyl ether, methallyl glycidyl ether, acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, vinyl cyanide, acrylamide, A Acrylamide, α-chloropropenylamine, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 1,3-butadiene, isoamylene, chlorobutadiene or a mixture thereof; preferably, the third unsaturated single system is methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate , second butyl acrylate, tert-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic acid Propyl ester, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , glycidyl methacrylate, vinyl acetate, acrylonitrile, methacrylonitrile, 1,3-butadiene, isoamylene or a mixture thereof. Preferably, the third unsaturated single system is styrene, α-methylstyrene, phenyl methacrylate, phenyl acrylate, N-phenyl maleimide (PMI), N- o-Hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, glycidyl methacrylate, methacrylic acid Ester monomer, propylene A methyl ester monomer, 2-methylglycidyl methacrylate (MGMA), benzyl methacrylate (BzMA) or a mixture thereof.

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-2-1), the alicyclic hydrocarbon group-containing unsaturated compound (a-2-) based on the alkali-soluble resin (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) as 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 acrylonitrile group, and the The total number of the acrylonitrile groups contained in the polyisocyanate 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 propylene oximes). Base), UV6300B (having 7 propylene fluorenyl groups) or UV7640B (having 7 propylene fluorenyl groups), etc.; manufactured by Nippon Kayaku Co., Ltd., and its model can be DPHA40H (weight average molecular weight is 7000 and it has 10 Acryl sulfhydryl) or UX5001T (with 8 A propylene sulfhydryl group; etc.; a product manufactured by Gensei Industrial Co., Ltd., and its model number can be UN3320HS (weight average molecular weight is 5000 and it has 15 propylene sulfhydryl groups), UN904 (weight average molecular weight is 4900 and it has 10 Acrylsulfonyl), UN3320HC (weight average molecular weight of 1500 and having 10 propylene fluorenyl groups), etc.; or a product manufactured by Shin-Nakamura Chemical Co., Ltd., and its model may be U15HA (weight average molecular weight 2000 and 15 propylene) Sulfhydryl), UA-33H (having 9 propylene groups) or UA-53H (having 15 propylene groups).

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

Preferably, the aforementioned first compound (B-1) may be UV6300B, UX5001T, DPHA40H, UN3320HS, U15HA or any combination of 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 compound (B) of the ethylenically unsaturated group of the present invention contains the first compound (B-1), the photosensitive resin composition obtained has a good 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, Di(meth)acrylic acid Dicyclopentenyl ester, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tris(2-hydroxyethyl)isocyanate di(meth) acrylate, three (2-hydroxyethyl) isocyanate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tris(meth)acrylic acid Hydroxymethyl propyl ester, trimethylolpropyl tris(meth)acrylate modified with ethylene oxide (EO), tris(meth)acrylic acid modified with propylene oxide (PO) Methyl propyl ester, tripropylene glycol di(meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (a) Acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra(meth) acrylate, Ester-modified dipentaerythritol hexa(meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, di(trimethylolpropyl) tet tetrakis(meth)acrylate Ra(meth)acrylate], EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, EO modified hydrogenated bisphenol A II Methyl) acrylate, PO modified hydrogenated bisphenol A di(meth) acrylate, PO modified glycerol tri(meth) acrylate, EO modified bisphenol F di(methyl) Acrylate, novolak polyglycidyl ether (meth) acrylate, or any combination of the above.

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

Preferably, the second compound (B-2) may be dipentaerythritol hexa(meth) acrylate modified by caprolactone, tris(meth) acrylate modified by ethylene oxide (EO). Hydroxymethyl propyl ester, dipentaerythritol hexa(meth) acrylate, dipentaerythritol five (a 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. It is up to 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).

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 independently of the formula ( 5) the group represented; However, the condition is that 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) The group represented, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl group being unsubstituted or via one or more of the following groups Group substitution: halogen, 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 with 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 each independently 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 with one of the carbon atoms 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; and R ₁₃ represents a C ₁ - C ₂₀ alkane a 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 has no inter a plurality of O, CO or NR ₂₆ , wherein the inter-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; Or R ₁₃ represents a C ₄ -C ₈ cycloalkenyl group, a C ₂ -C ₁₂ alkynyl group or a C ₃ -C ₁₀ cycloalkyl group having one or more O, S, CO or NR ₂₆ without inter or hetero-hetero; or R ₁₃ 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 , COR ₁₆ , CN, NO ₂ , halogen, C ₁ -C _{a 20} alkyl group, a C ₁ -C ₄ haloalkyl group, a heterocyclic one or more C ₂ -C ₂₀ alkyl groups of 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 ₂₆ of the C ₃ -C ₁₀ cycloalkyl; K represents an integer of from 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 substituted with one or more of the following groups: Halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or CN; or R ₁₄ represents phenyl or naphthyl, each unsubstituted or substituted by 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 C ₃ -C ₂₀ heteroaryl, C ₁ -C ₈ alkoxy, benzyloxy Or a phenoxy group, which is unsubstituted or substituted with one or more of the following groups: 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 with one or more of the following groups: phenyl, halo, 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, interstitial or Multiple O, S or NR The ₂ -C ₂₀ C ₂₆ alkyl group; or each warp substituted C ₁ -C ₂₀ 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 , 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 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 a C ₆ -C ₂₀ aryloxycarbonyl 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 , phenyl, a group represented by the 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 interstitial C ₂ -C ₂₀ alkyl group is unsubstituted or has one or more of the following groups Group substitution: 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 C ₂ -C ₂₀ alkanoyl or benzoyl A thiol 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 unsubstituted Or a naphthylmethyl group substituted by 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 unintercalated or heterozygous one or more And the interstitial or unintercalated C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R ₁₅ represents a phenoxycarbonyl group which is unsubstituted or passed through a or more of the following groups: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkoxy , 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 , S(O) _m -phenyl which is unsubstituted or substituted by C ₁ -C ₁₂ alkyl or SO ₂ -C ₁ -C ₆ alkyl; or R ₁₅ represents SO ₂ O-phenyl, which is not Substituted or substituted by C ₁ -C ₁₂ alkyl; or diphenylphosphonium or di-(C ₁ -C ₄ alkoxy)-phosphonium; m represents 1 or 2; R' ₁₄ has One of the meanings given by 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 heterocyclic one or more C ₁ -C ₂₀ alkyl groups of O, S or NR ₂₆ ; or each of one or more C ₁ -C ₂₀ alkanes 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, the C ₁ -C ₂₀ alkyl group Is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenoxy, 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 with one or more O, S or NR _{26 in between} ; 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 Bonding to the direct bond of 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 a C ₂ -C ₂₀ alkyl group, wherein 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 ₁₂ alkenyl, C ₃ - acyl or C ₆ alkenyl interrupted or not interrupted with one or more O, S, CO or NR ₂₆ of the C ₃ -C ₂₀ cycloalkyl; or R ₁₇ represents C ₁ -C ₈ alkyl -C ₃ -C ₁₀ a cycloalkyl group which has no or hetero or one or more O; or R ₁₇ represents a benzhydryl group which is unsubstituted or has one or more C ₁ -C ₆ alkyl groups, halogen, OH or C ₁ -C ₃ alkoxy substituted; 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, phenyl sulfide a group, N(C ₁ -C ₁₂ 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 C _2- C ₂₀ alkyl group with one or more O, S, CO, NR ₂₆ or COOR _{17 in between} ; 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 alkenyl; or R ₁₈ represents a benzinyl group which is unsubstituted or one or more of the following Group substitution: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio; or R ₁₈ represents phenyl, naphthyl or C ₃ -C ₂₀ a heteroaryl group, 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 (7) the group represented, 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 alkenyloxy, C ₃ -C ₁₂ alkenyl, SO ₂ -( a C ₁ -C ₄ haloalkyl group or a benzylidene group; or R ₁₉ and R ₂₀ represent a phenyl group, a naphthyl group or a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or has one or more of the following groups; Group substitution: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzhydryl or C ₁ -C ₁₂ alkoxy; or R ₁₉ and R ₂₀ Together with the N atom to which it is attached, it forms a 5- or 6-membered saturated or unsaturated ring which is not intermixed or intermixed with O, S or NR ₁₇ , and the 5 or 6 member saturated or unsaturated ring is unsubstituted or Substituted by 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 unintercalated or heterozygous, or represented by formula (7) Group, 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 are attached thereto The N atoms together form a 5- or 6-membered saturated or unsaturated ring without inter- or inter-organic O, S or NR ₂₆ , and the 5- or 6-membered saturated or unsaturated ring is unfused or the 5 or 6 a saturated or unsaturated ring fused to a benzene ring; R ₂₃ represents hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, hetero or one or more O, CO or C _{2 of} NR ₂₆ a C ₂₀ alkyl group, a C ₃ -C ₂₀ cycloalkyl group which is undoped or intermixed with O, S, CO or NR ₂₆ or R ₂₃ represents a phenyl group, a naphthyl group, a phenyl-C ₁ -C ₄ alkyl group, 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 _{a 4-} haloalkyl group, a C ₂ -C ₂₀ alkyl group, optionally having one or more O or CO; or a phenyl-C ₁ -C ₄ alkyl group, a C ₃ -C ₈ cycloalkyl group, which is unintercalated or Miscellaneous with one or more O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, halogen, C ₁ a -C ₄ haloalkyl group, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a group represented by the formula (7); However, the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule.

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 with 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 of 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 also 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 The structure, as well as the Qiaolian or fused ring system, for example, the term is also 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 with 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 having one or more O interstitials 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 substituted by O atom of 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 alkyl group is substituted by a S atom of the 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.

Miscible with one or more C ₂ -C ₁₂ alkenyl groups of O, CO or NR ₂₆ via 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 ethyl, propyl, butyl, isobutyl, pentylene, hexyl, decyl, octyl, fluorenyl, fluorenyl, fluorenyl, tetradecyl, fifteen Base, hexadecanyl, octadecyl, and decyl, preferably acetyl. The C ₁ -C ₈ alkano group has the same meaning as given above for the C ₂ -C ₂₀ alkano 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-alkyloxycarbonyl 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 refers to a trans-heterocycloalkyl-CO- wherein the inter-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 refers to a transheterocycloalkyl-O-(CO)- group, wherein the interheterocycloalkyl 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.

The C ₆ -C ₂₀ aryl group is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, tetracylphenyl, tert-triphenyl, etc., especially phenyl or naphthyl, preferably Is a phenyl group. 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- 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-oxazole , 2,7-dimethyl-8-fluorenyl, 2-methoxy-7-methyl-8-fluorenyl, 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl , 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolinyl, 2-methoxy-3-quinolyl , 2-methoxy-6-quinolyl, 6-pyridazinyl, 7-pyridazinyl, 1-methoxy-6-pyridazinyl, 1,4-dimethoxy-6-pyridazine 1,1,8-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 - porphyrinyl, 3-methoxy-7-carbolinyl, 2-acridinyl, 6-acridinyl, 7-acridinyl, 6,7-dimethoxy-2-indolyl, 2-咔, 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-phenanthryl, 2-acridinyl, 3-acridinyl, 2-naphthyldiazophenyl, 1-methyl- 5-naphthyl-dinitrophenyl, 5-phenanol, 6-phenanol, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5- Isothiazolyl, 2-phenothiazine, 3-phenothiazine, 10-methyl-3-phenothiazine, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl , 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 in the interstitial). 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, , 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 and the 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.

When R ₁₇ is formed having bonded thereto a group 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 the 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 the COR ₁₆ group is attached, the thioxanthene The base moiety 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, optionally mixed 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 of O, S or NR ₁₇ as appropriate, an inter- or inter-molecular O is formed. Or NR ₁₇ , especially the 5- or 6-member saturated ring of 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 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) but also a plurality of defined substitutes (substituents) may be present, ie A mixture of different substitutes (substituents).

The term "at least" is intended to define one or more, such as one or both or three, preferably one or both.

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

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

Throughout this specification and the claims below, the words "comprise" or variant (eg, "comprises" or "comprising") are understood to include the integer or A step or integer group or 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 acrylate and the corresponding methacrylate.

The oxime ester of formula (1) is prepared by the methods described in the literature, for example by reacting the corresponding hydrazine with a hydrazine halide, especially a chloride or an anhydride, under the following conditions: in an inert solvent (eg, tert-butyl methyl ether, tetrahydrofuran) In (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 enthalpy is by using an alkyl nitrite (such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite). Nitrification to synthesize. The esterification is then carried out under the same conditions as described above:

Thus, the subject matter of the invention is also a process for the preparation of a compound of formula (1) as defined above by reacting the corresponding hydrazine compound with a hydrazine 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 Cl, and R ₁₄ is as defined above.

The desired starting material can be obtained by standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992) or monographs (eg SRSandler & W. Karo, Organic functional group preparations, A variety of methods are described in Volume 3, 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, add a base such as sodium acetate or pyridine to control the reaction. The pH of the mixture should be. 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. An alkaline solvent such as pyridine can also be used as the base and/or solvent or co-solvent. 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. Such 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 Volume V, pages 32 and 373, coll. Volume III, pages 191 and 513, coll. Volume II, pages 202, 204 and 363) It is suitable for the preparation of hydrazine used as a starting material in the present invention. 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 independently of each other Is -(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 independently of each other are a group represented by the formula (5), However, the condition is that 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) Represented group, 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 with 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 with one of the carbon atoms of 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 is} independent 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 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 inter-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 a C ₄ -C ₈ cycloalkenyl group, a C ₂ -C ₁₂ alkynyl group or a C ₃ -C ₁₀ cycloalkyl group having one or more O, S, CO or NR ₂₆ without inter or hetero-hetero; or R ₁₃ 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 , _{, 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 group; or via their respective C ₃ -C ₁₀ cycloalkyl, or interrupted by one or more O, S, CO or NR ₂₆ of the C ₃ -C ₁₀ cycloalkyl; K represents an integer of from 1 to 10; R ₁₅ represents a C ₆ - a C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halo, 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, hetero or one or more O, S or NR C ₂₆ of ₂ -C ₂₀ alkyl group; or each warp substituted C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups: halo, 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, which has no or hetero or one or more O, CO or NR ₂₆ ; or R ₁₅ represents C ₁ -C ₂₀ Group, which is unsubstituted or substituted with one or more of the following groups: _{halo, OR 17, SR 18, C} 3 -C 8 cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryl Oxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , phenyl, Or a group represented by the formula (6) 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 interstitial C ₂ -C ₂₀ alkyl group is unsubstituted or has one or more of the following groups Group substitution: 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 C ₂ -C ₂₀ alkanoyl or benzoyl A thiol 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 unsubstituted Or a naphthylmethyl group substituted by 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 unintercalated or heterozygous one or more And the interstitial or unintercalated C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R ₁₅ represents a phenoxycarbonyl group which is unsubstituted or passed through a Or substituted by a plurality of groups: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkane Base, 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 alkane a S(O) _m -phenyl group which is unsubstituted or substituted with a C ₁ -C ₁₂ alkyl group or a SO ₂ -C ₁ -C ₆ alkyl group; or R ₁₅ represents a SO ₂ O-phenyl group which is not Substituted or substituted by C ₁ -C ₁₂ alkyl; or diphenylphosphinyl or bis-(C ₁ -C ₄ alkoxy)-phosphonium; m represents 1 or 2; R' ₁₅ has One of the meanings given by 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 C ₃ - C _{a 20} heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halo, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ Or interscribing with one or more C ₁ -C ₂₀ alkyl groups of O, S or NR ₂₆ ; or each of them substituted by 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 aryloxy Carbonyl, 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: halo, 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 C ₂ -C ₁₂ alkyl, with one or a plurality of O, S or NR ₂₆ ; 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 - a C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl group; or R ₁₆ represents a phenyl group substituted with SR ₁₈ , wherein the group R ₁₈ represents a bond to the carbazole moiety to which the COR ₁₆ group is attached a direct bond of the phenyl or naphthyl ring; n represents 1 to 20; R ₁₇ represents hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or subjected to one or Substituted by a plurality of 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 , C 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 ₂₆ An alkyl group having one or more O, S or NR _{26 in between} ; 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 group, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenyl or acyl not interrupted or is interrupted by one or more O, S, CO or NR ₂₆ C ₃ of -C ₂₀ cycloalkyl; or R ₁₇ represents a C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl group which is undoped or heterozygous with one or more O; or R ₁₇ represents a benzamidine group, It is unsubstituted or substituted by one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or R ₁₇ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl a group, 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-amine or Or R ₁₇ forms a bond to have a group thereon, or a direct bond of one of the carbon atoms of the phenyl or naphthyl ring; 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 cycloalkyl or phenyl-C ₁ -C ₃ alkyl group is undoped or heterozygous with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; Or R ₁₈ is C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenoxy, 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 C ₂ -C ₂₀ alkyl with one or more O, S, CO, NR ₂₆ or COOR _{17 in between} ; 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 alkenyl; or R ₁₈ represents benzene A fluorenyl 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 ; 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 groups, 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 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 alkenyloxy, C ₃ -C ₁₂ olefinyl, SO ₂ - (C ₁ -C ₄ haloalkyl) or benzhydryl; or R ₁₉ and R ₂₀ represent phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or one or more of the following Group substitution: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzhydryl or C ₁ -C ₁₂ alkoxy; or R ₁₉ and R ₂₀ together with the N atom to which it is attached, forms a 5- or 6-membered saturated or unsaturated ring which is unintermixed or intermixed with O, S or NR ₁₇ , and the 5 or 6 member saturated or unsaturated ring is unsubstituted Or substituted by 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 without intermixing or intermixing; 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 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 inter or hetero or hetero; R ₂₁ and R ₂₂ are each independently hydrogen, C _{a 1-} C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group, a C ₃ -C ₁₀ cycloalkyl group or a phenyl group; or R ₂₁ and R ₂₂ together with the N atom to which they are attached form an unintermixed or intervening O, S or NR ₂₆ of 5 or 6 members of a saturated or unsaturated ring, and the 5 or 6 membered saturated or unsaturated 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, hetero or one or more O, CO or C ₂ -C ₂₀ alkyl of NR ₂₆ , 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 ; 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.'s) R _17; or R ₂₅ R ₁₇ Suo for having one of the meanings given by; R ₂₆ represents hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ Group, a heteroaryl therebetween or more O or CO; or phenyl -C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl which is interrupted or not interrupted by one or more O or CO; or Is (CO)R ₁₉ ; or a phenyl group which is unsubstituted or substituted with one or more of 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 group defined by the compound of formula (1A) corresponds to that 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 photoinitiator. Accordingly, the present invention is also directed to a mixture of configurational isomers of the compound of formula (1).

Preferable is a compound 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 each independently 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, the condition is that 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) 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 a C ₂ -C ₂₀ alkyl group with one or more of O, S, NR ₂₆ or CO interposed therebetween; or R ₁₃ represents a phenyl or naphthyl group, Unsubstituted or via one or more COR ₁₆ or Substituted; R ₁₄ represents C ₁ -C ₂₀ alkyl, phenyl or C ₁ -C ₈ alkoxy; R ₁₅ represents phenyl, naphthyl, C ₃ -C ₂₀ heteroaryl, each unsubstituted or Substituted by one or more of the following groups: phenyl, halo, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or C ₂ -C ₂₀ alkyl, interspersed with one or more O or S; or each Substituted by one or more C ₁ -C ₂₀ alkyl groups, 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 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 naphthenic a group, a C ₃ -C ₂₀ heteroaryl group, 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 the meanings for R ₁₅ Suo one of those given; R ₁₆ represents phenyl, which is unsubstituted or substituted with one or more of the following _{groups: oR 17, SR 18, NR} 19 R ₂₀ or a heterocyclic one or more C ₂ -C ₂₀ alkyl groups of O, S or NR ₂₆ or R ₁₆ represents a phenyl group substituted by one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl 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 ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents C ₁ -C ₂₀ alkyl, unsubstituted or via Group substitution: 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 C ₁ -C ₂₀ alkyl, 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 or a C ₃ -C ₂₀ cycloalkyl group having one or more O; or R ₁₇ representing a C ₂ -C ₂₀ alkyl group having one or more O in between; R ₁₈ representing 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 alkenyloxy; 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 bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group; R ₁₄ represents a C ₁ -C ₂₀ alkyl group; and R ₁₅ represents a C ₁ -C ₂₀ alkyl group. Or a phenyl group substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl groups; R ₁₆ represents a phenyl group substituted with one or more C ₁ -C ₂₀ alkyl groups or OR ₁₇ ; and R ₁₇ represents unsubstituted or substituted with one or more of halogen or C ₁ -C ₂₀ alkyl interrupted by one or more O of C ₂ -C ₂₀ alkyl group.

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

The subject matter of the invention is further 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; R ₁₃ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or one or more Substituted by: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H _2k+1 ) ₂ ; or R ₁₃ represents C ₂ -C ₂₀ alkyl with one or more O; or R ₁₃ Represents phenyl; k represents an integer of 2; R ₁₄ represents C ₁ -C ₂₀ alkyl or thienyl; R ₁₅ represents phenyl or naphthyl, each unsubstituted or via one or more OR ₁₇ or C ₁ - substituted C ₂₀ alkyl 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 ; or R ₁₅ represents C ₂ -C ₂₀ alkyl with intervening SO ₂ ; R ₁₆ represents phenyl or naphthyl, each 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; R ₁₇ represents hydrogen, C ₁ -C ₈ alkanoyl a C ₁ -C ₂₀ alkyl group which is unsubstituted or has one or more of the following groups: halogen, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ ) an 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 having one or more O in between; R ₁₈ represents C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted by one or more OH, O(CO)-(C ₂ -C ₄ )alkenyl or (CO)OR ₁₇ ; or R ₁₈ a phenyl group which is unsubstituted or substituted by one or more halogens; R ₁₉ and R ₂₀ are each independently C ₁ -C ₈ alkanoyl or C ₁ -C ₈ alkenyloxy; or R ₁₉ and R ₂₀ together with the N atom to which it is attached forms a 5- or 6-membered saturated ring interspersed with O; provided that at least one group represented by formula (2) is present in the molecule

Examples of compounds of the invention are the compounds 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 form a 5 or 6-membered ring with a carbon atom naphthyl 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 via a group R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ with one carbon atom of the naphthyl ring.

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, independently of each other, 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 the meantime, 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, both of which unsubstituted or substituted with one 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 Multiple halogen or phenyl substituted; or R ₁₄ represents phenyl or naphthyl, both unsubstituted or substituted by 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 benzamidine group, a C ₂ -C ₁₂ alkoxy group. Alkylcarbonyl, 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.

The 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)-phenyl , (CO) OH, (CO ) O (C 1 -C 4 alkyl), C ₃ -C ₂₀ cycloalkyl interrupted by one or more O or of C ₃ -C ₂₀ cycloalkyl; or R ₁₇ represents C _{a 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 olefin group or a C ₃ -C ₂₀ cycloalkyl group, optionally having one or more O; or R ₁₇ representing benzene Mercapto, which is unsubstituted or substituted by one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or R ₁₇ represents phenyl, naphthyl or C ₅ -C _{a 20} heteroaryl group, 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-amine or 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 -C ₈ alkyl fluorenyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ olefinic group, heterochromic one or more C ₂ -C ₂₀ alkyl groups, optionally with one or more C ₃ a -C ₂₀ cycloalkyl group; or a benzylidene 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 phenyl or naphthyl, each unsubstituted or substituted by one or more of the following: halo, 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, unsubstituted or via one or more of the following groups Substitution: halogen, C ₃ -C ₂₀ cycloalkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or miscellaneous one or more O C ₂ -C ₂₀ alkyl, or R ₁₇ represents C ₂ -C ₂₀ alkyl with one or more O intervening.

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 alkane a group of 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, wherein 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 alkenyl group, a benzamidine group; 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 haloalkane Base, 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, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₂ -C ₈ alkanoyl , benzylidene, 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 alkenyloxy group, a C ₃ -C ₁₂ alkenyl group or a benzhydryl group; or R ₁₉ and R ₂₀ The attached N 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 unsubstituted 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 alkyl fluorenyl group, a C ₁ -C ₈ alkyl fluorenyloxy group, a C ₃ -C ₁₂ olefinic fluorenyl group or a benzhydryl group; or R ₁₉ and R ₂₀ are attached thereto The atoms together form a 5- or 6-membered saturated ring, optionally mixed with 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 alkenyl group or a benzhydryl group; or R ₁₉ and R ₂₀ together with the N atom to which it is attached Form a 5- or 6-membered saturated ring with O or NR ₁₇ as appropriate.

Preferably, R ₁₉ and R ₂₀ are, independently of each other, a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkenyloxy 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.

The preferred of R ₂₄ is as given for R ₁₉ and R ₂₀ . The preferred of R ₂₅ is 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 O-acyloxime or non-oxo-indenyl quinone photoinitiators.

Other oxygen-indenyl steroids

Specific examples of other oxy-indenyl steroids include 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzene).醯 肟), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinium), 1-[4-(phenylthio) Phenyl]-octane-1,2-dione-2-(O-phenylhydrazinium), or a combination of the above compounds. 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinium) may be manufactured by Ciba Specialty Chemicals Co., Ltd. The model number is IRGACURE OXE-01.

Further, specific examples of other oxo-indenyl steroids include 1-[4-(benzoquinone) Phenyl]-heptane-1,2-dione-2-(O-phenylhydrazinyl), 1-[9-ethyl-6-(2-methylphenylindenyl)-9H-indole Zyridin-3-substituted]-ethanone-1-(O-ethylindenyl), 1-[9-ethyl-6-(3-methylphenylindenyl)-9H-indazole-3- Substituent]-ethanone-1-(O-acetamidoxime), 1-[9-ethyl-6-benzoin-9H-indazole-3-substituted]-ethanone-1- (O-Ethylhydrazine), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-indazole-3-Substituent]-1 -(O-acetylhydrazine), ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylphenyl)-9H-carbazole-3-substituted ]]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylphenyl)-9H-carbazole-3- Substituent]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)-9H-oxime Zyridin-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl) -9H-carbazole-3-substituted]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyl) Methoxybenzoinyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl- 5-four Furyl methoxyphenyl fluorenyl)-9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-A 5--5-tetrahydropyranylmethoxyphenylhydrazinyl)-9H-indazole-3-substituted]-1-(O-ethenylhydrazine), ethanoketone-1-[9-ethyl -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)phenylhydrazino}-9H-indazole-3-substituted]-1-( O-acetyl hydrazine), ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) Methoxybenzoquinone}-9H-indazole-3-substituted]-1-(O-ethylindenyl), or a combination of the above compounds. 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazole-3-substituted]-ethanone-1-(O-ethylindenyl) can be obtained from Ciba Made by Jinghua Co., Ltd., model IRGACURE OXE-02.

Other oxy-indenyl steroids may be used singly or in combination of two or more.

Non-oxy-indenyl quinone photoinitiator

Specific examples of the non-oxo-indenyl quinone 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, a phosphonium 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-methoxy B -naphthyl-1-substituted]-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphtho-1 -Substituent]-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1-yl]-4, 6-bis(trichloromethyl)-s-triazabenzene, 2-(2-methoxy-naphtho-1-substituted)-4,6-di(trichloromethyl)-s-three Azabenzene, 2-(6-methoxy-5-methyl-naphtho-2-substituted)-4,6-di(trichloromethyl)-s-triazabenzene, 2-(6 -methoxy-naphtho-2-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(5-methoxy-naphtho-1-enyl) -4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-di(trichloromethane) -s-triazene, 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-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(phenyl)aminobenzene 2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloromethyl) -s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[Inter-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo- For -N,N- Di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-di(B Oxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-di(ethoxycarbonyl) Methyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-di(ethoxycarbonylmethyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-di(ethoxycarbonylmethyl)aminobenzene -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(three Chloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s -Triazabenzene, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[Inter-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro -p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4- [m-Fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-(m-bromo-pair -N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonyl) Aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethane) -s-triazene, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triaza Benzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo) -p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-chloroethylaminobenzene) Base)-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-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-bis(trichloromethyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonyl) 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)aminophenyl]-2,6-di(trichloromethyl)- S-triazabenzene, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, or a combination of the above compounds.

Specific examples of the acetophenone compound include p-dimethylacetonone, α , α' -dimethoxy oxy acetophenone, 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-anthracene, benzophenone, and 4,4'-bis(dimethylamine) 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 benzophenone, 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 diphenylethanol ketone methyl ether, benzophenone ethyl ether, diphenylethanol ketone isopropyl ether, or a combination of the above compounds. Ketoether ethers The compounds may be used singly or in combination of two or more.

Specific examples of the phosphonium oxide compound include 2,4,6-trimethylphenylnonyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoquinone)-2,4,4-tri Methylphenylphosphine oxide, or a combination of the above compounds. The phosphonium phosphide 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 benzoquinone methyl chloride, tribromomethylphenylhydrazine, 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 is not opposite to the components. Should, and have the appropriate volatiles.

In one 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; methyl ethyl ketone, cyclohexanone, 2- Ketones such as heptanone and 3-heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -ethyl methacrylate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP) Ethoxyacetic acid Ester, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionic 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 Propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate Other esters such as esters; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide a solvent such as a solvent, preferably, the solvent is selected from the group consisting of propylene glycol methyl ether acetate and ethyl 3-ethoxypropionate, and the foregoing solvent may be used alone. Kind or mix a plurality of uses.

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, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 or (e- 1) Red pigment of the compound or the like represented; 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 Yellow pigment of 199, 200, 202, 203, 204, 205, 206, 207 or 208; CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38 Orange pigment of 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79; CI Pigment Violet 1 , purple pigments of 14, 19, 23, 29, 32, 33, 36, 37, 38, 39, 40, 50, etc.; CI pigment blue 1, 2, 15, 15:1, 15:2, 15:3, Blue pigments such as 15:4, 15:5, 15:6, 16, 21, 22, 60, 61, 64, 66; green pigments of CI pigment green 7, 36, 37, 42, 58; CI pigment Brown pigments of 23, 25, 28, etc.; and black pigments of CI Pigment Black 1, 7, etc. 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 produced by a synthesis method disclosed in a known patent document (Publication No. WO 2009/144115).

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. The above synthesis method is merely illustrative, and the synthesis method of the brominated diketopyrrolopyrrole pigment is not limited thereto.

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

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 acryl fluorenyl group or a methacryl fluorenyl 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).

In the formulae (f-3) and (f-4), J ⁹ and J ¹⁰ each independently represent a hydrogen atom or a methyl group; and V ¹ , V ² , V ³ and V ⁴ each independently represent substituted or unsubstituted. An alkanediyl group having a carbon number of 1 to 12; Q ¹ represents or ; Q ² represents a divalent alicyclic hydrocarbon group; b represents an integer of 0 to 12; and c and d each independently represent an integer of 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)acryloxy group or a phenoxy group, 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) propylene decyloxyalkyl group. Further, the (meth) propylene decyloxyalkyl 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 acrylonitrile group or a group Acryl fluorenyl. 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) acrylonitrile group in the compound, and the number of bonds and bonds of the hydroxy group and the (meth) acryl fluorenyl group. The knot position is not particularly limited. 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)acrylinyl 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)acrylinyl 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)acrylinyl 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; f and g each independently represent an integer of 0 to 2; and 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-hydroxyhexyloxy)ethyl (meth)acrylate and 3-(6-hydroxyhexanyl)(meth)acrylate. Oxy)propyl ester, 4-(6-hydroxyhexyloxy)butyl (meth)acrylate, 5-(6-hydroxyhexyloxy)pentyl (meth)acrylate or (meth)acrylic acid 6 (6-hydroxyhexyloxy) hexyl ester (6-hydroxyhexyloxy) alkyl ester, etc.; (6-hydroxyhexyloxy) 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]ethyl acrylate, 3-hydroxybicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, (meth)acrylic acid (3-Hydroxymethylbicyclo[2.2.1]hept-5-en-2-yl)methyl ester, 2-[3-(2-hydroxyethyl)bicyclo[2.2.1]heptyl-(meth)acrylate 5-en-2-yl]ethyl ester, 8-hydroxybicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, 2-hydroxyoctahydro-4,7 (meth)acrylate - (meth)acrylic acid 2-hydroxy octahydro-4,7-methanoindene-5-yl ester), (meth)acrylic acid (2-hydroxymethyl octahydro-4,7) -methylene hydrazin-5-yl)methyl ester, 2-[2-(2-hydroxyethyl) octahydro-4,7-methylene fluoren-5-yl]ethyl (meth)acrylate, ( 3-hydroxyadamantan-1-yl (meth)acrylate, (3-hydroxymethyladamantan-1-yl)methyl (meth)acrylate or 2-[3-(2-hydroxyl)(meth)acrylate Ethyl)adamantan-1-yl]ethyl ester and the like.

In these compounds having a hydroxyl group and a (meth)acrylinyl group, from reactivity From the viewpoint of the above, a compound wherein f and g in the formula (f-2-1) are 0 and h is 2 to 6; 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 is a compound of 1; k in the formula (f-2-3) is 2 Or a compound in which m is 1; n in the formula (f-2-4) is 1 or 2, or q is 1 or 2, and A is a group represented by the formula (fI) or the formula (fIV) Compound.

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

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

In the present invention, the compound having a hydroxyl group and a (meth)acrylinyl 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) ^- , tetraphenylborate, tetrakis(monofluorophenyl) Borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)boron Acid salt, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(dimethylphenyl)borate Salt, (triphenyl, pentafluorophenyl) borate, [e (pentafluorophenyl), phenyl] borate or tridecahydro-7,8-dicarbonyl undecanoate (tridecahydride-7,8) In addition to the organic-boron anion, it is also disclosed in Japanese Laid-Open Patent Publication No. Hei 10-195119, JP-A-2010-094807, JP-A-2006-243594, and JP-A-2002- A boron anion described in Japanese Laid-Open Patent Publication No. Hei. No. 041-533.

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 methanesulfonic acid (methanesulfonic) Acid), alkylsulfonate anion such as ethanesulfonic acid, trifluoromethanesulfonic acid or nonafluorobutanesulfonic acid; benzenesulfonic acid, benzenedisulfonate ion, p-toluenesulfonic acid, p-trifluoromethylsulfonate An arylsulfonic acid anion such as an acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid or naphthalene disulfonate ion, in addition to 2-(meth)acryloxyloxy-1,1,2,2- Tetrafluoroethanesulfonic acid, 2-(4-vinylphenoxy)-1,1,2,2-tetrafluoroethanesulfonic acid, in International Publication No. 2011/037195, Japanese Patent No. 3372221, or Japan An organic sulfonic acid anion described in Japanese Laid-Open Patent Publication 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 alkali-soluble resin (A) used is 100 parts by weight, the dye (F-1) The amount may be used in an amount of from 3 parts by weight to 90 parts by weight, preferably from 5 parts by weight to 85 parts by weight, and more preferably from 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 can be further optionally 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 oxygen. a compound of a heterocyclobutane group, 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 vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxy Propyl propyl trimethoxy decane, 3-glycidyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 3-chloropropyl group Dimethoxy decane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane 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, a decyloxy 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 a decyloxy group having 1 to 4 carbon atoms (for example, ethoxylated (CH ₃ COO ^- )), an alkoxy group having 1 to 4 carbon atoms a carbonyl group (for example, a methoxycarbonyl group (CH ₃ OC(=O)-O-)) or an aralkoxycarbonyl group having a carbon number of 7 to 10 (for example, a benzyloxycarbonyl group (PhCH ₂ OC (=O) And -O-)), more preferably an ethoxy group; Gx ² and Gx ³ each independently represent an alkyl group or a fluorenyl group having a carbon number of 1 to 4, preferably Gx ² or Gx ^3, any one of which is a carbon number The alkyl group (especially methyl) of 1 to 4 is the fluorenyl 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 4-ethenyloxyphenyldimethylhydrazine cation, 4-hydroxyphenylbenzylmethylphosphonium cation, 4-ethylidene a decyloxyphenylmercaptomethyl sulfonium cation, a 4-methoxycarbonylphenyl group, a decylmethyl sulfonium cation, a 4-hydroxyphenyl fluorenyl sulfonium cation or a 4-ethoxy phenyl phenyl dibenzyl group Salts of phosphonium cations with PF ₆ ^- , SBF ₆ ^- , trifluoromethanesulfonate anions or bis(trifluoromethanesulfonate) anions; 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, Compounds such as 2-ethyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl acrylate, and 2-butyl-2-adamantyl acrylate.

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 group of a hydrocarbon group having 1 to 20 carbon atoms and a mercapto group; Gb may be the same or different; and Gc is selected from a hydrogen atom. a substituted or unsubstituted group of hydrocarbon groups having 1 to 15 carbon atoms, an anthracenyl group and a nitro group; Gc may be the same or different; s represents 0, 1 or 2; and Gd ¹ represents Wherein Gd ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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 bonded to the nitrogen-substituted position (1,3-position) of 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 a nitrogen-substituted position of two five-membered rings (1, 3, 5, 7-bit).

In the formula (g-4), Gb is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a mercapto group. Preferably, Gb has a carbon number of from 1 to 15; more preferably, Gb has a carbon number of from 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 mercapto 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 hydrocarbon group can be packaged A narrowly defined aromatic group, that is, an alkaryl or aralkyl group composed 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. On the other hand, 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, a decyl group or a decyloxy 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 absence 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 values for all carbon atoms also apply to the 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 according to Gc may be an alkyl group or an alkenyl group having a linear or/or branched carbon group having 1 to 15 carbon atoms; and an aryl group. The description of Gb also applies to Gc, so the aryl group also contains an alkaryl or aralkyl group and the description of the cycloalkyl, cycloalkenyl and heterocyclic groups 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 a decyloxy group. The Gc may have one or more substituents as described above. Preferably, Gc has 1 to 3 substituents; more preferably, Gc has a substituted or unsubstituted alkyl group, and the definition of the 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.

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.

<Method for Preparing Photosensitive Resin Composition>

A method which can be used to prepare a photosensitive resin composition, for example, to dissolve an alkali The resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the solvent (D), and the pigment (E) are placed in a stirrer and stirred to uniformly mix into a solution state. The dye (F) and the 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). It is prepared by the compound (B) having an ethylenically unsaturated group, a photoinitiator (C), and a solvent (D). 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.

<Method for Manufacturing Pixel Layer and Color Filter>

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 the pixel layers. The preparation method of the color filter will be described in detail below.

First, a photosensitive resin group 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. The object is formed 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, and the like, and is used for a photoelectric conversion device (such as a solid). A substrate (for example, a germanium substrate) of the photographing device; or a substrate having a black matrix for shielding light from which a pixel layer such as red, green or blue is isolated.

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 citrate, sodium methyl citrate, aqueous ammonia, 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. the amount%.

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 (that is, 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-described processing steps, a specific pattern can be fixed on the substrate, thereby forming a pixel layer. Repeat the above steps to form red, green, blue and other pixel layers on the substrate in sequence.

Finally, an ITO (Indium Tin Oxide) protective film (evaporated film) was formed on the surface of the pixel layer by sputtering in a vacuum environment 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 (polyimine for liquid crystal alignment film) is applied onto the surface of the ITO protective film, thereby forming a color filter having a pixel layer.

<Method of Manufacturing Liquid Crystal Display Device>

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 is provided between the two (crystal) 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, by color filtering The other side of the light sheet that contacts the liquid crystal layer and the other side of the substrate that contacts the liquid crystal layer provide a polarizing plate 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, that is, the liquid crystal compound or the liquid crystal composition, is not particularly limited herein, and any liquid crystal compound and 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 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 concentration of 50% by weight was obtained. Then, the pale yellow transparent mixture is subjected to the steps of extraction, filtration, and heat drying to obtain a solid content of 99.9% by weight of the compound (A-1-1-a).

Next, 1.0 mol of compound (A-1-1-a), 0.1 mol of biphenyltetracarboxylic acid, 1.4 mol of maleic acid, 1.9 g of benzyltriethylammonium chloride, 0.6 g 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 at the same time. 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 Reaction solution. Add 0.8 moles of benzophenone tetracarboxylic dianhydride and The reaction was carried out 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 decyltriethylammonium 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, 1.0 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-1-3) 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 four-necked cone of 1000 ml volume, and nitrogen gas was introduced. Then, 20 parts by weight of 2-methylpropenyl ethoxy succinate (hereinafter abbreviated as HOMS), 50 Parts by weight of dicyclopenteny acrylate (hereinafter abbreviated as FA-511A), 30 parts by weight of benzyl methacrylate (hereinafter abbreviated as BzMA) are dissolved in 100 parts by weight of 3-ethoxypropionic acid In the ester (hereinafter referred to as EEP), the monomer mixture is fed continuously, and after mixing and mixing uniformly, the oil bath temperature of the four-necked flask is raised to 100 ° C, and then 10 parts by weight. The polymerization initiator 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) is dissolved in 100 parts by weight of EEP and divided into two equal portions, and an aliquot is added every hour to The four-necked flask is in the bottle. 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, 1.4 parts by mass of 4-(N,N-dimethylamino)pyridine, and 18 parts by mass of basic violet 10 were added. 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 preliminarily dissolved. 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 simply as a dye F-). 1-1).

Synthesis Example F-1-2

20 parts by mass of a 500 mL Erlenmeyer flask filled with a stir bar F-1-1 and 14.5 parts by mass of lithium bis(trifluoromethanesulfonyl) rutheide, 130 parts by mass of chloroform and 100 parts by mass of ion-exchanged water were added, followed by stirring 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) ruthenium 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-methylbenzoinyl)-9H- Oxazol-3-substituted]-ethane ketone-1-(O-ethinyl hydrazine) (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) were added to 800 parts by weight of propylene glycol methyl ether acetate (abbreviated as D-1), and after being uniformly stirred by a rocking stirrer, 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 Examples 1 to 10 were prepared in the same manner as in Example 1, and were different in that the kinds of components of the photosensitive resin composition and the amounts thereof 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 can be formed. The prebaked coating film was exposed through a reticle having a strip pattern of 25 μm width (pitch 50 μm) by using 300 mJ/cm ² of ultraviolet light (exposure model AG500-4N), and then exposed. The developer was immersed in a developing solution at 23 ° C for 1 minute and 2 minutes, and then washed with pure water, and 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 evaluation grades are as follows: ◎: good linearity in 1 minute, good linearity in 2 minutes; ○: good linearity in 1 minute, poor linearity in 2 minutes; △: poor linearity in 1 minute, poor linearity in 2 minutes ; ×: 1 minute of poor linearity, 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

×: 10 nm < 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), followed by 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 of degassing amount <30 ppm.

×: The amount of degassing was ppm30 ppm.

<evaluation result>

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.

In addition, when the alkali-soluble resin (A-1) and the alkali-soluble resin When the weight ratio range (A-1)/(A-2) of the use amount of (A-2) is outside the range of 5/95 to 95/5 (Comparative Examples 5 and 6), the film is formed with high fineness. The degree of pattern is not linear and the outgassing is poor.

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 of (A-1) to the amount of the alkali-soluble resin (A-2) used is (A-1) / (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.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

Claims (18)

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); 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 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, a tetracarboxylic acid or An acid dianhydride (a-1-3) and a dicarboxylic acid or an anhydride thereof (a-1-4); the epoxy compound (a-1-1) having at least two epoxy groups having the following formula (aI) -1) or the structure shown in 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 of 0 to 10; the number average molecular weight of the alkali-soluble resin (A-1) is from 1,000 to 8,000; and the alkali-soluble resin (A-2) is an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a- 2-1) an alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) and another unsaturated compound (a-2-3) obtained by copolymerization; the alkali-soluble resin (A-2) The weight average molecular weight is 3,000 to 30,000; the weight ratio range (A-1)/(A-2) 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 the formula (1); Wherein R ₁ , R ₂ , R ₃ , R ₄ , 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); 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, the condition is that 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) The group represented, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen; X represents a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group; and R ₁₄ represents a hydrogen or a C ₁ -C ₂₀ alkyl group. R ₁₅ represents a C ₆ -C ₂₀ aryl group, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ or C ₁ -C ₂₀ alkyl substituted; or R ₁₅ represents C ₁ -C ₂₀ Alkyl; R ₁₆ represents C ₆ -C ₂₀ aryl, each of which is unsubstituted or substituted with one or more of the following: each substituted with one or more C ₁ -C ₂₀ alkyl groups; R ₁₇ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen; or R ₁₇ represents a C ₂ -C ₂₀ alkyl group with one or more O intervening; provided that There is at least one group represented by the formula (2) in the formula (1); 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 an unsaturated compound having a dicyclopentenyl group and a mixture thereof. The photosensitive resin composition according to claim 2, wherein the alicyclic hydrocarbon group-containing unsaturated compound (a-2-2) is selected from the group consisting of dicyclopentanyl (meth)acrylate, A group consisting of dicyclopentenyl (meth)acrylate, 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 includes a first compound (B-1), wherein the first compound (B-1) ) having a urethane group and at least 7 propylene groups. The photosensitive resin composition according to claim 4, 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 6, 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 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; IN ^- represents an anion; and a represents an integer of 1 to 5. The photosensitive resin composition according to claim 7, 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 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 ⁸ represents a group having a polymerizable unsaturated group; and IN ^- represents an anion. The photosensitive resin composition according to claim 8, wherein J ⁸ is a group represented by the formula (f-3) or a group represented by the formula (f-4). In the formulae (f-3) and (f-4), J ⁹ and J ¹⁰ each independently represent a hydrogen atom or a methyl group; and V ¹ , V ² , V ³ and V ⁴ each independently represent substituted or unsubstituted. An alkanediyl group having a carbon number of 1 to 12; Q ¹ represents or ; Q ² represents a divalent alicyclic hydrocarbon group; b represents an integer of 0 to 12; and c and d each independently represent an integer of 0 to 6. The photosensitive resin composition according to the first aspect of the invention, wherein the ethylenically unsaturated group-containing compound (B) is based on 100 parts by weight of the total amount of the alkali-soluble resin (A) used. The amount used ranges from 20 parts by weight to 200 weights. 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. The photosensitive resin composition according to claim 6, 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. Up to 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-containing hydrocarbon The ethylenically 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 4, wherein the first compound (B-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 the first aspect of the invention, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the photoinitiator (C-1) is used. The range is from 5 parts by weight to 100 parts by weight. The photosensitive resin composition according to claim 7, wherein the dye (F-1) is used in an amount of 3 based on the total amount of the alkali-soluble resin (A) used in an amount of 100 parts by weight. Parts by weight to 90 parts by weight. A method of producing a color filter, which comprises forming a pixel layer by using a photosensitive resin composition according to any one of claims 1 to 15. A color filter produced by the method of claim 16 of the patent application. A liquid crystal display device comprising the color filter of claim 17 of the patent application.