TWI665523B - Photosensitive resin composition for black matrix, black matrix, color filter, and liquid crystal display device - Google Patents

Abstract

The invention provides a photosensitive resin composition for a black matrix, a black matrix, a color filter, and a liquid crystal display device. The obtained black matrix can still obtain a proper bluish chromaticity without increasing the amount of black pigment used. The photosensitive resin composition for a black matrix includes an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D), a black pigment (E), and Compound (F) having an epoxy group structure represented by formula (FI). The photoinitiator (C) includes a photoinitiator (C-1) having a structure of the formula (CI).

Description

Photosensitive resin composition for black matrix, black matrix, color filter, and liquid crystal display device

The present invention relates to a photosensitive resin composition for a black matrix, a black matrix, a color filter, and a liquid crystal display device, and more particularly, to a method capable of obtaining a proper bluishness without increasing the amount of black pigment used. A chromaticity black matrix, a black matrix photosensitive resin composition, a black matrix prepared from the black matrix photosensitive resin composition, a color filter including the black matrix, and the color filter Sheet of liquid crystal display device.

In recent years, with the vigorous development of various technologies of liquid crystal displays, and in order to improve the contrast and display quality of liquid crystal displays, a black matrix is usually provided in the stripes and dots of the color filters in the liquid crystal display. (dot). The black matrix can prevent defects such as a decrease in contrast ratio and a decrease in color purity caused by light leakage between pixels.

In general, the black matrix can be a vapor-deposited film having chromium, chromium oxide, or the like. However, when the black matrix is fabricated by using the aforementioned vapor-deposited film, it has the disadvantages of complicated manufacturing process and expensive materials. In order to solve the problems encountered by the black matrix, a technology of forming the black matrix by photo lithographic technology has been developed. Japanese Patent Laid-Open No. 2006-259716 discloses a photosensitive resin composition for a black matrix. This photosensitive resin composition contains a high-use amount of a black pigment, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer having a difunctional group, and an organic solvent. The difunctional reactive monomer can improve the reaction between the compounds, and can form a fine pattern. Therefore, the obtained photosensitive resin composition has good light-shielding property and sensitivity.

In recent years, the industry no longer pursues pure black for touch panels or smart wearable devices, but has a bluish taste. Therefore, although the use of black pigments can increase the shading to achieve high blackness, it is too dark to meet customers The blue taste. In addition, increasing the amount of black pigment also increases the cost burden.

Therefore, how to obtain a proper bluish chromaticity without increasing the amount of black pigment used to meet the requirements of the current industry is a problem urgently sought by those skilled in the art.

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-259716

In view of this, the present invention provides a black matrix for a color filter. The black matrix prepared by using the photosensitive resin composition can obtain an appropriate blueness without increasing the amount of black pigment.

The present invention provides a photosensitive resin composition for a black matrix, comprising: an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D), and a black pigment ( E) and a compound (F) having an epoxy group structure represented by the formula (FI). Wherein, the photoinitiator (C) includes a photoinitiator (C-1) having a structure of formula (CI);

In Formula (CI), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R _7, and R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, COR ₁₆ , OR ₁₇ , a halogen atom, NO ₂ , a group represented by the formula (C-II) or a group represented by the formula (C-III); Or any two of R ₁ to R ₈ whose relative positional relationship is adjacent to each other independently represent an alkenyl group substituted by a group represented by formula (C-IV) and having a carbon number of 2 to 10; ₁ ~ R ₈ or the relative positional relationship of both R ortho to one another independently of any common is _{- (CH 2) p -Y- (} CH 2) q - , or a group represented by the formula (CV) represents; However, the condition is that at least one pair of any of the two in which the relative positional relationship among R ₁ to R ₈ is adjacent is a group represented by the formula (CV).

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and the above-mentioned alkyl group having 1 to 20 carbon atoms is unsubstituted or has one or more of the following groups Substitution: halogen atom, phenyl, CN, OH, SH, alkoxy group having 1 to 4 carbon atoms, COOH or COOR ^X ; R ^X represents an alkyl group having 1 to 4 carbon atoms; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently an unsubstituted phenyl group or a phenyl group substituted with one or more of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OR ₁₇ , SR _18, or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a halogen atom, 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 a carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and / or R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ And R ₁₂ are each independently a group represented by COR ₁₆ , NO ₂ or formula (C-II); Y represents O, S, NR ₂₆ or a single bond; p represents an integer of 0 to 3; q represents 1 to 3 Integer; X represents CO or a single bond.

R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: halogen atom, 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 formula (C-VI); Or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms, interspersed with more than one O, S, SO, SO ₂ , NR ₂₆ or CO, or an alkenyl group having 2 to 12 carbon atoms, which is not interspersed Or interspersed with more than one O, NR ₂₆ or CO, in which the above-mentioned alkyl group having 2 to 20 carbon atoms and the unsubstituted or alkenyl group having 2 to 12 carbon atoms are unsubstituted or Substituted by more than one halogen atom; or R ₁₃ represents a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or one or more O, S, NR ₂₆ or CO without interspersed or interspersed A cycloalkyl group having a carbon number of 3 to 10; or R ₁₃ represents a phenyl group or a 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 atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, carbon number having 2 to 20 interspersed with more than one O, S, NR ₂₆ or CO Alkyl group, or a group represented by formula (C-VII); Or each of them is substituted by a cycloalkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms interspersed with one or more O, S, NR ₂₆ or CO; k represents an integer of 1 to 10;

R ₁₄ represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, which is Unsubstituted or substituted with more than one of the following: a halogen atom, a phenyl group, an alkylphenyl group having 1 to 20 carbon atoms or CN; or R ₁₄ represents a phenyl group or a naphthyl group, each of which is unsubstituted or substituted One or more of the following groups substituted: an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, CN, OR ₁₇ , SR _18, and / or NR ₁₉ R ₂₀ ; or R ₁₄ represents Heteroaryl group having 3 to 20 carbon atoms, alkoxy group, benzyloxy group or phenoxy group having 1 to 8 carbon atoms, said benzyloxy group and phenoxy group being unsubstituted or having more than one of the following groups Group substitution: an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and / or a halogen atom.

R ₁₅ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a phenyl group, a halogen atom, a carbon number of 1 To 4 haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , SO- (alkyl group having 1 to 10 carbons), SO _2- (An alkyl group having 1 to 10 carbons), an alkyl group having 2 to 20 carbon atoms interspersed with one or more O, S or NR ₂₆ ; or each substituted with an alkyl group having 1 to 20 carbon atoms, the above Alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl group, cycloalkane having 3 to 8 carbon atoms A heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OR ₁₇ , SR _18, or NR ₁₉ R ₂₀ ; or R ₁₅ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms that is not interspersed or interspersed with more than one O, CO, or NR ₂₆ ; or R ₁₅ is a carbon group having 1 to 20 alkyl groups, which are unsubstituted or substituted with more than one of the following groups: halogen atom, OR ₁₇ , S R ₁₈ , cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aryloxycarbonyl having 6 to 20 carbons, heteroaryloxycarbonyl having 3 to 20 carbons, NR ₁₉ R ₂₀ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , phenyl, a group represented by formula (C-VI) or a formula (C-VIII) Group Or the alkyl group having 1 to 20 carbon atoms is substituted by a phenyl group, the phenyl group is substituted by a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ substitution; or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms, in which one or more O, SO, or SO ₂ is interspersed, and the above-mentioned intercalated alkyl group having 2 to 20 carbons A radical is unsubstituted or substituted with more than one of the following groups: halogen atom, OR ₁₇ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; Or R ₁₅ represents an alkyl or benzamyl group having 2 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, benzene OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is a naphthylmethyl group which is unsubstituted or substituted with more than one OR ₁₇ or a heteroarylcarbonyl group having 3 to 14 carbons; or R ₁₅ Represents an alkoxycarbonyl group having 2 to 12 carbons, which is unsubstituted or interspersed with more than one O, and the aforementioned alkoxycarbonyl group having 2 to 12 is unsubstituted Or via more than one hydroxyl group Substituents; or R ₁₅ represents a phenoxycarbonyl group which is unsubstituted or substituted with one or more of the following groups: alkyl having 1 to 6, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, benzene Group, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , haloalkyl having 1 to 4 carbon atoms, S (O) _m- (carbon number 1 to 6 Alkyl), unsubstituted or S (O) _m- (phenyl) substituted with alkyl having 1 to 12 carbon atoms or SO _2- (alkyl having 1 to 6 carbon atoms); or R ₁₅ Represents S (O ₂ ) O- (phenyl), which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms; or is diphenylphosphinofluorenyl or di- (carbon group having 1 to 4 carbon atoms) Alkoxy) -phosphinofluorenyl; m represents 1 or 2; R _'14 has one of the meanings given for R ₁₄ ; R' ₁₅ has one of the meanings given for R ₁₅ ; X ₁ represents O, S, SO or SO ₂ ; X ₂ represents O, CO, S or a single bond.

R ₁₆ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a phenyl group, a halogen atom, and a carbon number of 1 To 4 halogenated alkyl groups, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or alkyl groups having 1 to 20 carbon atoms interspersed with more than one O, S or NR ₂₆ ; Is substituted by an alkyl group having 1 to 20 carbon atoms, and the aforementioned alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following groups: a halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , Phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aryloxycarbonyl having 6 to 20 carbons, heteroaryloxycarbonyl having 3 to 20 carbons OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and the above alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following Group substitution: halogen atom, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (carbon number 1 to 4 Alkyl), O (CO)-(alkyl with 1 to 4 carbons), O (CO) -phenyl, (CO) OH or (CO) O- (Alkyl group having 1 to 4 carbons); or R ₁₆ represents an alkyl group having 2 to 12 carbons, which is interspersed with more than one O, S or NR ₂₆ ; or R ₁₆ represents (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), alkenyl group having 2 to 12 carbon atoms or cycloalkyl group having 3 to 8 carbon atoms; Or R ₁₆ represents a phenyl substituted with SR ₁₈ , wherein the group R ₁₈ represents a single bond bonded to a phenyl or naphthyl ring of a carbazole moiety to which a COR ₁₆ group is attached; n represents 1 to 20 Integer.

R ₁₇ represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 3 carbon atoms), and an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, OH , SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms), O (CO)-(carbon Alkyl groups of 1 to 4), O (CO)-(alkenyl groups of 2 to 4 carbons), O (CO)-(phenyl), (CO) OH, (CO) O- (carbon numbers 1 to 4 alkyl), cycloalkyl having 3 to 20 carbons, SO _2- (haloalkyl having 1 to 4 carbons), O- (haloalkyl having 1 to 4 carbons) or hetero A cycloalkyl group having more than one oxygen atom having a carbon number of 3 to 20; or R ₁₇ representing an alkyl group having a carbon number of 2 to 20 with one or more O, S or NR ₂₆ interposed therebetween; or R ₁₇ representing ( CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), alkyl group having 1 to 8 carbon atoms, and carbon number 2 Alkenyl to 12, alkenyl having 3 to 6 carbons, or cycloalkyl having 3 to 20 carbons without interspersed or interspersed with more than one O, S, CO or NR ₂₆ ; or R ₁₇ represents Alkyl of 1 to 8 carbons (cycloalkyl of 3 to 10 carbons), which Mixed with one or more oxygen atoms; or R ₁₇ represents a benzoyl group which is unsubstituted or substituted with one or more carbon atoms, an alkyl group, a halogen atom, OH, or 1 to 6 carbon atoms, alkoxy of 1 to 3 Oxy-substituted; or R ₁₇ represents phenyl, naphthyl, or heteroaryl having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with more than one of the following groups: halogen atom, OH, carbon number 1 Alkyl to 12, alkoxyl having 1 to 12 carbons, CN, NO ₂ , phenyl- (alkoxyl having 1 to 3 carbons), phenoxyl, alkane having 1 to 12 carbons An alkylthio group, a phenylthio group, N (an alkyl group having 1 to 12 carbons) ₂ , a diphenyl-amino group, or a group represented by the formula (C-VII); or R ₁₇ forms a bond To a single bond having one of the carbon atoms of the phenyl or naphthyl ring in which the group represented by formula (C-II) or the group represented by formula (C-VII) is located.

R ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl group (an alkyl group having 1 to 3 carbon atoms), in which the carbon number is 2 to 12 Alkenyl, cycloalkyl with 3 to 20 carbons or phenyl- (alkyl with 1 to 3 carbons) are unsaturated or interspersed with more than one O, S, NR ₂₆ , CO or (CO) OR ₁₇ ; or R ₁₈ is an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl group with 1 to 4 carbons), O (CO)-(alkenyl group with 2 to 4 carbons), O (CO)-(carbon An alkyl group having 1 to 4), O (CO)-(phenyl) or (CO) OR ₁₇ ; or R ₁₈ represents an alkyl group having 2 to 20 carbons, with more than one O, S, NR ₂₆ , CO or (CO) OR ₁₇ ; or R ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), carbon Alkyl groups of 2 to 8 or alkenyl groups of 3 to 6 carbons; or R ₁₈ represents benzamyl, which is unsubstituted or substituted with more than one of the following groups: carbon number 1 to 6 alkyl group, halogen atom, OH, 1 to 4 carbon alkoxy group or carbon number is An alkylthio group of 1 to 4; or R ₁₈ represents a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with more than one of the following groups: halogen atom, carbon Alkyl groups of 1 to 12, haloalkyl groups of 1 to 4 carbons, alkoxy groups of 1 to 12 carbons, CN, NO ₂ , phenyl- (alkoxy groups of 1 to 3 carbons) , Phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N (alkyl having 1 to 12 carbons) ₂ , diphenylamino, (CO) O- (carbon number Is an alkyl group of 1 to 8), C (O)-(alkyl group of 1 to 8 carbons), C (O) N- (alkyl group of 1 to 8 carbons) ₂ or formula (C-VII ).

R ₁₉ and R ₂₀ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms 5 alkenyl, cycloalkyl having 3 to 20 carbons, phenyl- (alkyl having 1 to 3 carbons), alkylsulfonyl having 1 to 8 carbons, alkyl having 1 to 8 carbons Fluorenyloxy, alkenyl with 3 to 12 carbons, SO _2- (haloalkyl with 1 to 4 carbons) or benzamyl; or R ₁₉ and R ₂₀ represent phenyl, naphthyl, or carbon Heteroaryl groups of 3 to 20, each of which is unsubstituted or substituted with one or more of the following: a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, Alkyl, benzamyl, or alkoxy having 1 to 12 carbons; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached are free of or interspersed with O, S Or 5 or 6 membered NR ₁₇ saturated or unsaturated ring, and the above 5 or 6 membered saturated or unsaturated ring is unsubstituted or substituted with more than one of the following groups: alkane having 1 to 20 carbon atoms group, an alkoxy group having a carbon number of 1 to _{20, = O, OR 17, SR} 18, NR 21 R 22, C (O) R 23, NO 2, Atom, a haloalkyl group having a carbon number of 1 to 4, CN, phenyl, or interrupted by intermingled not more than one O, S, CO or NR ₁₇ carbon atoms of the cycloalkyl group having 3 to 20, or of formula ( C-VII); or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a heteroaromatic ring system, the above heteroaromatic ring system is unsubstituted or substituted with more than one of the following groups : Alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 20 carbon atoms, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , COR ₂₃ , halogen Atoms, NO ₂ , CN, phenyl, or cycloalkyl groups having 3 to 20 carbon atoms, or a group represented by formula (C-VII), which are not interspersed or interspersed with more than one O, S, CO, or NR ₁₇ .

R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; or R ₂₁ and R ₂₂ and the nitrogen atom attached to it form a saturated or unsaturated ring without 5 or 6 members of O, S or NR ₂₆ , and the saturated or unsaturated ring of 5 or 6 members mentioned above is unsaturated Condensation or condensation with benzene ring.

R ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms interspersed with one or more O, CO, or NR ₂₆ , A cycloalkyl group having a carbon number of 3 to 20 without being interspersed or interspersed with O, S, CO, or NR ₂₆ , or R ₂₃ represents a phenyl group, a naphthyl group, or a phenyl group (an alkyl group having 1 to 4 carbon atoms) , OR ₁₇ , SR _18, or NR ₂₁ R ₂₂ .

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

R ₂₅ means (CO) OR ₁₇ , (CO) R ₁₇ , (CO) NR ₁₉ R ₂₀ , or one of the meanings given for R ₁₇ .

R ₂₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, COR ₁₉ , and an alkyl group having 2 to 20 carbon atoms, with one or more O or CO interposed therebetween; or Is phenyl-an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, which is unsaturated or interspersed with more than one O or CO; or phenyl, which is unsubstituted Or substituted by more than one of the following groups: an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or formula (C-VII) Represented by the formula; provided that at least one of the groups represented by the formula (C-II) or the formula (C-VII) is present in the photoinitiator (C-1) having the structure of the formula (CI) group,

In Formula (FI), each of Z independently represents a halogen atom or an alkyl group having 1 to 5 carbon atoms; each of W ₁ independently represents a single bond or an alkylene group having 1 to 10 carbon atoms; multiple W ₂ Each independently represents a single bond, O, or an alkylene group having 1 to 10 carbon atoms; multiple W ₃ each independently represents a hydrogen atom, a group represented by formula (F-II) or formula (F-III); multiple L ₁ each independently represents a hydrogen atom or a methyl group; i each independently represents an integer of 0 to 4; j represents an integer of 0 to 2.

In formula (F-II) and formula (F-III), each of a plurality of L ₂ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; L ₃ represents a single bond or an alkylene group having 1 to 10 carbon atoms * Indicates a bonding site. Among the alkylene groups having 1 to 10 carbon atoms in the W ₁ , W _2, and L ₃ , any -CH ₂ -can be replaced with -O- , -CH = CH- or -C≡C-, and an arbitrary hydrogen atom may be replaced with a halogen atom.

In an embodiment of the present invention, the alkali-soluble resin (A) includes a resin (A-1) having an unsaturated group, and the resin (A-1) having an unsaturated group is polymerized from a mixture, and the mixture includes A diol compound (a-1-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride (a-1-2) thereof, and a dicarboxylic acid or an acid anhydride (a-1-3) thereof. The diol compound (a-1-1) containing a polymerizable unsaturated group is obtained by reacting an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. The epoxy compound having at least two epoxy groups includes a compound having a structure represented by formula (a-1-I), formula (a-1-II) or formula (a-1-III), or a combination thereof:

In the formula (a-1-I), A ¹ , A ² , A ^3, and A ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. An aryl group having 6 to 12 carbons or an aralkyl group having 6 to 12 carbons.

In the formula (a-1-II), A ⁵ to A ¹⁸ each 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 0 to 10 Integer.

In the formula (a-1-III), Ar ₃ represents a naphthalene ring, A ¹⁹ represents a cyano group, a halogen or a hydrocarbon group, and A ²⁰ represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkoxy group, or an alkane group. Thio, cycloalkylthio, arylthio, aralkylthio, fluorenyl, halogen, nitro, cyano, or substituted amino, A ²¹ represents an alkylene group, a represents an integer from 0 to 4, and b And c represents an integer of 0 or more.

In one embodiment of the present invention, in the photoinitiator (C-1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom. , An alkyl group having 1 to 20 carbons, a group represented by formula (C-II), COR ₁₆ or NO ₂ ; or any two of R ₁ to R ₈ whose relative positional relationship is adjacent to each other are mutually independent Is a group represented by formula (CV), provided that at least one of the two in which the relative positional relationship among R ₁ to R ₈ is ortho is a group represented by formula (CV); X represents CO or single bond.

R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, (CO) OR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , PO ( OC _k H _{2k + 1} ) ₂ ; or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms with one or more O, S, NR ₂₆ or CO interposed therebetween; or R ₁₃ represents phenyl or naphthyl, both These are unsubstituted or substituted with more than one COR ₁₆ or a group represented by formula (C-VII).

R ₁₄ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms; R ₁₅ represents a phenyl group, a naphthyl group, and a heteroaryl group having 3 to 20 carbon atoms, each of which is not Substituted or substituted with more than one of the following groups: phenyl, halogen atom, haloalkyl having 1 to 4 carbons, OR ₁₇ , SR _18, or alkyl having 2 to 20 carbons, in which more than one O or S; or each of them is substituted with more than one alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aryloxycarbonyl having 6 to 20 carbons, 4 to carbon 20's heteroaryloxycarbonyl group, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₅ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted One or more of the following groups substituted: OR ₁₇ , SR ₁₈ , cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, NR ₁₉ R ₂₀ , (CO) OR 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 Having one of the meanings given for R ₁₅ .

R ₁₆ represents a phenyl group, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a carbon number of 2 to 20 with one or more O, S, or NR ₂₆ interspersed. alkyl.

Or R ₁₆ represents a phenyl group, which is substituted by one or more alkyl groups having 1 to 20 carbon atoms, and the alkyl groups having 1 to 20 carbon atoms are unsubstituted or substituted by one or more of the following groups: a halogen atom, (CO OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl with 3 to 8 carbons, heteroaryl with 3 to 20 carbons, aryloxycarbonyl with 6 to 20 carbons, 4 carbons Heteroaryloxycarbonyl to 20, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with the following group: halogen atom, phenyl group , OH, SH, CN, alkenyloxy groups having 3 to 6 carbon atoms, OCH ₂ CH ₂ (CO) O- (alkyl groups having 1 to 4 carbon atoms), O (CO)-(carbon numbers from 1 to 4 alkyl) or (CO) O- (alkyl having 1 to 4 carbons).

R ₁₇ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms) , O- (alkyl group having 1 to 4 carbons), (CO) O- (alkyl group having 1 to 4 carbons), cycloalkyl group having 3 to 20 carbon atoms or interspersed with more than one oxygen atom A cycloalkyl group having a carbon number of 3 to 20; or R ₁₇ represents an alkyl group having a carbon number of 2 to 20 with one or more oxygen atoms interposed therebetween.

R ₁₈ represents a methyl group substituted with (CO) OR ₁₇ ; R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms or carbon Alkyloxy groups of 1 to 8; or R ₁₉ and R _{20 together} with the nitrogen atom to which they are attached form a heteroaromatic ring system, and the above heteroaromatic ring system is unsubstituted or via the formula (C- VII), but provided that at least one group represented by the formula (C-II) is present in the photoinitiator (C-1) having the structure of the formula (CI) or the formula (C -VII).

In one embodiment of the present invention, in the photoinitiator (C-1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom. ; Or R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ independently of each other are groups represented by formula (CV), provided that R ₁ and R ₂ , R ₃ and R ₄ or R At least one of ₅ and R ₆ is a group represented by formula (CV); or R ₂ represents a group represented by formula (C-II), COR ₁₆ , NO ₂ or by formula (C-III) A group represented by; or R ₇ represents a group represented by formula (C-II) or COR ₁₆ .

R ₉ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom; R ₁₀ represents a hydrogen atom, OR ₁₇ or COR ₁₆ ; X represents CO or a single bond; R ₁₃ represents a phenyl group; or R ₁₃ represents a carbon number of 1 to 20 Alkyl, which is unsubstituted or substituted with more than one of the following groups: a halogen atom, R ₁₇ , OR ₁₇ , SR ₁₈ or PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₃ represents a carbon number of 2 to 20 Alkyl group with one or more oxygen atoms interposed there; k represents 2.

R ₁₄ represents an alkyl or thienyl group having 1 to 20 carbons; R ₁₅ represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more OR ₁₇ or alkyl groups having 1 to 20 carbons; or R ₁₅ represents a thienyl group, a hydrogen atom, and an alkyl group having 1 to 20 carbon atoms. The above-mentioned alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , carbon A cycloalkyl group having a number of 3 to 8, NR ₁₉ R ₂₀ or (CO) OR ₁₇ ; or R ₁₅ represents an alkyl group having a carbon number of 2 to 20 with SO ₂ interposed therebetween.

R ₁₆ represents phenyl or naphthyl, each of which is unsubstituted or substituted with more than one of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or an alkyl group having 1 to 20 carbons; or R ₁₆ represents thiophene R ₁₇ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or have more than one of the following groups: a halogen atom, O (CO)- (Alkyl group having 1 to 4 carbons), O (CO)-(alkenyl group having 2 to 4 carbons) or a cycloalkyl group having 3 to 20 carbon atoms interspersed with one or more oxygen atoms; or R ₁₇ represents an alkyl group having 2 to 20 carbon atoms with one or more oxygen atoms interposed therebetween.

R ₁₈ represents a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and it is unsubstituted or substituted with more than one OH, O (CO)-(alkenyl group having 2 to 4 carbon atoms) ) Or (CO) OR ₁₇ ; or R ₁₈ represents a phenyl group, which is unsubstituted or substituted with one or more halogen atoms; R ₁₉ and R ₂₀ each independently represent an alkyl group or carbon number having 1 to 8 carbon atoms Is an alkanoyloxy group of 1 to 8; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a 5-membered or 6-membered saturated ring having an oxygen atom; provided that the compound has the formula (CI) The photoinitiator (C-1) has at least one group represented by the formula (C-II).

In one embodiment of the present invention, the inorganic oxide particles (G) further include silicon compound particles, aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, or barium compound particles. Or these composite particles.

In an embodiment of the present invention, the amount of the alkali-soluble resin (A) is 100 parts by weight, the amount of the ethylenically unsaturated group-containing compound (B) is 15 to 150 parts by weight, and the photoinitiator ( C) is used in an amount of 10 to 100 parts by weight, solvent (D) is used in an amount of 1000 to 6000 parts by weight, black pigment (E) is used in an amount of 100 to 600 parts by weight, and contains a compound represented by formula (FI) The compound (F) having an epoxy group structure is used in an amount of 10 to 180 parts by weight.

In one embodiment of the present invention, the amount of the alkali-soluble resin (A) is 100 parts by weight, and the amount of the resin (A-1) having an unsaturated group is 30 to 100 parts by weight.

In one embodiment of the present invention, the amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the light initiator (C-1) having the structure of the formula (C-I) is 5 to 100 parts by weight.

In one embodiment of the present invention, the amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the inorganic oxide fine particles (G) used is 2 to 10 parts by weight.

The present invention further provides a black matrix formed by using the above-mentioned photosensitive resin composition for a black matrix, which is sequentially subjected to a pre-baking process, an exposure process, a development process, and a post-baking process.

The present invention further provides a color filter including the black matrix described above.

The present invention further provides a liquid crystal display device including the above-mentioned color filter.

Based on the above, since the photosensitive resin composition for a black matrix of the present invention contains a specific photoinitiator (C-1) and a compound (F) having an epoxy group structure represented by formula (FI), it can be used in Without increasing the amount of black pigment, an appropriate bluish chromaticity can still be obtained.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

<Photosensitive resin composition for black matrix>

The present invention provides a photosensitive resin composition for a black matrix, comprising: an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D), and a black pigment ( E) and a compound (F) having an epoxy group structure represented by the formula (FI). The photosensitive resin composition for a black matrix of the present invention may further contain inorganic oxide fine particles (G) and additives (H).

Hereinafter, each component of the photosensitive resin composition for black matrices used for this invention is demonstrated in detail.

Here, it is explained that acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acrylate and / or methacrylic acid ester are represented by (meth) acrylic acid ester; similarly, (meth) Acrylofluorenyl refers to acrylfluorenyl and / or methacrylfluorenyl.

Alkali soluble resin (A)

The alkali-soluble resin (A) includes a resin (A-1) having an unsaturated group and other alkali-soluble resins (A-2).

Resin with unsaturated group (A-1)

The resin (A-1) having an unsaturated group is obtained by polymerizing a mixture. The mixture includes a diol compound (a-1-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride (a-1-2) thereof, and a dicarboxylic acid or an acid anhydride (a-1-3) thereof.

Polymerizable unsaturated group-containing diol compound (a-1-1)

The diol compound (a-1-1) containing a polymerizable unsaturated group is obtained by reacting an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. .

The epoxy compound having at least two epoxy groups includes a structure represented by the formula (a-1-I), a structure represented by the formula (a-1-II), and a structure represented by the formula (a-1-III) , Or the above three structures. Hereinafter, the structure represented by Formula (a-1-I), the structure represented by Formula (a-1-II), and the structure represented by Formula (a-1-III) will be specifically described.

Specifically, the structure represented by formula (a-1-I) is as follows:

In the formula (a-1-I), A ¹ , A ² , A ^3, and A ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. An aryl group having 6 to 12 carbons or an aralkyl group having 6 to 12 carbons.

The epoxy compound having at least two epoxy groups containing a structure represented by formula (a-1-I) may include a bisphenol fluorene having an epoxy group obtained by reacting a bisphenol fluorene type compound with a halogenated propylene oxide. Type compound.

Specifically, specific examples of the bisphenol hydrazone compound include: 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) 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) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4 -Hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, or an analogue thereof, or a combination thereof.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-propylene oxide or 3-bromo-1,2-propylene oxide or the like, or a combination thereof.

Specific examples of the bisphenol amidine compound having an epoxy group include (1) a product manufactured by Nippon Steel Chemical: for example, ESF-300 or the like; (2) a product manufactured by Osaka Gas: for example, PG-100, EG- 210 or its analog; (3) SMS Technology Co. Goods manufactured: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.

In addition, specifically, the structure represented by the formula (a-1-II) is as follows:

In the formula (a-1-II), A ⁵ to A ¹⁸ each 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 0 to 10 Integer.

The epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-1-II) may be included in the presence of an alkali metal hydroxide such that the compound having the structure of the following formula (a-1-II ') The compound is obtained by reacting a halogenated propylene oxide.

In the formula (a-1-II ') , A and A ¹⁸ s to ⁵ defined in formula, respectively (a-1-II) A 5 to A ^18, and s is the same as defined, which is not repeated herein.

For a method for synthesizing an epoxy compound having a structure represented by formula (a-1-II) and having at least two epoxy groups, refer to Taiwan Patent Publication No. TW201508418.

Specific examples of the epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-1-II) include trade names such as NC-3000, NC-3000H, NC-3000S, and NC-3000P. A product made by Nippon Kayaku.

In addition, specifically, the structure represented by the formula (a-1-III) is as follows:

In the formula (a-1-III), Ar ₃ represents a naphthalene ring, A ¹⁹ represents a cyano group, a halogen or a hydrocarbon group, and A ²⁰ represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkoxy group, or an alkane group. Thio, cycloalkylthio, arylthio, aralkylthio, fluorenyl, halogen, nitro, cyano, or substituted amino, A ²¹ represents an alkylene group, a represents an integer from 0 to 4, and b And c represents an integer of 0 or more.

Specific examples of the epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-1-III) include 9,9-bis (glycidyloxynaphthyl) fluorene and, for example, 9 , 9-bis (6-glycidyloxy-2-naphthyl) fluorene or 9,9-bis (5-glycidyloxy-1-naphthyl) fluorene and the like.

The compound having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from one of the group consisting of (1) to (3): (1) acrylic acid, methacrylic acid, 2-methacrylic acid Phenoxyethylsuccinic acid, 2-methacrylic acid, oxybutyl succinic acid, 2-methacrylic acid, oxyethyl adipic acid, 2-methacrylic acid, oxybutyl adipate, 2-methyl Acrylic acid oxyethyl hexahydrophthalic acid, 2-methacrylic acid oxyethyl maleic acid, 2-methacrylic acid oxypropyl maleic acid, 2-methacrylic acid oxybutyl maleic acid Acid, 2-methacryloxypropyl succinic acid, 2-methacryloxypropyl succinic acid Diacid, 2-methacrylic acid oxytetrahydrophthalic acid, 2-methacrylic acid oxypropyl phthalic acid, 2-methacrylic acid oxybutyl phthalic acid, 2-methyl Acrylic acid, oxybutyl hydrophthalic acid, or the like; (2) Compound obtained by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound, and specific examples of the dicarboxylic acid compound Including adipic acid, succinic acid, maleic acid, phthalic acid or the like; and (3) a half-ester compound obtained by reacting a (meth) acrylic acid ester having a hydroxyl group with a carboxylic acid anhydride compound, wherein Specific examples of the hydroxy (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4- Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate or the like.

In addition, the carboxylic acid anhydride compound described here is the same as the tetracarboxylic dianhydride or dicarboxylic anhydride described below, and will not be repeated here.

Tetracarboxylic acid or its dianhydride (a-1-2)

The tetracarboxylic acid or its acid dianhydride (a-1-2) includes a tetracarboxylic acid or an acid dianhydride containing a fluorine atom, and a tetracarboxylic acid other than the tetracarboxylic acid or an acid dianhydride containing a fluorine atom. Acid or acid dianhydride or a combination of both.

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

In formulae (K-1) and (K-2), K ² is a tetravalent aromatic group having fluorine, and preferably has a benzene ring. Specifically, it is preferably one selected from the group represented by 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.

Specifically, specific examples of the tetracarboxylic acid or an acid dianhydride containing a fluorine atom include 4,4'-hexafluoroisopropylidene diphthalic acid, 1,4-difluoropyrellitic acid, 1- Fluorine-containing aromatic tetracarboxylic acids such as monofluoropyrellitic acid and 1,4-bis (trifluoromethyl) pyromellitic acid, or the dianhydride compounds of the aforementioned tetracarboxylic acids, or a combination of the aforementioned compounds.

Specific examples of the tetracarboxylic acid containing a fluorine atom or an acid dianhydride thereof include 3,3'-hexafluoroisopropylidene diphthalic acid, 5,5 '-[2,2,2-trifluoro-1 -[3- (trifluoromethyl) phenyl] ethylene] diphthalic acid, 5,5 '-[2,2,3,3,3-pentafluoro-1- (trifluoromethyl) Propylene] diphthalic acid, 5,5'-oxybis [4,6,7-trifluoro-pyrellitic acid], 3,6-bis (trifluoromethyl) pyromellitic acid, Fluorine-containing tetracarboxylic acids such as 4- (trifluoromethyl) pyromellitic acid, 1,4-bis (3,4-dicarboxylic acid trifluorophenoxy) tetrafluorobenzene, or two of the aforementioned tetracarboxylic acids An anhydride compound, or a combination thereof.

Other tetracarboxylic acids or acid dianhydrides thereof include saturated linear hydrocarbon tetracarboxylic acids, alicyclic tetracarboxylic acids, aromatic tetracarboxylic acids, or dianhydride compounds of the aforementioned tetracarboxylic acids, or a combination thereof.

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

Specific examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, norbornane tetracarboxylic acid, or a combination of the foregoing compounds. The alicyclic tetracarboxylic acid may have a substituent.

Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenylphosphonium tetracarboxylic acid, 1,2,3,6 -Tetrahydrophthalic acid, or a combination of the above. Aromatic tetracarboxylic acids may have substitutions base.

Dicarboxylic acid or its anhydride (a-1-3)

The dicarboxylic acid or its anhydride (a-1-3) includes a dicarboxylic acid or an anhydride thereof containing a fluorine atom, and a dicarboxylic acid or an anhydride thereof other than the dicarboxylic acid or an anhydride thereof containing the fluorine atom or the above A combination of both.

A fluorine atom-containing dicarboxylic acid 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 acid anhydride compound represented by the formula (M-2) . Specifically, 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) are as follows.

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

Specific examples of the fluorine atom-containing dicarboxylic acid or its anhydride include 3-fluorophthalic acid, 4-fluorophthalic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, and tetrafluoro Succinic acid, or an anhydride compound of the aforementioned dicarboxylic acid, or a combination of the aforementioned 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, an acid anhydride of the aforementioned dicarboxylic acid compound, or a combination of the aforementioned compounds.

Specific examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetosuccinic acid, adipic acid, azelaic acid, citrate, malonic acid, glutaric acid, citric acid, tartaric acid, oxopent Diacid, pimelic acid, sebacic acid, suberic acid, diethylene glycol acid, or a combination thereof. Hydrocarbon groups in saturated linear hydrocarbon dicarboxylic acids 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 above compounds combination. The saturated cyclic hydrocarbon dicarboxylic acid may also be a saturated hydrocarbon substituted alicyclic dicarboxylic acid.

Specific examples of unsaturated dicarboxylic acids include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl bridge methylenetetrahydrophthalic acid, chlorinic acid, trimellitic acid , Or a combination of the above.

Specific examples of other dicarboxylic acids or anhydrides thereof include trimethoxysilylpropylsuccinic anhydride, triethoxysilylpropylsuccinic anhydride, methyldimethoxysilylpropylsuccinic anhydride, methyl Diethoxysilylpropylsuccinic anhydride, trimethoxysilylbutylsuccinic anhydride, triethoxysilylbutylsuccinic anhydride, methyldiethoxysilylbutylsuccinic anhydride, (Trimethoxysilyl) phenylsuccinic anhydride, p- (triethoxysilyl) phenylsuccinic anhydride, p- (methyldimethoxysilyl) phenylsuccinic anhydride, p- (methyldimethoxysilyl) (Ethoxysilyl) phenylsuccinic anhydride, m- (trimethoxysilyl) phenylsuccinic anhydride, m- (triethoxysilyl) phenylsuccinic anhydride, m- (methyldiethoxysilane) Group) a dicarboxylic anhydride such as phenylsuccinic anhydride, a dicarboxylic acid compound of the aforementioned dicarboxylic anhydride, or a combination of the aforementioned compounds.

The method for synthesizing the resin (A-1) having an unsaturated group is not particularly limited, The diol compound (a-1-1) containing a polymerizable unsaturated group, the tetracarboxylic dianhydride or its tetracarboxylic acid (a-1-2), and the dicarboxylic anhydride or its dicarboxylic acid (a-1) -3) The reaction can be obtained, and it can be synthesized by referring to the patent of Taiwan Publication No. TW201508418.

The polystyrene-equivalent weight average molecular weight of the resin (A-1) having an unsaturated group according to the present invention as measured by Gel Permeation Chromatography (GPC) is 1000 to 8000, preferably 1500. To 7500, more preferably 2000 to 7000.

The use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the resin (A-1) having an unsaturated group is 30 to 100 parts by weight, preferably 50 to 100 parts by weight, and more preferably 70. To 100 parts by weight.

When the resin (A-1) having an unsaturated group is contained in the photosensitive resin composition for a black matrix, the obtained black matrix can further obtain a more appropriate bluishness.

Other alkali-soluble resins (A-2)

The alkali-soluble resin (A) may optionally include other alkali-soluble resins (A-2). The other alkali-soluble resin (A-2) is a resin other than the resin (A-1) having an unsaturated group. The other alkali-soluble resin (A-2) is, for example, a resin having a carboxylic acid group or a hydroxyl group, but is not limited to a resin having a carboxylic acid group or a hydroxyl group. Specific examples of the other alkali-soluble resin (A-2) include resins such as acrylic resins, polysiloxanes, urethane resins, and novolac resins.

Acrylic resin is composed of unsaturated carboxylic acid or unsaturated carboxylic anhydride compound, And other unsaturated compounds are obtained by copolymerization in a solvent in the presence of a suitable polymerization initiator.

Polysiloxane is synthesized by polycondensation of silane monomer, or by polycondensation using silane monomer and other polymerizable compounds. Silane monomers include monofunctional silane monomers, difunctional silane monomers, trifunctional silane monomers and tetrafunctional silane monomers; other polymerizable compounds include siloxane prepolymers, silicon dioxide particles, Or a combination.

Based on the use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the other alkali-soluble resin (A-2) is 0 to 70 parts by weight, preferably 0 to 50 parts by weight, and more preferably 0 to 30. Parts by weight.

Compound (B) with ethylenically unsaturated group

The compound (B) having an ethylenically unsaturated group may be selected from a compound having one ethylenically unsaturated group or a compound having two or more (including two) ethylenically unsaturated groups.

The aforementioned compound having one ethylenically unsaturated group may include, but is not limited to, (meth) acrylamidoamine, (meth) acrylamidomorpholine, (meth) acrylic acid 7-amino-3,7-dimethyl Octyl ester, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Ethyl diethylene glycol (meth) acrylate, third octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, ( Dodecyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromo (meth) acrylate Phenyl ester, 2-tribromophenoxyethyl (meth) acrylate, ethyl 2-hydroxy- (meth) acrylate, propyl 2-hydroxy- (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene mono (meth) acrylate, polymono Compounds such as propylene (meth) acrylate or norbornyl (meth) acrylate. The compound having one ethylenically unsaturated group may be used alone or in combination.

The aforementioned compound having two or more ethylenically unsaturated groups may include, but is not limited to, ethylene glycol di (meth) acrylate, dicyclopentene di (meth) acrylate, and triethylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanate di (meth) acrylate, tris (2-hydroxyethyl) isocyanate (Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanate tris (meth) acrylate, tris (methyl) acrylate trimethylolpropyl, ethylene oxide ( (EO for short) modified trimethylol propyl (meth) acrylate, propylene oxide modified (PO for short) trimethylol propyl (meth) acrylate, tripropylene glycol di (meth) acrylic acid Ester, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyester di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone Pentaerythritol hexa (a Base) acrylate, dipentaerythritol penta (meth) acrylate modified by caprolactone, ditrimethylolpropyl tetra (meth) acrylate, bisphenol A bis (methyl) modified by ethylene oxide ) Acrylate, bisphenol A di (meth) acrylate modified by propylene oxide, hydrogenated bisphenol A di (meth) acrylate modified by ethylene oxide, hydrogenated by propylene oxide Compounds such as bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate modified by ethylene oxide, or novolac polyglycidyl ether (meth) acrylate. The compounds having two or more (including two) ethylenically unsaturated groups may be used alone or in combination.

Specific examples of the compound (B) having an ethylenically unsaturated group may include, but are not limited to, trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified with ethylene oxide, and propylene oxide Modified trimethylolpropyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate Esters, ditrimethylol propyl tetraacrylate, glycerol triacrylate modified with propylene oxide, or any combination thereof.

The compound (B) having an ethylenically unsaturated group may preferably be trimethylolpropyl triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or any combination thereof.

The use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the compound (B) having an ethylenically unsaturated group is 15 to 150 parts by weight, preferably 20 to 130 parts by weight, and more preferably 25 to 100 parts by weight.

Photoinitiator (C)

The photoinitiator (C) includes a photoinitiator (C-1) having a structure of the formula (C-I) and other photoinitiators (C-2).

Here, it is explained that the following "any of the relative positional relationship between R ¹ to R ⁸ is an ortho position" means any two substituents whose relative position is an ortho position in the structure of the following formula (CI). For example: 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 and so on.

Photoinitiator (C-1) having the structure of formula (C-I)

The photoinitiator (C-1) having the formula (CI) structure is shown below:

In Formula (CI), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R _7, and R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, COR ₁₆ , OR ₁₇ , a halogen atom, NO ₂ , a group represented by the formula (C-II) or a group represented by the formula (C-III); Or any two of R ₁ to R ₈ whose relative positional relationship is adjacent to each other independently represent an alkenyl group substituted by a group represented by formula (C-IV) and having a carbon number of 2 to 10; ₁ ~ R ₈ or the relative positional relationship of both R ortho to one another independently of any common is _{- (CH 2) p -Y- (} CH 2) q - , or a group represented by the formula (CV) represents; However, the condition is that at least one pair of any of the two in which the relative positional relationship among R ₁ to R ₈ is adjacent is a group represented by formula (CV).

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or has one or more of the following groups Substitution: halogen atom, phenyl, CN, OH, SH, alkoxy group having 1 to 4 carbon atoms, COOH or COOR ^X ; R ^X represents an alkyl group having 1 to 4 carbon atoms; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently an unsubstituted phenyl group or a phenyl group substituted with one or more of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OR ₁₇ , SR _18, or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a halogen atom, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substituent OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally form a 5- or 6-membered ring with one carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and / or R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ , NO ₂ or formula (C-II); Y represents O, S, NR ₂₆ or a single bond; p represents an integer of 0 to 3; q Represents an integer from 1 to 3; X represents CO or a single bond.

R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, R ₁₇ , (CO) OR 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 formula (C-VI); Or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms, interspersed with more than one O, S, SO, SO ₂ , NR ₂₆ or CO, or an alkenyl group having 2 to 12 carbon atoms, which is not interspersed Or interspersed with more than one O, NR ₂₆ or CO, wherein the alkyl group having 2 to 20 carbon atoms and the alkenyl group having 2 to 12 carbon atoms Substituted or substituted with more than one halogen atom; or R ₁₃ represents a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or one or more O, S, and NR ₂₆ not interspersed or interspersed Or a cycloalkyl group having a carbon number of 3 to 10; or R ₁₃ represents a phenyl group or a 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 atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, carbon number having 2 or more O, S, NR ₂₆ or CO interspersed with 2 An alkyl group to 20, or a group represented by formula (C-VII); Or each of them is substituted by a cycloalkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms interspersed with one or more O, S, NR ₂₆ or CO; k represents an integer of 1 to 10;

R ₁₄ represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, which is Unsubstituted or substituted with more than one of the following: a halogen atom, a phenyl group, an alkylphenyl group having 1 to 20 carbon atoms or CN; or R ₁₄ represents a phenyl group or a naphthyl group, each of which is unsubstituted or substituted One or more of the following groups substituted: an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, CN, OR ₁₇ , SR _18, and / or NR ₁₉ R ₂₀ ; or R ₁₄ represents Heteroaryl group having 3 to 20 carbon atoms, alkoxy group, benzyloxy group or phenoxy group having 1 to 8 carbon atoms, said benzyloxy group and phenoxy group being unsubstituted or having more than one of the following groups Group substitution: an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and / or a halogen atom.

R ₁₅ is an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen atom, carbon number 1 To 4 haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , SO-carbon number 1 to 10, SO ₂ -number of carbon An alkyl group of 1 to 10, an alkyl group of 2 to 20 carbons interspersed with more than one O, S or NR ₂₆ ; or each of which is substituted with an alkyl group of 1 to 20 carbons, the carbon number is 1 to 20 alkyl groups are unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, carbon number A heteroaryl group of 3 to 20, an aryloxycarbonyl group of 6 to 20 carbons, a heteroaryloxycarbonyl group of 3 to 20 carbons, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents hydrogen Atoms, alkenyl groups having 2 to 12 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms that are not interspersed or interspersed with more than one O, CO, or NR ₂₆ ; or R ₁₅ is 1 to 20 carbon atoms alkyl, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, oR _17, SR _18, A cycloalkyl group having 3 to 8 carbon atoms, a hetero aryl group of 3-20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbons, aryloxycarbonyl heteroaryl group having 3 to 20, NR ₁₉ R ₂₀ (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , phenyl, a group represented by formula (C-VI) or a group represented by formula (C-VIII); Or the alkyl group having 1 to 20 carbon atoms is substituted by a phenyl group, the phenyl group is substituted by a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ substitution; or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms, interspersed with more than one O, SO or SO ₂ , and the alkyl group having 2 to 20 carbon atoms interspersed A radical is unsubstituted or substituted with more than one of the following groups: halogen atom, OR ₁₇ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; Or R ₁₅ represents an alkyl or benzamyl group having 2 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, benzene OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is a naphthylmethyl group which is unsubstituted or substituted with more than one OR ₁₇ or a heteroarylcarbonyl group having 3 to 14 carbons; or R ₁₅ Represents an alkoxycarbonyl group having a carbon number of 2 to 12, which is an unsubstituted or unsubstituted one, and the alkoxycarbonyl group having an unsubstituted or unsubstituted carbon number of 2 to 12 is unsubstituted. Or via more than one hydroxyl group ; Or R ₁₅ represents a phenoxycarbonyl group which is unsubstituted or substituted with one or more of the following groups: alkyl having 1 to 6, a halogen atom, a C 1-4 haloalkyl group, a phenyl group OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , haloalkyl having 1 to 4 carbons, S (O) _m -alkane having 1 to 6 carbons Group, unsubstituted or S (O) _m -phenyl substituted with alkyl having 1 to 12 carbons or SO ₂ -alkyl having 1 to 6 carbons; or R ₁₅ represents S (O ₂ ) O -Phenyl, which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms; or a diphenylphosphinofluorenyl group or a di- (alkoxy group having 1 to 4 carbon atoms) -phosphinofluorenyl group; m represents 1 or 2; R _'14 has one of the meanings given for R ₁₄ ; R' ₁₅ has one of the meanings given for R ₁₅ ; X ₁ represents O, S, SO or SO ₂ ; X ₂ represents O, CO, S or a single bond.

R ₁₆ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a phenyl group, a halogen atom, and a carbon number of 1 To 4 halogenated alkyl groups, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or alkyl groups having 1 to 20 carbon atoms interspersed with more than one O, S or NR ₂₆ ; Is substituted by an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: a halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , Phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aryloxycarbonyl having 6 to 20 carbons, heteroaryloxycarbonyl having 3 to 20 carbons OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following Group substitution: halogen atom, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (carbon number 1 to 4 Alkyl), O (CO)-(alkyl with 1 to 4 carbons), O (CO) -phenyl, COOH or (CO) O- (carbon Alkyl of 1 to 4); or R ₁₆ represents alkyl having 2 to 12, have therebetween one or more heteroatoms O, S or NR _26; or R ₁₆ represents _{(CH 2 CH 2 O) n} + 1 H (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), alkenyl group having 2 to 12 carbon atoms or cycloalkyl group having 3 to 8 carbon atoms; or R ₁₆ represents SR ₁₈ substituted phenyl, wherein the group R ₁₈ represents a single bond bonded to a phenyl or naphthyl ring of a carbazole moiety having a COR ₁₆ group attached thereto; n represents an integer of 1-20.

R ₁₇ represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 3 carbon atoms), and an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, OH , SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms), O (CO)-(carbon Alkyl groups of 1 to 4), O (CO)-(alkenyl groups of 2 to 4 carbons), O (CO)-(phenyl), COOH, (CO) O- (carbon numbers of 1 to 4 alkyl), cycloalkyl having 3 to 20 carbons, SO _2- (haloalkyl having 1 to 4 carbons), O- (haloalkyl having 1 to 4 carbons), or more than one A cycloalkyl group having 3 to 20 carbon atoms in the oxygen atom; or R ₁₇ represents an alkyl group having 2 to 20 carbon atoms with one or more O, S or NR ₂₆ interposed therebetween; or R ₁₇ represents (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), alkyl fluorenyl group having 1 to 8 carbon atoms, and 2 to 12 carbon atoms Alkenyl, alkenyl having 3 to 6 carbon atoms, or cycloalkyl having 3 to 20 carbon atoms without interspersed or interspersed with more than one O, S, CO, or NR ₂₆ ; or R ₁₇ represents a carbon number of 1 to 8 alkyl-cycloalkyl groups having 3 to 10 carbon atoms Has more than one oxygen atom; or R ₁₇ represents benzamidine, which is unsubstituted or has more than one alkyl group having 1 to 6 carbon atoms, a halogen atom, OH, or an alkoxy group having 1 to 3 carbon atoms Or R ₁₇ represents a phenyl group, a naphthyl group, or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a halogen atom, OH, and a carbon number of 1 to Alkyl group 12, carbon number 1 to 12, alkoxy group, CN, NO ₂ , phenyl- (alkoxy group number 1 to 3), phenoxy group, alkyl group number 1 to 12 A thio group, a phenylthio group, N (an alkyl group having 1 to 12 carbons) ₂ , a diphenyl-amino group, or a group represented by the formula (C-VII); or R ₁₇ forms a bond to the group A single bond having one of the carbon atoms of the phenyl or naphthyl ring in which the group represented by formula (C-II) or the group represented by formula (C-VII) is located.

R ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl group (an alkyl group having 1 to 3 carbon atoms), wherein the carbon number is 2 to Alkenyl of 12, cycloalkyl having 3 to 20 carbon atoms or phenyl- (alkyl having 1 to 3 carbon atoms) is unsubstituted or interspersed with more than one O, S, NR ₂₆ , CO, or ( CO) OR ₁₇ ; or R ₁₈ is an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: OH, SH, CN, and an alkenyl group having 3 to 6 carbon atoms , OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl having 1 to 4 carbons), O (CO)-(alkenyl having 2 to 4 carbons), O (CO)- (Alkyl group having 1 to 4 carbons), O (CO)-(phenyl) or (CO) OR ₁₇ ; or R ₁₈ represents an alkyl group having 2 to 20 carbons, with one or more O, S, NR ₂₆ , CO or (CO) OR ₁₇ ; or R ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons) 2, an alkylfluorenyl group having 2 to 8 carbons or an alkenyl group having 3 to 6 carbons; or R ₁₈ represents a benzamyl group, which is unsubstituted or substituted with more than one of the following groups: the carbon number is 1 to 6 alkyl, halogen atom, OH, 1 to 4 alkoxy or Alkyl having 1 to 4 group; R ₁₈ represents a phenyl or naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted by one or more of the following groups: a halogen atom , Alkyl group having 1 to 12 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 12 carbon atoms, CN, NO ₂ , phenyl- (alkoxy group having 1 to 3 carbon atoms Group), phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (alkyl group having 1 to 12 carbon atoms) ₂ , diphenylamino group, (CO) O- ( (C1-C8 alkyl group), (CO)-(C1-C8 alkyl group), C (O) N- (C1-C8 alkyl group) ₂ or formula (C- VII).

R ₁₉ and R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and 2 carbon atoms Alkenyl to 5, cycloalkyl having 3 to 20 carbons, phenyl- (alkyl having 1 to 3 carbons), alkylsulfonyl having 1 to 8 carbons, and 1 to 8 carbons Alkyl alkoxy, alkenyl with 3 to 12 carbons, SO _2- (haloalkyl with 1 to 4 carbons) or benzamyl; or R ₁₉ and R ₂₀ represent phenyl, naphthyl or Heteroaryl groups having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with more than one of the following groups: halogen atom, haloalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 20 carbon atoms , An alkyl group having a carbon number of 1 to 12, a benzamyl group, or an alkoxy group having a carbon number of 1 to 12; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached are not interspersed or interspersed with O, 5 or 6 membered S or NR ₁₇ saturated or unsaturated rings, and the 5 or 6 membered saturated or unsaturated ring is unsubstituted or substituted with more than one of the following groups: 1 to 20 carbons alkyl group, an alkoxy group having a carbon number of 1 to _{20, = O, OR 17, SR} 18, NR 21 R 22, COR 23, NO 2, halogen Atoms, a haloalkyl group having a carbon number of 1 to 4, CN, phenyl, or interrupted by intermingled not more than one O, S, CO or NR ₁₇ carbon atoms of the cycloalkyl group having 3 to 20, or Formula (C -VII); or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a heteroaromatic ring system that is unsubstituted or substituted with more than one of the following groups: the carbon number is Alkyl group of 1 to 20, haloalkyl group of 1 to 4 carbons, alkoxy group of 1 to 20 carbons, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , COR ₂₃ , halogen atom, NO ₂ , CN, phenyl, or a cycloalkyl group having 3 to 20 carbon atoms, or a group represented by formula (C-VII), which is unsubstituted or interspersed with one or more O, S, CO, or NR ₁₇ .

R ₂₁ and R ₂₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; or R ₂₁ and R ₂₂ together with the nitrogen atom to which it is attached form a 5- or 6-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S, or NR ₂₆ , and the 5- or 6-membered saturated or unsaturated ring is unsaturated Condensation or the 5- or 6-membered saturated or unsaturated ring is condensed with a benzene ring.

R ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms interspersed with one or more O, CO, or NR ₂₆ , A cycloalkyl group having a carbon number of 3 to 20 without being interspersed or interspersed with O, S, CO, or NR ₂₆ , or R ₂₃ represents a phenyl group, a naphthyl group, or a phenyl group (an alkyl group having 1 to 4 carbon atoms) , OR ₁₇ , SR _18, or NR ₂₁ R ₂₂ .

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

R ₂₅ represents (CO) OR ₁₇ , (CO) NR ₁₉ R ₂₀ , (CO) R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ .

R ₂₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, COR ₁₉ , and an alkyl group having 2 to 20 carbon atoms, with one or more O or CO interposed therebetween; or Is phenyl-an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, which is unsaturated or interspersed with more than one O or CO; or phenyl, which is unsubstituted Or substituted by more than one of the following groups: an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or formula (C-VII) Group provided that at least one group represented by the formula (C-II) or the formula (C-VII) is present in the photoinitiator (C-1) having the structure of the formula (CI).

The compound of formula (CI) is characterized in that it contains more than one annelated unsaturated ring on the carbazole moiety. In other words, at least one of any two of R ₁ to R ₈ whose relative positional relationship is adjacent is a group represented by formula (CV).

An alkyl group having 1 to 20 carbons is a straight or branched chain and is, for example, an alkyl group having 1 to 18 carbons, an alkyl group having 1 to 4 carbons, an alkyl group having 1 to 12 carbons, An alkyl group having 1 to 8 carbons, an alkyl group having 1 to 4 carbons, an alkyl group having 4 to 12 carbons, or an alkyl group having 4 to 8 carbons. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Amyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and icosyl. An alkyl group having 1 to 6 carbons has the same meaning as given above for an alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms.

An unsubstituted or substituted alkyl group having 1 to 20 carbon atoms containing more than one C-C multiple bond refers to an alkenyl group as explained below.

Haloalkyl having 1 to 4 carbons is an alkyl having 1 to 4 carbons as defined above substituted with a halogen atom as defined below. Alkyl groups are, for example, mono- or polyhalogenated until all hydrogen atoms are replaced with halogen atoms. Which is (e.g.) C _z H _x Hal _y, wherein x + y = 2z + 1 and Hal is a halogen atom, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. A hydroxyalkyl group having 2 to 4 carbons means an alkyl group having 2 to 4 carbons substituted with one or two oxygen atoms. Alkyl groups are 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. An alkoxyalkyl group having 2 to 10 carbons is an alkyl group having 2 to 10 carbons interspersed with an oxygen atom. An alkyl group having 2 to 10 carbons has the same meaning as given above for an alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, Propoxypropyl.

Interrupted by one or more O, C S, NR ₂₆ CO, or an alkyl group of atoms by O 2 to 20, S, NR ₂₆ or CO interrupted (e.g.) 1-9 times, 1-5 times, 1-3 times Or once or twice. If more than one mesohetero group is present, they are the same kind or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylene). The isoalkyl is linear or branched. For example, the following structural units will exist: -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 ) -NR 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 .

A cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms are to be understood in the context of this application as an alkyl group containing at least one ring. It is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. A cycloalkyl group having 3 to 10 carbons is also intended to encompass bicyclic rings in the context of the present invention, in other words, bridged rings such as

And the corresponding ring. Other examples are such as (E.g ) Or And other structures, as well as bridged or condensed ring systems, for example, the terms are intended to cover: , , And other structures.

A cycloalkyl group having 3 to 20 carbon atoms 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 with O, S, CO, or NR ₂₆ . Examples are such as (E.g ), , And other structures.

Alkyl groups of 1 to 8-cycloalkyls of 3 to 10 carbons are cycloalkanes of 3 to 10 carbons as defined above substituted with one or more alkyl groups having up to 8 carbon atoms base. Examples are: , Wait.

Alkyl groups having 1 to 8 carbons interspersed with more than one oxygen atom ((cycloalkyls having 3 to 10 carbons)) are substituted with one or more alkyl groups having up to 8 carbon atoms as defined above A cycloalkyl group having 3 to 10 hetero carbons between oxygen atoms. Examples are: , Wait.

An alkoxy group having 1 to 12 carbon atoms is substituted with an oxygen atom having a carbon number of 1 To 12 alkyl. An alkyl group having 1 to 12 carbons has the same meaning as given above for an alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms. Alkoxy groups having 1 to 4 carbon atoms are straight or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy Or third butoxy. The alkoxy group having 1 to 8 carbons and the alkoxy group having 1 to 4 carbons have the same meaning as described above and have the highest corresponding number of carbon atoms.

The alkylthio group having 1 to 12 carbons is an alkyl group having 1 to 12 carbons substituted with one S atom. An alkyl group having 1 to 20 carbons has the same meaning as given above for an alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms. Alkylthio groups having 1 to 4 carbon atoms are straight or branched, such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, second butyl Thio, isobutylthio, and third butylthio.

The phenyl-alkyl group having 1 to 3 carbon atoms is, for example, benzyl, phenylethyl, α-methylbenzyl or α, α-dimethyl-benzyl, especially benzyl.

Phenyl-alkoxy having 1 to 3 carbon atoms is, for example, benzyloxy, phenylethoxy, α-methylbenzyloxy or α, α-dimethylbenzyloxy, especially benzyloxy.

Alkenyl groups having 2 to 12 carbons are mono- or polyunsaturated and are, for example, alkenyl groups having 2 to 10 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, and alkenyl groups having 2 to 5 carbon atoms , Such as vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentane Alkenyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. Alkenyl groups having 2 to 5 carbons have the same meaning as given above for alkenyl groups having 2 to 12 carbons and have the highest corresponding number of carbon atoms.

Interrupted by one or more O, CO or NR carbon ₂₆ of the alkenyl group via O 2 to 12, CO or NR ₂₆ interrupted (e.g.) 1-9 times, 1-5 times, 1-3 times or once or 2 times. If more than one mesohetero group is present, they are the same kind or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylene). Alkenyl is straight or branched and is as defined above. For example, the following structural units may be formed: -CH = CH-O-CH ₂ CH ₃ , -CH = CH-O-CH = CH ₂ and the like.

A cycloalkenyl group having 4 to 8 carbon atoms has one or more double bonds and is, for example, a cycloalkenyl group having 4 to 6 carbon atoms or a cycloalkenyl group having 6 to 8 carbon atoms. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

Alkenyloxy groups having 3 to 6 carbons are mono- or polyunsaturated and have one of the meanings given above for alkenyl groups, and the attached oxygen group has the highest corresponding number of carbon atoms. Examples are allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.

Alkynyl groups having 2 to 12 carbons are mono- or polyunsaturated straight or branched and are, for example, alkynyl groups having 2 to 8 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, or 2 to 6 carbon atoms 4 alkynyl. Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, Octynyl and others.

Alkyl groups having 2 to 20 carbons are straight or branched and are, for example, alkyl groups having 2 to 18 carbons, alkyl groups having 2 to 14 carbons, and 2 to 12 carbons Alkyl, alkyl with 2 to 8 carbons, alkyl with 2 to 6 carbons, alkyl with 2 to 4 carbons, alkyl with 4 to 12 carbons or carbon Alkyl group of 4 to 8. Examples are ethenyl, propionyl, butyryl, isobutyryl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl Base, hexadecanoyl, octadecyl, and icosyl, preferably ethenyl. Alkyl groups having 1 to 8 carbons have the same meaning as given above for alkyl groups having 2 to 20 carbons and have the highest corresponding number of carbon atoms.

Alkoxycarbonyl groups having 2 to 12 carbons are straight or branched and are, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1 1,1-dimethylpropoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonoxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially methyl An oxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, or an isobutoxycarbonyl group is preferred, and a methoxycarbonyl group is preferred.

An alkoxycarbonyl group having 2 to 12 carbon atoms interspersed with more than one oxygen atom is straight or branched. The two oxygen atoms are separated by at least two methylene (ie, ethylene). The meta-heteroalkoxycarbonyl group is unsubstituted or substituted with more than one hydroxyl group. The aryloxycarbonyl group having 6 to 20 carbon atoms is, for example, a phenyloxycarbonyl group [= phenyl-O (CO)-], a naphthyloxycarbonyl group, an anthryloxycarbonyl group, and the like. The heteroaryloxycarbonyl group having 5 to 20 carbon atoms is (heteroaryl group having 5 to 20 carbon atoms) -OCO-.

A cycloalkylcarbonyl group having 3 to 10 carbons is (cycloalkyl having 3 to 10 carbons) -CO-, wherein the cycloalkyl group has one of the meanings shown above and has the highest corresponding number of carbon atoms. A cycloalkylcarbonyl group having 3 to 10 carbon atoms interspersed with more than one O, S, CO, NR ₂₆ refers to a metacycloalkyl group CO, wherein the metacycloalkyl group is as defined above.

A cycloalkoxycarbonyl group having 3 to 10 carbon atoms is a cycloalkyl-O (CO)-group having 3 to 10 carbon atoms, wherein the cycloalkyl group has one of the meanings shown above and has the highest corresponding carbon atom number. A cycloalkoxycarbonyl group having 3 to 10 carbon atoms interspersed with more than one O, S, CO, NR ₂₆ refers to metacycloalkyl-O (CO)-, wherein the metacycloalkyl group is as described above. Describing as defined.

The alkylphenyl group having 1 to 20 carbons refers to a phenyl group substituted with more than one alkyl group, and the total number of carbon atoms is 20 at most.

Aryl groups having 6 to 20 carbon atoms are, for example, phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, chryl, tetraphenyl, diphenyltriphenyl, etc., especially phenyl or naphthyl Preferred is phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

In the context of the present invention, heteroaryl groups having 3 to 20 carbons are intended to include monocyclic or polycyclic systems, such as condensed ring systems. Examples are thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienanyl, furanyl, dibenzofuranyl, xanthyl, thioxanthyl, phenoxathienyl , Pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, midazinyl, isoindolyl, indolyl, indazolyl, purinyl, quinazinyl, isoquinoline Quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, fluorinyl, pyridinyl, carbazolyl, β-fluorinyl, phenanthryl, acridinyl, Naphthylazine, phenanthroline, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furyl, phenoxal, 7-phenanthryl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b ] Thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl Base, 3-xanthexyl, 2-phenoxathiol, 2,7-phenoxathiol, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl- 4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazole Base, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindole Indolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7 -Isoquinolinyl, 3-methoxy-6-isoquinolinyl, 2-quinolinyl, 6-quinolinyl, 7-quinolinyl, 2-methoxy-3-quinolinyl, 2 -Methoxy-6-quinolinyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxaline, 6-quinoxaline, 2,3-dimethyl-6-quinoxaline, 2,3-dimethoxy-6 -Quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-fluorinyl, 6-fluorinyl, 7 -Fluorinyl, 3-methoxy-7-fluorinyl, 2-fluorinyl, 6-fluorinyl, 7-fluorinyl, 6,7-dimethoxy-2-fluorinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-fluorin-3-yl, 1-methyl-β- Fluorin-3-yl, 1-methyl-β-fluorin-6-yl, 3-phenanthridinyl, 2-acridyl, 3-acridyl, 2-naphthylazine, 1 -Methyl-5-naphthalene-isodiazophenyl, 5-phenanthroline, 6-phenanthroline, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl Methyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isooxazolyl, 4-isooxazolyl, 5- Isoxazolyl, 4-methyl-3-furanyl, 2-phenoxal, 10-methyl-2-phenoxal, and the like.

Heteroaryl groups having 3 to 20 carbon atoms are especially thienyl, benzo [b] thienyl, Thianthryl, thioxantyl, 1-methyl-2-indolyl or 1-methyl-3-indolyl; especially thienyl.

A heteroaryl heteroarylcarbonyl group having 4 to 20 carbon atoms is a heteroaryl group having 3 to 20 carbon atoms as defined above, which is connected to the rest of the molecule via a CO group.

Substituted aryl (phenyl, naphthyl, aryl having 6 to 20 carbons or heteroaryl having 5 to 20 carbons) is 1 to 7 times, 1 to 6 times, or 1 to 4 times, respectively. , Especially one, two or three substitutions. Obviously, the defined aryl group cannot have more substituents than there are free positions at the aryl ring.

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

Interstitial groups that are interspersed one or more times (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 inter-hetero atoms depends on the number of carbon atoms to be inter-hetero-hetero). A substituted group substituted one or more times has, for example, 1 to 7, 1 to 5, 1 to 4, 1 or 3, or 1 or 2 of the same or different substituents.

A group substituted with more than one defined substituent is intended to have one substituent or multiple substituents with the same or different definitions as given. The halogen atom is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, and preferably fluorine and chlorine. If any two of R ¹ to R ⁸ whose relative positional relationship is adjacent are a group represented by formula (CV), for example, the following (C-Ia)-(C-Ii) structure is formed:

The structure (C-Ia) is preferred.

The compound of formula (C-I) is characterized in that at least one phenyl ring is condensed with a carbazole moiety to form a "naphthyl" ring. That is, one of the above structures is given by the formula (C-I).

If any two of R ¹ to R ⁸ whose relative position is adjacent are independent of each other and are collectively-(CH ₂ ) _P -Y- (CH ₂ ) _q- , then, for example, such as: , And other structures.

If the substituents OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ on the phenyl or naphthyl ring are through the groups R ₁₇ , R ₁₈ , R ₁₉ and / or R ₂₀ and the naphthyl ring When a carbon atom forms a 5-membered or 6-membered ring, a structure including 3 or more rings (including a naphthyl ring) is obtained. Examples are: , And other structures.

If R ₁₇ forms a single bond bonded to one carbon atom of a phenyl or naphthyl ring having a group represented by formula (C-II) or formula (C-VII) thereon, it forms, for example, such as , And other structures.

If R ₁₆ represents a phenyl substituted with SR ₁₈ , where the group R ₁₈ represents a direct bond to a phenyl or naphthyl ring bonded to the carbazole moiety to which the COR ₁₆ group is attached, then, for example, such as , , And other structures.

That is, if R ₁₆ is a phenyl substituted with SR ₁₈ , where the group R ₁₈ represents a direct bond to a phenyl or naphthyl ring bonded to a carbazole moiety having a COR ₁₆ group attached, then thioxanthine The base moiety is formed with a phenyl or naphthyl ring of the carbazole moiety.

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

If R ₂₁ and R ₂₂ together with the nitrogen atom attached thereto form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S or NR ₂₆ , and the benzene ring is condensed with the saturated or unsaturated ring as appropriate , Then form a saturated or unsaturated ring, such as aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine or the corresponding ring ,E.g Wait.

If R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a heteroaromatic ring system, the ring system is intended to include more than one ring (e.g., 2 or 3 rings) and one or More than one heteroatom. Suitable heteroatoms are, for example, N, S, O or P, especially N, S or O. Examples are carbazole, indole, isoindole, indazole, purine, isoquinoline, quinoline, oxoline, phenothiazine, and the like.

The term "and / or" or "or / and" in the context of the present invention is intended to express that not only one of the defined substitutions (substituents) may exist, but also a total of several defined substitutions (substituents), that is, 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 refers is unsubstituted or substituted.

The term "as the case may be" means that the group to which it refers is not or is not.

Throughout this specification and the scope of patent applications below, unless the context requires otherwise, the word "comprise" or variations (e.g., "comprises" or "comprising") shall be understood to imply the inclusion of the stated 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 step groups. The term "(meth) acrylate" in the context of this application is intended to refer to acrylates and corresponding methacrylates.

Compounds of formula (CI) are prepared by methods described in the literature, for example by reacting the corresponding oxime with a halogen, especially a chloride or an acid anhydride, under the following conditions: in an inert solvent (such as a third butyl methyl ether, tetrahydrofuran ( THF) or dimethylformamide), in the presence of a base such as triethylamine or pyridine, or in a basic solvent such as pyridine. In the following, as an example, the preparation of compounds of formula (C-Ia) is explained, in which R ₇ represents an oxime ester group and X represents a direct bond [the reaction of compounds (C-Ib)-(C-Ih) is carried out starting from an appropriate oxime] :

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 methyl.

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

When X represents CO, the corresponding oxime is obtained by dividing the methylene methylene group with 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:

Therefore, the subject of the present invention is also to prepare a compound of formula (CI) method.

Where Hal is a halogen atom, especially Cl, and R ₁₄ is as defined above.

The oxime required as a starting material can be obtained through standard chemistry textbooks (such as J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) or monographs (such as SRSandler & W. Karo, Organic functional group preparations, Section 3, Academic Press).

One of the most convenient methods is, for example, reacting an aldehyde or ketone with hydroxylamine or a salt thereof in a polar solvent such as dimethylacetamide (DMA), DMA aqueous solution, ethanol or ethanol aqueous solution. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH-dependent, and the base can be added continuously at the beginning or during the reaction. It is also possible to use a basic solvent such as pyridine 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 generally about 20 ° C to 120 ° C.

The corresponding ketone intermediate is, for example, prepared by a method described in the literature (for example, standard chemistry textbooks, such as J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992). In addition, the continuous Friedel-Crafts reaction can be effectively used for the synthesis of intermediates. These reactions are well known to those skilled in the art.

Another convenient synthesis of oximes is the nitration of "active" methylene groups with nitrite or alkyl nitrite. Alkaline conditions (e.g., Organic Syntheses coll. Volume VI (J. Wiley & Sons, New York, 1988), pages 199 and 840) and acidic conditions (such as, for example, Organic Synthesis coll. Vol. V, pages 32 and 373, coll. Volume III, pages 191 and 513, coll. Volume II, pages 202, 204, and 363) are both suitable for preparing the oximes used as starting materials in the present invention. Nitrite is generally produced from sodium nitrite. The alkyl nitrite may be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, or isoamyl nitrite.

Another embodiment of the present invention is a free (C-IA) oxime compound

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COR ₁₆ , OR ₁₇ , a halogen atom, NO ₂ or a group represented by formula (C-III); or any two of R ¹ to R ⁸ whose relative positional relationship is adjacent to each other independently represent A substituted alkenyl group having a carbon number of from 2 to 10; or R ¹ ~ R ⁸ in the relative positional relationship of any two vicinal independently of one another together for _{- (CH 2) p -Y- (} CH 2) q -; Or any two of R ¹ to R ⁸ whose relative position relationship is adjacent to each other independently are a group represented by formula (CV); provided that the relative positional relationship between R ¹ to R ⁸ is any two of adjacent positions. At least one of these is a group represented by formula (CV).

R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or has one or more of the following groups Group substitution: halogen atom, phenyl, CN, OH, SH, alkoxy group having 1 to 4 carbon atoms, COOH or (CO) O- (alkyl group having 1 to 4 carbon atoms); or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently an unsubstituted phenyl group or a phenyl group substituted with one or more of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, 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 a halogen atom, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein said etc. The substituent OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring with one carbon atom in the naphthyl ring via the equivalent groups R ₁₇ , R ₁₈ , R ₁₉ and / or R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other , COR ₁₆ or NO ₂ ; Y represents O, S, NR ₂₆ or single bond; p represents an integer from 0 to 3; q represents an integer from 1 to 3; X represents CO or a single bond.

R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: halogen atom, R ₁₇ , (CO) OR 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 formula (C-VI); or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms with one or more of them intermingled O, S, SO, SO ₂ , NR _26, or CO, or an alkenyl group having 2 to 12 carbon atoms, which is not interspersed or interspersed with more than one O, CO, or NR ₂₆ , wherein Alkyl groups having 2 to 20 carbons and the alkenyl groups having 2 to 12 carbon atoms which are unsaturated or heterosaturated are unsubstituted or substituted with more than one halogen atom; or R ₁₃ represents 4 to 3 carbon atoms 8 cycloalkenyl, alkynyl having 2 to 12 carbons, or cycloalkyl having 3 to 10 carbons without interspersed or interspersed with more than one O, S, NR ₂₆ or CO; or R ₁₃ represents benzene Or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , , COR ₁₆ , CN, NO ₂ , halogen atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, carbon number having 2 or more O, S, NR ₂₆ or CO interspersed with 2 To 20 alkyl groups; or each substituted with a cycloalkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms interspersed with more than one O, S, NR ₂₆ or CO; k represents 1 Integer to 10.

R ₁₅ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a phenyl group, a halogen atom, a carbon number of 1 To 4 haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , SO- (alkyl group having 1 to 10 carbons), SO _2- (Alkyl group having 1 to 10 carbons), an alkyl group having 2 to 20 carbons interspersed with one or more O, S or NR ₂₆ ; or each of them is substituted with an alkyl group having 1 to 20 carbons, so The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: a halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , a phenyl group, and a cycloalkane having 3 to 8 carbon atoms. A heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OR ₁₇ , SR _18, or NR ₁₉ R ₂₀ ; or R ₁₅ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms, which are not interspersed or interspersed with more than one O, CO, or NR ₂₆ ; or R ₁₅ represents a carbon number alkyl group having 1 to 20, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, oR ₁₇ SR _18, carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 3 to 20 carbons, an aryloxycarbonyl group having 6 to 20 carbons, aryloxycarbonyl heteroaryl group having 3 to 20, NR ₁₉ R ₂₀ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , phenyl, Or a group represented by formula (C-VI); or the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, the phenyl group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, Substituted with haloalkyl having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents an alkyl group with 2 to 20 carbon atoms, in which one or more O, SO or SO _{2 are} interspersed, and The alkyl group having 2 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: halogen atom, OR ₁₇ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl group, or OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ substituted phenyl; or R ₁₅ represents an alkyl or benzoyl group having 2 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: carbon alkyl having 1 to 6, a halogen atom, a phenyl, oR _17, SR ₁₈ or NR ₁₉ R _20; or R ₁₅ represents an unsubstituted or substituted by one or more of oR ₁₇ or naphthoyl acyl carbon number A heteroarylcarbonyl group of 3 to 14; or R ₁₅ represents an alkoxycarbonyl group having 2 to 12 carbons, which is an interspersed or interspersed carbon with one or more oxygen atoms Alkoxycarbonyl groups of 2 to 12 are Substituted with one or more hydroxyl substituents; or R ₁₅ represents a phenoxycarbonyl group which is unsubstituted or substituted by one or more of the following groups: alkyl having 1 to 6, a halogen atom, a carbon atoms 1 to 4 haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , haloalkyl having 1 to 4 carbon atoms, S (O) _m -(Alkyl group having 1 to 6 carbons), unsubstituted or substituted by alkyl group having 1 to 12 carbon atoms or SO _2- (alkyl group having 1 to 6 carbon atoms) S (O) _m- (Phenyl); or R ₁₅ represents SO ₂ O- (phenyl), which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms; or is diphenylphosphinofluorenyl or di- (carbon number Is an alkoxy) -phosphinofluorenyl group of 1 to 4; m represents 1 or 2; R _'15 has one of the meanings given for R ₁₅ ; X ₁ represents O, S, SO or SO ₂ ; X ₂ Represents O, CO, S, or a single bond.

R ₁₆ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a phenyl group, a halogen atom, and a carbon number of 1 To 4 halogenated alkyl groups, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or alkyl groups having 1 to 20 carbon atoms interspersed with more than one O, S or NR ₂₆ ; Is substituted by an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: a halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , Phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aryloxycarbonyl having 6 to 20 carbons, heteroaryloxycarbonyl having 3 to 20 carbons OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following Group substitution: halogen atom, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (carbon number 1 to 4 Alkyl), O (CO)-(alkyl with 1 to 4 carbons), O (CO)-(phenyl), COOH or (CO) O- (carbon Alkyl of 1 to 4); or R ₁₆ represents alkyl having 2 to 12, have therebetween one or more heteroatoms O, S or NR _26; or R ₁₆ represents _{(CH 2 CH 2 O) n} + 1 H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), alkenyl group having 2 to 12 carbon atoms or cycloalkyl group having 3 to 8 carbon atoms; or R ₁₆ Represents a phenyl substituted with SR ₁₈ , wherein the group R ₁₈ represents a single bond bonded to a phenyl or naphthyl ring of a carbazole moiety to which a COR ₁₆ group is attached; n represents 1 to 20.

R ₁₇ represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 3 carbon atoms), and an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, OH , SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms), O (CO)-(carbon 1 to 4 alkyl), O (CO)-(2 to 4 carbon) alkenyl, O (CO) -phenyl, COOH, (CO) O- (1 to 4 carbon Alkyl), cycloalkyl with 3 to 20 carbons, SO _2- (haloalkyl with 1 to 4 carbons), O- (haloalkyl with 1 to 4 carbons) or interspersed with more than one oxygen A cycloalkyl group having 3 to 20 carbon atoms; or R ₁₇ represents an alkyl group having 2 to 20 carbon atoms with one or more O, S or NR ₂₆ interposed therebetween; or R ₁₇ represents (CH ₂ CH ₂ O ) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 12 carbon atoms , An alkenyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms without interspersed or interspersed with more than one O, S, NR ₂₆ or CO; or R ₁₇ represents a carbon number from 1 to Alkyl of 8-cycloalkyl having 3 to 10 carbon atoms, which is uninducted One or more oxygen atoms; or R ₁₇ represents a benzoyl group which is unsubstituted or substituted with one or more carbon atoms, an alkyl group, a halogen atom, OH, or 1 to 6 carbon atoms, an alkoxy group having 1 to 3 Substitution; or R ₁₇ represents phenyl, naphthyl or heteroaryl having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with more than one of the following groups: halogen atom, OH, carbon number 1 to 12 Alkyl, alkoxy having 1 to 12 carbons, CN, NO ₂ , phenyl- (alkoxy having 1 to 3 carbons), phenoxy, alkyl sulfur having 1 to 12 carbons Radical, phenylthio, N (alkyl having 1 to 12 carbons) ₂ , diphenyl-amino or ; Or R ₁₇ forms a bond to which has a group or A single bond of one of the carbon atoms of the phenyl or naphthyl ring.

R ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-alkyl group having 1 to 3 carbon atoms, wherein the carbon number is 2 to 12 Alkenyl, cycloalkyl having 3 to 20 carbon atoms or phenyl-alkyl having 1 to 3 carbon atoms are unincorporated or interspersed with more than one O, S, NR ₂₆ , CO, or (CO) OR ₁₇ ; Or R ₁₈ is an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl group with 1 to 4 carbons), O (CO)-(alkenyl group with 2 to 4 carbons), O (CO)-(carbon number is 1 to 4 alkyl), O (CO)-(phenyl), or (CO) OR ₁₇ ; or R ₁₈ represents an alkyl group having 2 to 20 carbon atoms, with more than one O, S, NR ₂₆ interposed therebetween , CO or (CO) OR ₁₇ ; or R ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), carbon number is Alkyl groups of 2 to 8 or alkenyl groups of 3 to 6 carbons; or R ₁₈ represents benzamidine, which is unsubstituted or substituted with more than one of the following: carbons of 1 to 6 Alkyl, halogen atom, OH, alkoxy with 1 to 4 carbons or carbon Is an alkylthio group of 1 to 4; or R ₁₈ represents a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with more than one of the following groups: a halogen atom, Alkyl having 1 to 12 carbons, haloalkyl having 1 to 4 carbons, alkoxy having 1 to 12 carbons, CN, NO ₂ , phenyl-alkoxy having 1 to 3 carbons, Phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N (alkyl having 1 to 12 carbons) ₂ , diphenylamino, (CO) O- (carbon number is 1 to 8 alkyl), (CO)-(alkyl with 1 to 8 carbons), (CO) N- (alkyl with 1 to 8 carbons) ₂ or .

R ₁₉ and R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and 2 carbon atoms Alkenyl to 5; Cycloalkyl having 3 to 20 carbons; Phenyl-alkyl having 1 to 3 carbons; Alkyl group having 1 to 8 carbons; Alkyl group having 1 to 8 carbons An alkoxy group, an alkenyl group having 3 to 12 carbon atoms, an SO _2- (haloalkyl group having 1 to 4 carbon atoms) or a benzamidine group; or R ₁₉ and R ₂₀ represent a phenyl group, a naphthyl group or a carbon number Heteroaryl groups of 3 to 20, each of which is unsubstituted or substituted with more than one of the following groups: halogen atom, haloalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon 1 to 12, alkyl, benzamidine, or alkoxy having 1 to 12 carbons; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached are not interspersed or interspersed with O, S, or NR ₁₇ 5- or 6-membered saturated or unsaturated ring, and the 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 20 carbon atoms carbons, alkoxy having 1 to _{20, = O, OR 17, SR} 18, NR 21 R 22, COR 23, NO 2, halogen Promoter, a haloalkyl group having a carbon number of 1 to 4, CN, phenyl, Either unsaturated or interspersed with more than one O, S, CO or NR ₁₇ carbon group having 3 to 20 carbon atoms; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a heteroaromatic ring system The ring system is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , COR ₂₃ , , A halogen atom, NO ₂ , CN, phenyl, or a cycloalkyl group having 3 to 20 carbon atoms without any interspersed or interspersed O, S, CO, or NR ₂₆ .

R ₂₁ and R ₂₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; or R ₂₁ and R ₂₂ together with the nitrogen atom to which it is attached form a 5- or 6-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S, or NR ₂₆ , and the 5- or 6-membered saturated or unsaturated ring is unsaturated Condensation or the 5- or 6-membered saturated or unsaturated ring is condensed with a benzene ring.

R ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms interspersed with one or more O, CO, or NR ₂₆ , A cycloalkyl group having a carbon number of 3 to 20 that is not interspersed or interspersed with O, S, CO, or NR ₂₆ ; or R ₂₃ represents a phenyl group, a naphthyl group, a phenyl-alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ .

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

R ₂₅ represents (CO) OR ₁₇ , (CO) NR ₁₉ R ₂₀ , (CO) R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ .

R ₂₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkyl group having 2 to 20 carbon atoms, with more than one O or CO interposed therebetween; or a phenyl group -(Alkyl group having 1 to 4 carbon atoms) and cycloalkyl group having 3 to 8 carbon atoms, which are not interspersed or interspersed with more than one O or CO; or COR ₁₉ ; or phenyl, which Is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , ; Provided that at least one group is present in the compound of formula (C-IA) or .

The preferred groups defined for compounds of formula (C-IA) correspond to those given for compounds of formula (CI) as given above, except that each defined oxime ester group (e.g. ) Are replaced by the corresponding free oxime group

Each oxime ester group can exist in two configurations (Z) or (E). Isomers can be separated by conventional methods, but it is also possible to use a mixture of isomers as, for example, a photoinitiator. Therefore, the present invention also relates to a mixture of configurational isomers of a compound of formula (C-I).

Preferred are compounds of formula (CI) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently a hydrogen atom and a carbon number of 1 Alkyl to 20, COR ₁₆ , NO ₂ or a group represented by formula (C-II); or any two of R ₁ to R ₈ in which the relative positional relationship is adjacent to each other independently form a formula (CV) As long as at least one of any two of R ₁ to R ₈ whose relative positional relationship is adjacent is a group represented by formula (CV); X represents CO or a direct bond.

R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, (CO) OR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , PO ( OC _k H _{2k + 1} ) ₂ ; or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms with one or more O, S, NR ₂₆ or CO interposed therebetween; or R ₁₃ represents phenyl or naphthyl, both These are unsubstituted or substituted with more than one COR ₁₆ or a group represented by formula (C-VII).

R ₁₄ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms.

R ₁₅ represents a phenyl group, a naphthyl group, and a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a phenyl group, a halogen atom, and a halogenated alkyl group having 1 to 4 carbon atoms OR ₁₇ , SR _18, or an alkyl group having 2 to 20 carbon atoms, intermixed with more than one O or S; or each of them substituted with one or more alkyl groups having 1 to 20 carbon atoms, the carbon number is The alkyl group of 1 to 20 is unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, carbon having 3 to 20 heteroaryl, 6 to 20 carbon aryloxycarbonyl, 4 to 20 carbon heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO (OC _k H _{2k +1} ) ₂ ; or R ₁₅ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , a cycloalkyl group having 3 to 8 carbon atoms, Heteroaryl groups having 3 to 20 carbon atoms, NR ₁₉ R ₂₀ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ . R _'14 has one of the meanings given for R ₁₄ ; R' ₁₅ has one of the meanings given for R ₁₅ .

R ₁₆ represents a phenyl group, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a carbon number of 2 to 20 with one or more O, S, or NR ₂₆ interspersed. Alkyl, or R ₁₆ represents phenyl, which is substituted with one or more alkyl groups having 1 to 20 carbons, the alkyl group having 1 to 20 carbons being unsubstituted or substituted with one or more of the following groups: Halogen atom, (CO) OR ₁₇ , (CO) NR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aromatic having 6 to 20 carbons Oxycarbonyl, heteroaryloxycarbonyl having 4 to 20 carbons, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents an alkyl having 1 to 20 carbons, which is unsubstituted or substituted by Group substitution: halogen atom, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms), O (CO )-(Alkyl group having 1 to 4 carbons) or (CO) O- (alkyl group having 1 to 4 carbons).

R ₁₇ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms) , O- (alkyl group having 1 to 4 carbons), (CO) O- (alkyl group having 1 to 4 carbons), cycloalkyl group having 3 to 20 carbon atoms or interspersed with more than one oxygen atom A cycloalkyl group having a carbon number of 3 to 20; or R ₁₇ represents an alkyl group having a carbon number of 2 to 20 with one or more oxygen atoms interposed therebetween.

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

R ₁₉ and R ₂₀ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbons, an alkyl group having 1 to 8 carbons or an alkyl group having 1 to 8 carbons; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a heteroaromatic ring system that is unsubstituted or substituted with a group represented by formula (C-VII); provided that it is in the molecule There is at least one group represented by the formula (C-II) or a group represented by the formula (C-VII).

Attention must be paid to compounds of formula (CI) as defined above, in which R ₁ , R ₂ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other a hydrogen atom, COR ₁₆ , NO ₂ or formula (C-II) R ₃ and R ₄ together represent a group represented by formula (CV); R ₉ , R ₁₀ , R _11, and R _{12 each} represent a hydrogen atom; and X represents a direct bond.

R ₁₃ represents an alkyl group having 1 to 20 carbon atoms. R ₁₄ represents an alkyl group having 1 to 20 carbon atoms. R ₁₅ represents an alkyl group or a phenyl group having 1 to 20 carbon atoms, which is substituted with one or more OR ₁₇ or an alkyl group having 1 to 20 carbon atoms.

R ₁₆ represents a phenyl group which is substituted with one or more alkyl groups having 1 to 20 carbon atoms or OR ₁₇ ; and R ₁₇ represents an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms It may be an alkyl group having 2 to 20 carbon atoms with one or more oxygen atoms interspersed, provided that at least one group represented by the formula (C-II) is present in the compound of the formula (CI).

The subject of the present invention is further a compound of formula (CI) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, or R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ independently of each other are groups represented by formula (CV); provided that R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ at least one pair independently of each other is a group represented by formula (CV); or R ₂ is a group represented by formula (C-II), COR ₁₆ , NO ₂ or is represented by formula (C-III) Or R ₇ is a group represented by COR ₁₆ or formula (C-II).

R ₉ , R ₁₁ and R ₁₂ represent a hydrogen atom; R ₁₀ represents a hydrogen atom, OR ₁₇ or COR ₁₆ ; X represents CO or a single bond.

R ₁₃ represents a phenyl group; or R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, R ₁₇ , OR ₁₇ , SR _18, or PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms with one or more oxygen atoms interposed therebetween; k represents 2.

R ₁₄ represents an alkyl or thienyl group having 1 to 20 carbons; R ₁₅ represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more OR ₁₇ or alkyl groups having 1 to 20 carbons; or R ₁₅ represents a thienyl group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , carbon A cycloalkyl group having a number of 3 to 8, NR ₁₉ R ₂₀ or (CO) OR ₁₇ ; or R ₁₅ represents an alkyl group having a carbon number of 2 to 20 with SO ₂ interposed therebetween.

R ₁₆ represents phenyl or naphthyl, each of which is unsubstituted or substituted with more than one of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or an alkyl group having 1 to 20 carbons; or R ₁₆ represents thiophene base.

R ₁₇ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or have one or more of the following groups: a halogen atom, O (CO)-(carbon 1 to 4 alkyl), O (CO)-(alkenyl having 2 to 4 carbons) or a cycloalkyl having 3 to 20 carbons with one or more oxygen atoms interspersed; or R ₁₇ represents An alkyl group having 2 to 20 carbon atoms is intermixed with one or more oxygen atoms.

R ₁₈ represents a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and it is unsubstituted or substituted with more than one OH, O (CO)-(alkenyl group having 2 to 4 carbon atoms) ) Or (CO) OR ₁₇ ; or R ₁₈ represents phenyl, which is unsubstituted or substituted with more than one halogen atom.

R ₁₉ and R ₂₀ are independently of each other an alkyl fluorenyl group having 1 to 8 carbons or an alkyl alkoxy group having 1 to 8 carbons; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form an intermolecular A 5- or 6-membered saturated ring of an oxygen atom; provided that at least one group represented by the formula (C-II) is present in the compound of the formula (CI).

Examples of compounds of the invention are compounds of formulae (C-Ia) to (C-Ig) as defined above. Formula (C-Ia), (C-Ib), (C-Ic), especially formula (C-Ia) or (C-Ic), or formula (C-Ia), (C-Ic), or (C- Id), in particular compounds of formula (C-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 a hydrogen atom, COR ₁₆ , a group represented by formula (C-II), Alternatively, any two of R ¹ to R ⁸ whose relative positional relationship is adjacent to each other are independently a group represented by formula (CV).

For example, R ₃ and R ₄ or R ₁ and R _{2 are} collectively a group represented by formula (CV); or R ₃ and R ₄ , R ₅ and R _{6 are} collectively a group represented by formula (CV) R ₃ and R _{4 are} particularly a group represented by formula (CV).

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

R _{7 is} especially a hydrogen atom, COR ₁₆ or a group represented by formula (C-II). Or R ₇ is a group represented by COR ₁₆ or formula (C-II), and particularly a group represented by formula (C-II).

R _{2 is} particularly a group represented by COR ₁₆ , a formula (C-II), or a group represented by a formula (C-III). Or R ₂ and R ₁ together are a group represented by formula (CV). R _{2 is} especially COR ₁₆ .

X is preferably a single bond.

For example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or a phenyl group substituted with more than one of the following groups : An alkyl group having 1 to 6 carbon atoms, a halogen atom, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a halogen atom, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ , Wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally form a 5- or 6-membered ring with one carbon atom 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 are each independently a group represented by COR ₁₆ or formula (C-II).

Specifically, R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or a phenyl group substituted with one or more of the following groups : An alkyl group having 1 to 6 carbon atoms, a halogen atom, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a halogen atom, 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 (C-II).

For example, R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or one having 1 to 6 carbon atoms. An alkyl-substituted phenyl group; or R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently a group represented by COR ₁₆ or formula (C-II).

In another embodiment, for example, R ₉ , R ₁₀ , R _11, and R ₁₂ are independently of each other a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or one or more Phenyl substituted by: alkyl having 1 to 6 carbon atoms, halogen atom, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen atom, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ , wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally form a 5-membered or a carbon atom of the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and / or R ₂₀ 6 member ring.

In addition, for example, R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or one substituted with more than one of the following groups Phenyl: an alkyl group having 1 to 6 carbon atoms, a halogen atom, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently a halogen atom, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or COR ₁₆ .

Or, for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or a benzene substituted with more than one of the following groups Group: an alkyl group having 1 to 6 carbon atoms, a halogen atom, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are a halogen atom, OR ₁₇ , COR ₁₆ or NR ₁₉ R ₂₀ .

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

R ₁₃ represents, for example, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: a halogen atom, (CO) OR ₁₇ or CONR ₁₉ R ₂₀ ; or R ₁₃ represents a carbon number An alkyl group of 2 to 20 is interspersed with more than one O, S, SO, SO ₂ , NR ₂₆ or CO, or an alkenyl group with 2 to 12 carbons, which is optionally interspersed with more than one O, CO or NR ₂₆ , or R ₁₃ represents a cycloalkyl group having 3 to 10 carbon atoms, optionally mixed with more than one O, S, CO, NR ₂₆ , or R ₁₃ represents phenyl or naphthyl, both of which Unsubstituted or substituted with more than one of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , NO ₂ , halogen atom, alkyl group having 1 to 20 carbon atoms, carbon group having 1 to 4 carbon atoms A halogenated alkyl group, an alkyl group having 2 to 20 carbon atoms, in which one or more oxygen atoms are mixed, or a group represented by formula (C-VII); or R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, Substituted or substituted by more than one of the following groups: halogen atom, R ₁₇ , (CO) OR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or carbon number An alkyl group of 2 to 20 with more than one oxygen in between atom.

In addition, R ₁₃ represents, for example, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: a halogen atom, R ₁₇ , (CO) OR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or an alkyl group having 2 to 20 carbon atoms with one or more oxygen atoms interposed therebetween; or an alkenyl group or carbon having 2 to 12 carbon atoms A cycloalkyl group having a number of 3 to 10; or R ₁₃ represents a phenyl group or a naphthyl group, both of which are unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkyl group having 2 to 20 carbon atoms, in which one or more oxygen atoms are intermixed, or the formula (C- VII).

In another embodiment, R ₁₃ represents, for example, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: a halogen atom, R ₁₇ , OR ₁₇ , SR _18, or PO (OC _k H _{2k + 1} ) ₂ ; or an alkyl group having 2 to 20 carbon atoms with one or more oxygen atoms interposed therebetween; or an alkenyl group having 2 to 12 carbon atoms and 3 to 10 carbon atoms Cycloalkyl, phenyl or naphthyl.

Or R ₁₃ represents, for example, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: a halogen atom, R ₁₇ , OR ₁₇ , SR _18, or PO (OC _k H _{2k + 1} ) ₂ ; or an alkyl group having 2 to 20 carbon atoms with one or more oxygen atoms interposed therebetween; or a phenyl group, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms .

Or R ₁₃ represents, for example, an alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkenyl group having 2 to 12 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Or R ₁₃ represents, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms.

Preferably, R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, especially an alkyl group having 1 to 8 carbon atoms, such as 2-ethylhexyl.

R ₁₄ represents, for example, a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms , Which is unsubstituted or substituted with more than one halogen atom or phenyl; or R ₁₄ represents phenyl or naphthyl, both of which are unsubstituted or substituted with more than one of the following groups: An alkyl group, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, OR ₁₇ , SR ₁₈ and / or NR ₁₉ R ₂₀ ; or R ₁₄ represents a heteroaryl group having 3 to 5 carbon atoms, such as thienyl, or Alkoxy, benzyloxy or phenoxy having 1 to 8 carbons.

Or R ₁₄ represents, for example, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more halogen atoms or phenyl groups; or R ₁₄ represents a heteroaryl group, such as thiophene, having 3 to 5 carbon atoms Group) or phenyl group which is unsubstituted or substituted with one or more of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, OR ₁₇ , SR _18, and / Or NR ₁₉ R ₂₀ ; or R ₁₄ represents an alkoxy group, a benzyloxy group or a phenoxy group having a carbon number of 1 to 8.

In another embodiment, R ₁₄ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with a phenyl group; or R ₁₄ represents a phenyl group, which is unsubstituted or substituted with one or more carbon atoms of 1 Alkyl to 6 substituted.

Preferably, R ₁₄ represents an alkyl group having 1 to 20 carbon atoms, a heteroaryl group such as thienyl group having 3 to 5 carbon atoms, or a phenyl group, especially an alkyl group having 1 to 20 carbon atoms or Thienyl, especially alkyl having 1 to 8 carbons.

R ₁₅ represents, for example, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: a phenyl group, a halogen atom, a carbon number 1 to 4 haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , alkyl having 1 to 20 carbons; or R ₁₅ representing a hydrogen atom and a cycloalkane having 3 to 8 carbons A cycloalkyl group having 3 to 8 carbon atoms is optionally mixed with more than one O, CO, or NR ₂₆ ; or R ₁₅ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one The following groups are substituted: halogen atom, OR ₁₇ , cycloalkyl having 3 to 8 carbons, heteroaryl having 5 to 20 carbons, phenoxycarbonyl having 8 to 20 carbons, 5 carbon Heteroaryloxy-carbonyl to 20, NR ₁₉ R ₂₀ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , a group represented by formula (C-VI), benzene Or phenyl substituted by: a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, OR ₁₇ or NR ₁₉ R ₂₀ ; or R ₁₅ representing a carbon number of alkyl of 2 to 20, during which more than one heteroatom O, S or SO _2, or R ₁₅ represents carbon number of 2 20 alkanoyl group, benzoyl group, a carbon number of alkoxycarbonyl group having 2 to 12, phenoxycarbonyl group, CONR ₁₉ R _20, NO ₂ carbon atoms or a haloalkyl group having 1 to 4.

In addition, R ₁₅ represents, for example, a hydrogen atom, an aryl group having 6 to 20 carbon atoms, especially a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms; or carbon Heteroaryl groups of 3 to 5, such as thienyl; or cycloalkyl groups of 3 to 8 carbons, alkyl groups of 1 to 20 carbons, which are unsubstituted or substituted with more than one of the following groups : OR ₁₇ , SR ₁₇ , a cycloalkyl group having 3 to 8 carbon atoms, NR ₁₉ R ₂₀ or (CO) OR ₁₇ ; or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms with one or more O interposed therebetween Or SO ₂ .

Compounds of formula (CI) are of interest, in which R ₁₅ represents, for example, a hydrogen atom, phenyl, naphthyl, each of which is unsubstituted or substituted with an alkyl group having 1 to 8 carbons; or R ₁₅ represents thienyl, An alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: OR ₁₇ , SR ₁₇ , a cycloalkyl group having 3 to 8 carbon atoms, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms with one or more O or SO ₂ interposed therebetween.

R ₁₅ is, for example, a cycloalkyl group having 3 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, especially an alkyl group having 1 to 20 carbon atoms, especially an alkyl group having 1 to 12 carbon atoms. base.

R _'14 and R' ₁₅ the preferred are those described above for R ₁₄ and R ₁₅ are given.

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

R ₁₆ represents, for example, an aryl group (especially phenyl or naphthyl group, especially phenyl group) having 6 to 20 carbon atoms or a heteroaryl group (especially thienyl group) having 5 to 20 carbon atoms, each of which is unsubstituted or Substituted by more than one of the following groups: phenyl, halogen atom, haloalkyl having 1 to 4 carbons, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R _20, or carbon interspersed with more than one oxygen atom Alkyl groups of 1 to 20; or each substituted with one or more alkyl groups having 1 to 20 carbons, the alkyl groups having 1 to 20 carbons being unsubstituted or substituted with more than one of the following groups : Halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 5 to 20 carbons, and aryloxy having 6 to 20 carbons A carbonyl group, a heteroaryloxycarbonyl group having 5 to 20 carbon atoms, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and the carbon number is 1 to 20 Alkyl 20 is unsubstituted or substituted with more than one of the following groups: halogen atom, phenyl, OH, SH, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ (CO) O- (carbon number Is an alkyl group of 1 to 4), O (CO)-(alkyl group of 1 to 4 carbons), O (CO)-( Phenyl), COOH, or (CO) O- (an alkyl group having 1 to 4 carbons); or R ₁₆ represents an alkyl group having 2 to 12 carbons with one or more oxygen atoms interposed therebetween; or (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbon atoms), alkenyl group having 2 to 12 carbon atoms or 3 to 8 carbon atoms Cycloalkyl, and n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

Furthermore, R ₁₆ represents, for example, phenyl or naphthyl, especially phenyl, thienyl, or carbazole, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen atom, carbon number 1 To 4 haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or alkyl having 1 to 20 carbons; or R ₁₆ represents an alkyl having 1 to 20 carbons, which is unsubstituted or substituted with more than one The following groups are substituted: halogen atom, phenyl, OH, SH, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms), O (CO )-(Alkyl group having 1 to 4 carbons), O (CO)-(phenyl), COOH or (CO) O- (alkyl group having 1 to 4 carbons); or R ₁₆ represents a carbon number of An alkyl group of 2 to 12 with one or more oxygen atoms interspersed therewith; or (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(carbon number of 1 to 8 Alkyl), alkenyl having 2 to 12 carbons or cycloalkyl having 3 to 8 carbons, and n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

Furthermore, R ₁₆ represents, for example, phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or an alkyl group having 1 to 20 carbons; or R ₁₆ represents a heteroaryl group having 3 to 5 carbons, especially a thienyl group.

R ₁₆ is, for example, phenyl, which is unsubstituted or substituted with more than one of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or an alkyl group having 1 to 20 carbons, or R ₁₆ represents thiophene base.

Preferably, R ₁₆ represents, for example, a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with one or more alkyl groups having 1 to 20 carbon atoms.

R _{16 is} especially phenyl, which is substituted by one or more alkyl groups having 1 to 20 carbon atoms.

R ₁₇ represents, for example, a hydrogen atom, a phenyl-alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or substituted with one or more of the following groups: a halogen atom, OH , OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbons), O (CO)-(alkyl group having 1 to 4 carbons), O (CO)-(carbon number from 2 to 4) alkenyl, O (CO)-(phenyl), COOH, (CO) O- (alkyl having 1 to 4 carbons), cycloalkyl having 3 to 20 carbons, or one or more interspersed O has a cycloalkyl group having 3 to 20 carbon atoms; or R ₁₇ represents an alkyl group having 2 to 20 carbon atoms with one or more oxygen atoms interposed therebetween; or R ₁₇ represents (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 12 carbon atoms, carbon number An alkenyl group of 3 to 6 or a cycloalkyl group of 3 to 20 carbons, optionally mixed with more than one oxygen atom; or R ₁₇ represents a benzyl group, which is unsubstituted or has more than one carbon 1 to 6 alkyl, halogen atom, OH, or alkoxy having 1 to 3 carbons; or R ₁₇ represents phenyl, naphthyl, or heteroaryl having 5 to 20 carbons, each of which is Replaced or replaced by more than one Under substituted: a halogen atom, OH, alkyl having 1 to 12 carbons, alkoxy having 1 to 12, CN, NO _2, phenyl - (alkoxy group having a carbon number of 1 to 3 ), Phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N (alkyl having 1 to 12 carbons) ₂ , diphenyl-amino or formula (C-VII) Represented groups.

In another embodiment, R ₁₇ represents, for example, a hydrogen atom, a phenyl-alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or have more than one of the following groups Group substitution: halogen atom, O (CO)-(alkyl group with 1 to 4 carbons), O (CO)-(alkenyl group with 2 to 4 carbons) or carbon number interspersed with more than one oxygen atom Is an alkyl group of 2 to 20; or an alkyl group of 1 to 8 carbons, an alkenyl group of 2 to 12 carbons, an alkenyl group of 3 to 6 carbons, and one or more oxygen atoms An alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms optionally mixed with one or more oxygen atoms, or a benzamidine group, which is unsubstituted or has more than one of the following groups Substitution: an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or an alkoxy group having 1 to 3 carbon atoms, or a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with one or more of the following groups : A halogen atom, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons.

R ₁₇ is also, for example, a hydrogen atom, a phenyl-alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. One or more of the following groups substituted: a halogen atom, a cycloalkyl group having 3 to 20 carbon atoms, O (CO)-(alkyl group having 1 to 4 carbon atoms), O (CO)-(carbon number 2 to Alkenyl of 4) or an alkyl group having 2 to 20 carbon atoms interspersed with one or more oxygen atoms, or R ₁₇ represents an alkyl group with 2 to 20 carbon atoms interspersed with one or more oxygen atoms.

R _{17 is} especially a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or substituted with more than one of the following groups: O (CO)-(carbon number An alkyl group of 1 to 4), O (CO)-(alkenyl group of 2 to 4 carbons) or an alkyl group of 2 to 20 carbons interspersed with one or more oxygen atoms, or R ₁₇ represents a carbon number An alkyl group of 2 to 20 with one or more oxygen atoms interposed therebetween.

R ₁₈ represents, for example, a cycloalkyl group having 3 to 20 carbon atoms, which is not interspersed or has more than one oxygen atom; or R ₁₈ represents an alkyl group, which is 1 to 20 carbon atoms, which is unsubstituted or substituted One or more of the following groups substituted: OH, O (CO)-(2 to 4 carbons) alkenyl, O (CO)-(1 to 4 alkyls) or (CO) OR ₁₇ ; Or R ₁₈ represents an alkyl group having 2 to 20 carbon atoms, and one or more O, S, CO, NR ₂₆ or (CO) OR ₁₇ are interposed therebetween; or R ₁₈ represents an alkyl fluorenyl group having 2 to 8 carbon atoms or An alkenyl group or a benzamyl group having 3 to 6 carbon atoms; or R ₁₈ represents a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or has one or more of the following groups Substitution: halogen atom, alkyl group having 1 to 12 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 12 carbon atoms or NO ₂ .

In another embodiment, R ₁₈ represents, for example, a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: OH, O (CO)-(2 to 4 carbons) alkenyl, O (CO)-(1 to 4 carbons) or (CO) OR ₁₇ ; or R ₁₈ represents phenyl or naphthyl, They are each unsubstituted or substituted with one or more halogen atoms or alkyl groups having 1 to 12 carbon atoms, especially halogen atoms.

R ₁₈ represents, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a phenyl-alkyl group having 1 to 3 carbon atoms, Alkyl, benzyl, phenyl or naphthyl having 2 to 8 carbons.

For example, R ₁₈ represents an alkyl group having 1 to 20 carbon atoms, which is substituted by one or more of the following groups: OH, O (CO)-(2 to 4 carbon atoms) alkenyl group, O (CO) -(Alkyl group having 1 to 4 carbons) or (CO) OR ₁₇ , or R ₁₈ represents a phenyl group, which is substituted with one or more halogen atoms.

Preferably, R ₁₈ represents an alkyl group having 1 to 8 carbon atoms, which is substituted as defined above.

For example, R ₁₉ and R ₂₀ are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. -An alkyl, phenyl or naphthyl group having 1 to 3 carbon atoms, an alkylfluorenyl group having 1 to 8 carbon atoms, an alkylfluorenyloxy group having 1 to 8 carbon atoms, and an alkenyl group having 3 to 12 carbon atoms Or benzamidine; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S, or NR ₁₇ ; or R ₁₉ and R ₂₀ Together with the nitrogen atom to which it is attached, a heteroaromatic ring system is formed, which ring system is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 20 carbon atoms, a haloalkane having 1 to 4 carbon atoms Group, or a group represented by formula (C-VII).

In addition, for example, R ₁₉ and R ₂₀ are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, Phenyl-alkyl with 1 to 3 carbons, alkyl with 1 to 8 carbons, alkyl with 1 to 8 carbons and alkenyloxy with 3 to 12 carbons Fluorenyl; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated ring optionally mixed with O or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached Carbazole ring.

For example, R ₁₉ and R ₂₀ are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. -Alkyl groups having 1 to 3 carbons, alkyl groups having 1 to 8 carbons, alkyl groups having 1 to 8 carbons, alkylene groups having 3 to 12 or benzyl groups Or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a 5-membered or 6-membered saturated ring optionally mixed with O or NR ₁₇ .

Preferably, R ₁₉ and R ₂₀ are independently of each other an alkylfluorenyl group having 1 to 8 carbon atoms and an alkylfluorenyloxy group having 1 to 8 carbon atoms; or R ₁₉ and R ₂₀ and the nitrogen atom to which they are attached Together form a morpholine ring.

For example, R ₂₁ and R ₂₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; Or R ₂₁ and R ₂₂ together with the nitrogen atom to which they are attached form a morpholine ring. R ₂₁ and R ₂₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

R ₂₃ represents, for example, a hydrogen atom, OH, phenyl, or an alkyl group having 1 to 20 carbon atoms. R _{23 is} especially a hydrogen atom, OH or an alkyl group having 1 to 4 carbon atoms.

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

R ₂₆ represents, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkyl group having 2 to 20 carbon atoms, with one or more O or CO interposed therebetween; or Is phenyl- (alkyl having 1 to 4 carbons), cycloalkyl having 3 to 8 carbons, optionally mixed with more than one O or CO; or COR ₁₉ or phenyl, which is not Substituted or substituted by more than one of the following groups: an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ .

Or R ₂₆ represents, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms; is a phenyl-alkyl group having 1 to 4 carbon atoms and 3 to 8 carbon atoms Cycloalkyl, COR ₁₉ or phenyl, which is unsubstituted or substituted with more than one alkyl group having 1 to 20 carbon atoms. In addition, R ₂₆ represents, for example, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms.

Examples of the photoinitiator (C-1) having the structure of the formula (CI) include the following compounds represented by the formula (CI-1) to (CI-84):

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the light initiator (C-1) having the structure of the formula (CI) is 5 to 100 parts by weight, preferably 10 to 90 parts by weight, More preferably, it is 15 to 80 parts by weight.

When the photosensitive resin composition for a black matrix does not contain a light initiator (C-1) having a structure of the formula (C-I), the obtained black matrix cannot obtain an appropriate bluishness.

Other photoinitiators (C-2)

The photoinitiator (C) may further include other photoinitiators (C-2).

Specific examples of the other photoinitiator (C-2) include other oxy-fluorenyl oxime-based compounds (O-acyloxime) or non-oxy-fluorenyl oxime-based photoinitiators.

Specific examples of other oxy-fluorenyl oxime compounds include 1- [4- (phenylthio) phenyl] -propane-3-cyclopentane-1,2-dione 2- (O-phenylfluorenyl oxime ), 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-phenylfluorenyloxime), 1- [4- (phenylthio) phenyl ] -Octane-1,2-dione-2- (O-phenylamidoxime), or a combination thereof. 1- [4- (phenylthio) phenyl] -octane-1,2-dione-2- (O-phenylamidoxime) can be manufactured by Ciba Specialty Chemicals Co., Ltd. , Model IRGACURE OXE-01.

In addition, specific examples of other oxy-fluorenyl oxime compounds include 1- [4- (phenylfluorenyl) phenyl] -heptane-1,2-dione-2- (O-phenylfluorenyl oxime), 1 -[9-ethyl-6- (2-methylphenylfluorenyl) -9H-carbazole-3-substituent] -ethanone-1- (O-acetamidooxime), 1- [9- Ethyl-6- (3-methylphenylfluorenyl) -9H-carbazole-3-substituent] -ethanone-1- (O-ethylfluorenyloxime), 1- [9-ethyl-6 -Phenylhydrazine-9H-carbazole-3-substituent] -ethanone-1- (O-acetamidooxime), acetone-1- [9-ethyl-6- (2-methyl -4-tetrahydrofuranylphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime), acetone-1- [9-ethyl-6- (2-methyl Methyl-4-tetrahydropyranylphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime), acetone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime), acetone-1- [9-ethyl-6 -(2-methyl-5-tetrahydropyranylphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-acetamidooxime), acetone-1- [9- Ethyl-6- (2-methyl-4-tetrahydrofuranyl (Methoxyphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime), acetone-1- [9-ethyl-6- (2-methyl- 4-tetrahydropyranylmethoxyphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime), acetone-1- [9-ethyl-6 -(2-methyl-5-tetrahydrofurylmethoxyphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-acetamidooxime), acetone-1- [9- Ethyl-6- (2-methyl-5-tetrahydropyranylmethoxyphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime), ethane Keto-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) phenyl}}-9H-carbazole- 3-substituent] -1- (O-acetamidoxime), acetone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1, 3-dioxolyl) methoxyphenylfluorenyl} -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime), or a combination of the above compounds. 1- [9-ethyl-6- (2-methylphenylfluorenyl) -9H-carbazole-3-substituent] -ethanone-1- (O-acetamidooxime) may be derived from Ciba Manufactured by Jinghua Co., Ltd. under the model number IRGACURE OXE-02.

Other oxy-fluorenyl oxime compounds may be used alone or in combination.

Specific examples of the non-oxy-fluorenyl oxime-based photoinitiator include triazabenzene compounds, acetophenone compounds, diimidazole compounds, benzophenone compounds, α-diketone compounds, and alcohol ketones. Compounds, alcohol ketone ether compounds, phosphonium oxide compounds, quinone compounds, halogen-containing compounds, peroxides, or a combination of the foregoing compounds.

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

Specific examples of the vinyl-halomethyl-s-triazabenzene compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazabenzene, 2 , 4-bis (trichloromethyl) -3- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazabenzene, 2-trichloromethyl- 3-amino-6-p-methoxystyryl-s-triazabenzene, or a combination thereof.

Specific examples of the 2- (naphtho-1-substituted) -4,6-bis (halomethyl) -s-triazabenzene compound include 2- (naphtho-1-substituted) -4,6 -Bis (trichloromethyl) -s-triazabenzene, 2- (4-methoxy-naphtho-1-substituted) -4,6-bis (trichloromethyl) -s-triazine Heterobenzene, 2- (4-ethoxy-naphtho-1-substituted) -4,6-bis (trichloromethyl) -s-triazabenzene, 2- (4-butoxy-naphthalene Benzo-1-substituent) -4,6-bis (trichloromethyl) -s-triazabenzene, 2- [4- (2-methoxyethyl) -naphtho-1-substituent] -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-substituted] -4,6-bis (trichloromethyl) -s -Triazabenzene, 2- (2-methoxy-naphtho-1-substituted) -4,6-bis (trichloromethyl) -s-triazabenzene, 2- (6-methoxy Methyl-5-methyl-naphtho-2-substituted) -4,6-bis (trichloromethyl) -s-triazabenzene, 2- (6-methoxy-naphtho-2-substituted ) -4,6-bis (trichloromethyl) -s-triazabenzene, 2- (5-methoxy-naphtho-1-substituted) -4,6-bis (trichloromethyl) ) -s-triazabenzene, 2- (4,7-dimethoxy-naphtho-1-substituted) -4,6-bis (trichloromethyl) -s-triaza Benzene, 2- (6-ethoxy-naphtho-2-substituted) -4,6-bis (trichloromethyl) -s-triazabenzene, 2- (4,5-dimethoxy -Naphtho-1-substituted) -4,6-bis (trichloromethyl) -s-triazabenzene, or a combination thereof.

Specific examples of the 4- (p-aminophenyl) -2,6-bis (halomethyl) -s-triazabenzene compound include 4- [p-N, N-bis (ethoxycarbonylmethyl) Yl) aminophenyl] -2,6-bis (trichloro (Methyl) -s-triazabenzene, 4- [o-methyl-p-N, N-bis (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-bis (trichloromethyl) -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-bis (phenyl) aminophenyl] -2,6-bis (trichloromethyl) -s -Triazabenzene, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [p-N- ( P-methoxyphenyl) carbonylaminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-N, N-bis (ethoxycarbonylmethyl) (Amino) aminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-bromo-p-N, N-bis (ethoxycarbonylmethyl) amine Phenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-chloro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-fluoro-p-N, N-bis (ethyl Oxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [o-bromo-p-N, N-bis (ethoxycarbonyl) (Methyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [o-chloro-p-N, N-bis (ethoxycarbonylmethyl) Aminophenyl-2,6-bis (trichloromethyl) -s-triazabenzene, 4- [o-fluoro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [o-bromo-p-N, N-bis (chloroethyl) aminophenyl] -2,6- Bis (trichloromethyl) -s-triazabenzene, 4- [o-chloro-p-N, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) ) -s-triazabenzene, 4- [o-fluoro-p-N, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine Heterobenzene, 4- [m-Bromo-p-N, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [ M-chloro-p-N, N-bis (chloroethyl) amine Phenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-fluoro-p-N, N-bis (chloroethyl) aminophenyl] -2 , 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -)-S-triazabenzene, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triaza Benzene, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-bromo -P-N-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-chloro-p-N-ethoxy (Carbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 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-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (M-fluoro-p-N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-bromo-p-N-chloroethyl Aminoaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (O-chloro-p-N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-fluoro-p-N-chloroethyl Aminoaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxycarbonylmethyl) amino] phenyl] -1,3,5-triazabenzene, or a combination thereof. Triazabenzene compounds can be used alone or in combination.

The triazabenzene compound preferably includes 4- [m-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl)- s-triazabenzene, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazabenzene, or a combination thereof.

Specific examples of the acetophenone-based compound include p-dimethylamine acetophenone, α, α'-dimethoxyoxy azoacetophenone, and 2,2'-dimethyl-2-phenylbenzene Acetone, P-methoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 2-benzyl-2-N, N-di Methylamine-1- (4-morpholinophenyl) -1-butanone, or a combination thereof.

The acetophenone compound may be used alone or in combination.

2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone may be a product manufactured by Ciba Refinery Co., Ltd. under the model number IRGACURE 907. 2-Benzyl-2-N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone may be a product manufactured by Ciba Refining Co., Ltd. under the model number IRGACURE 369.

The acetophenone compounds preferably include 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 2-benzyl-2-N, N-di Methylamine-1- (4-morpholinophenyl) -1-butanone, or a combination thereof.

Specific examples of the diimidazole compounds 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'-bis (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.

Diimidazole compounds can be used alone or in combination.

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

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

Specific examples of the α-diketone compound include benzodiazone, diethylhydrazone, or a combination of the foregoing compounds. The α-diketone compound may be used alone or in combination.

Specific examples of the ketol-based compound include benzophenone. The keto alcohol compounds can be used alone or in combination.

Specific examples of the ketol ether-based compound include benzophenone methyl ether, benzophenone ethyl ether, benzophenone isopropyl ether, or a combination of the foregoing compounds. The ketol ether compounds may be used alone or in combination.

Specific examples of the phosphonium oxide-based compound include 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide, bis (2,6-dimethoxyphenylphosphonium) -2,4,4-tri Methylphenylphosphine oxide, or a combination thereof. The phosphonium oxide compound may be used alone or in combination.

Specific examples of the quinone compound include anthraquinone, 1,4-naphthoquinone, or a combination of these compounds. The quinone compound can be used alone or in combination.

Specific examples of the halogen-containing compound include benzamidine chloride, tribromomethyl benzamidine, tris (trichloromethyl) -s-triazabenzene, or a combination thereof. The halogen-containing compound may be used alone or in combination.

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

Based on 100 parts by weight of the alkali-soluble resin (A) and 5 to 95 parts by weight of the other photoinitiator (C-2), preferably 5 to 80 parts by weight, and more preferably 5 to 65 Parts by weight.

In addition, based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the photoinitiator (C) is 10 to 100 parts by weight, preferably 15 to 90 parts by weight, and more preferably 20 to 80 parts by weight.

Solvent (D)

The solvent (D) means that an alkali-soluble resin (A), an ethylenically unsaturated compound (B) and a photoinitiator (C), a black pigment (E) described below, and The compound (F) having the shown epoxy group structure is a solvent which does not react with the above components, and is preferably one having an appropriate volatility.

Specific examples of the solvent (D) include: alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, diethylene glycol alkyl ethers, other ether compounds, ketone compounds, and alkyl lactate An ester compound, another ester compound, an aromatic hydrocarbon compound, a carboxylic acid amine compound, or a combination thereof.

Specific examples of the alkyl glycol monoalkyl ether compounds include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol mono-n-butyl ether. Ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether , Tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether or the like, or a combination of the above compounds.

Specific examples of the alkyl glycol monoalkyl ether acetate compounds include: ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate or the like, or the above compounds combination.

Specific examples of the diethylene glycol alkyl ether include diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether or the like, or a combination of the above compounds.

Specific examples of other ether compounds include tetrahydrofuran or the like.

Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, or the like, or a combination of the foregoing compounds.

Specific examples of the alkyl lactate-based compound include methyl lactate, ethyl lactate or the like, or a combination of the aforementioned compounds.

Specific examples of other ester compounds include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, and 3-methoxypropionate. Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, 2-hydroxy-3-methylbutyrate, 3 -Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Isobutyl, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvate Ethyl acetate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, ethyl 2-oxybutyrate or the like, or a combination thereof.

Specific examples of the aromatic hydrocarbon compound include toluene, xylene, or the like, or a combination of the foregoing compounds.

Carboxylic acid amine compounds N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide or an analog thereof, or a combination thereof.

The solvent (D) can be used alone or in combination.

The solvent (D) is preferably propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.

The use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the solvent (D) is 1,000 to 6000 parts by weight, preferably 1200 to 5500 parts by weight, and more preferably 1500 to 5000 parts by weight.

Black pigment (E)

The black pigment (E) is preferably a black pigment having heat resistance, light resistance, and solvent resistance.

Specific examples of the black pigment (E) include: black organic pigments such as perylene black, cyanine black, or aniline black; red, blue, green, purple, and yellow Among pigments such as cyanine, magenta, etc., two or more pigments are selected and mixed to form a black-colored mixed organic pigment; carbon black, chromium oxide, and oxidation A light-shielding material such as iron, titanium black, or graphite. Specific examples of the carbon black include CIpigment black 7 or commercially available products (trade names MA100, MA230, MA8, # 970, # 1000) manufactured by Mitsubishi Chemical Corporation. , # 2350 or # 2650). The black pigment (E) may be used alone or in combination.

The black pigment (E) is preferably carbon black, and the carbon black is, for example, a commercially available product MA100 or MA230 manufactured by Mitsubishi Chemical.

Based on the use amount of the alkali-soluble resin (A) described above, the use amount of the black pigment (E) is 100 to 600 parts by weight, preferably 120 to 550 parts by weight, and more preferably 150 to 500 parts by weight.

Contains a compound (F) having an epoxy group structure represented by the formula (F-I)

The compound (F) containing an epoxy group structure represented by the formula (FI) is shown below:

In Formula (FI), each of Z independently represents a halogen atom or an alkyl group having 1 to 5 carbon atoms; each of W ₁ independently represents a single bond or an alkylene group having 1 to 10 carbon atoms; multiple W ₂ Each independently represents a single bond, O, or an alkylene group having 1 to 10 carbon atoms; multiple W ₃ each independently represents a hydrogen atom, a group represented by formula (F-II) or formula (F-III), where W At least one of ₃ is a group represented by formula (F-II) or formula (F-III); a plurality of L ₁ each independently represent a hydrogen atom or a methyl group; i each independently represents an integer of 0 to 4; j represents 0 Integer to 2.

In formula (F-II) and formula (F-III), each of a plurality of L ₂ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; L ₃ represents a single bond or an alkylene group having 1 to 10 carbon atoms * Represents a bonding site, in the alkylene group having 1 to 10 carbon atoms in W ₁ , W ₂ and L ₃ , any -CH ₂ -can be replaced by -O-, -CH = CH- Or -C≡C-, and an arbitrary hydrogen atom may be replaced with a halogen atom.

Preferably, in the formula (FI), a plurality of Z each independently represent a fluorine atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms; each of a plurality of W ₁ independently represents a single bond or a carbon group having 1 to 5 carbon atoms; Alkyl; each of W ₂ independently represents a single bond, O or an alkylene group having 1 to 5 carbon atoms; each of W ₃ independently represents a hydrogen atom, and is represented by formula (F-II) or formula (F-III) A group in which at least one of W ₃ is a group represented by formula (F-II) or formula (F-III); a plurality of L ₁ each independently represent a hydrogen atom or a methyl group; i each independently represents 0 to An integer of 2; j represents an integer of 0 to 2.

In formula (F-II) and formula (F-III), each of a plurality of L ₂ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; L ₃ represents a single bond or an alkylene group having 1 to 5 carbon atoms *; At the bonding point, in the alkylene group having 1 to 5 carbon atoms in W ₁ , W ₂ and L ₃ , any -CH ₂ -can be replaced by -O-, and any hydrogen atom It can be replaced with a fluorine atom or a chlorine atom.

More preferably, in the formula (FI), a plurality of Z each independently represent a fluorine atom, a chlorine atom, or an alkyl group having 1 to 2 carbon atoms; each of a plurality of W ₁ independently represents a single bond or a carbon group having 1 or 2 carbon atoms; Alkyl; each of W ₂ independently represents a single bond, O, or an alkylene group having 1 or 2 carbon atoms; each of W ₃ independently represents a hydrogen atom, and is represented by formula (F-II) or formula (F-III) A group in which at least one of W ₃ is a group represented by formula (F-II) or formula (F-III); a plurality of L ₁ each independently represent a hydrogen atom or a methyl group; i each independently represents 0 to An integer of 2; j represents an integer of 0 to 2.

In formula (F-II) and formula (F-III), each of a plurality of L ₂ independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; L ₃ represents a single bond or an alkylene group having 1 or 2 carbon atoms *; At the bonding point, in the alkylene group having 1 or 2 carbon atoms in W ₁ , W ₂ and L ₃ , any -CH ₂ -can be replaced by -O-, and any hydrogen atom It can be replaced with a fluorine atom or a chlorine atom.

Particularly preferably, in the formula (FI), a plurality of Z each independently represent a fluorine atom or an alkyl group having 1 to 2 carbon atoms; a plurality of W ₁ each independently represent a single bond or an alkylene group having 1 or 2 carbon atoms; Each of W ₂ independently represents a single bond, O, or an alkylene group having 1 or 2 carbon atoms; each of W ₃ independently represents a hydrogen atom, or a group represented by formula (F-II) or (F-III) A group in which at least one of W ₃ is a group represented by formula (F-II) or formula (F-III); a plurality of L ₁ each independently represent a hydrogen atom or a methyl group; i each independently represents an integer of 0 or 1 ; J represents an integer from 0 to 2.

In formula (F-II) and formula (F-III), each of a plurality of L ₂ independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms; L ₃ represents a single bond or an alkylene group having 1 or 2 carbon atoms *; At the bonding point, in the alkylene group having 1 or 2 carbon atoms in W ₁ , W ₂ and L ₃ , any -CH ₂ -can be replaced by -O-, and any hydrogen atom It can be replaced with a fluorine atom or a chlorine atom.

Here, "containing the compound (F) having an epoxy group structure represented by Formula (FI)" means that as long as the partial structure of the compound contains an epoxy group structure represented by Formula (FI), the The compound belongs to the range of the compound (F) described in the present invention.

Specific examples of the compound containing the compound (F) having an epoxy group structure represented by the formula (FI) include a compound represented by the following formula (F-IV), a compound represented by the following formula (FV), or a commercially available compound. Products TECHMORE VG3101, TECHMORE VG3101L, TECHMORE VG3101H (made by Mitsui Chemicals), NC-6000, NC-6300, NC-6300C, NC-6300H, NC-6500 (made by Nippon Kayaku).

The compound (F) containing an epoxy group structure represented by the formula (F-I) of the present invention may be used in combination with a compound not having an epoxy group structure represented by the formula (F-I). In the compound (F) containing an epoxy group structure represented by the formula (FI), the amount of the compound having no epoxy group structure represented by the formula (FI) is preferably 50% by weight or less. It is more preferably 40% by weight or less, and particularly preferably 30% by weight or less. By using a compound that does not have an epoxy group structure represented by the formula (F-I) in combination, it is possible to increase the composition of the photosensitive resin for a black matrix containing the compound (F) having an epoxy group structure represented by the formula (F-I). Compatibility with other ingredients in the product.

Specific examples of the compound having no epoxy group structure represented by the formula (FI) include a homopolymer of a monomer having an epoxy group, and a copolymer of two or more monomers having an epoxy group. Copolymers of monomers with epoxy groups and monomers without epoxy groups, bisphenol A epoxy resin, glycidyl ester epoxy resin, alicyclic epoxy resin, glycidyl ether epoxy Resin, bisphenol A phenolic epoxy resin, phenolic phenolic epoxy resin, and cresol novolac epoxy resin.

The compound (F) containing an epoxy group structure represented by the formula (F-I) can be used alone or in combination.

The use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the compound (F) containing the epoxy group structure represented by the formula (FI) is 10 to 180 parts by weight, preferably 20 to 150. It is more preferably 30 to 120 parts by weight.

When the photosensitive resin composition for a black matrix does not include the compound (F) having an epoxy group structure represented by the formula (F-I), the obtained black matrix cannot obtain an appropriate bluishness.

Inorganic oxide fine particles (G)

The inorganic oxide fine particles (G) contained in the photosensitive resin composition for a black matrix of the present invention may be silicon compound particles, aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, barium compound particles, or the like. And other composite particles.

Specific examples of silicon compound particles: No. OSCAR 101 (average particle size is 12nm), OSCAR 105 (average particle size is 60nm), OSCAR 106 (average particle size is 120nm) or CATALOID-S (average particle size is 5nm to 80nm), etc., Nissan Chemical Manufacturing Products [Model is IPA-ST (average particle size is 12nm), IPA-ST-L (average particle size is 45nm), IPA-ST-ZL (average particle size is 100nm), MEK-ST, MIBK-ST ( (Average particle size is 12nm), NBA-ST, PGM-ST (average particle size is 15nm), XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-N, ST-O, ST-50, ST-OL or OZ-S30K, etc.], products made by KCM [model SG-SO100 (average particle size 100nm)], products made by Fuso Chemical [Models are KUOTORON PL-2L-PGME (average particle size is 16nm), KUOTORON PL-2L-BL (average particle size is 17nm), KUOTORON PL-2L-DAA (average particle size is 17nm), KUOTORON PL-2L ( (Average particle diameter is 18 nm to 20 nm) or GP-2L (average particle diameter is 18 nm to 20 nm), etc.], a product manufactured by TOKUYAMA [Reolosil (average particle diameter of 5 nm to 50 nm)].

Specific examples of the tin compound particles are products manufactured by the High Purity Chemical Research Institute.

Specific examples of titanium compound particles: products manufactured by Niwa Catalyst Co., Ltd. [model is OPTOLAKE TR-505], products manufactured by TAYCA [models are MT-05, MT-100W, MT-100SA, MT-100HD, MT-300HD, MT-150A, ND138, ND139, ND140, ND154, ND165, ND177, TS-063, TS-103 or TS-159, etc.].

Specific examples of zirconium compound particles OPTOLAKE TR-554], products made by Sumitomo Osaka Cement [models HXU-110JC, HXU-210C or NZD-3101, etc.].

Specific examples of composite particles: Products manufactured by Nissho Catalyst [Model: OPTOLAKE TR-502, OPTOLAKE TR-503, OPTOLAKE TR-504, OPTOLAKE TR-513, OPTOLAKE TR-520, OPTOLAKE TR-527, OPTOLAKE TR-528 Or silica dioxide-titanium dioxide composite particles such as OPTOLAKE TR-529], products made by Admatechs [models are Admafine SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, or SE3200-SEJ, etc. [Silicon oxide-alumina composite particles], and tin dioxide-zirconia composite particles manufactured by Niwa Catalyst.

The inorganic oxide fine particles (G) may be used alone or in combination.

The use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the inorganic oxide fine particles (G) is 2 to 10 parts by weight, preferably 3 to 9 parts by weight, and more preferably 4 to 8 parts by weight.

When the inorganic resin fine particles (G) are contained in the photosensitive resin composition for a black matrix, the obtained black matrix can further obtain a more appropriate bluishness.

Additive (H)

Without affecting the efficacy of the present invention, the photosensitive resin composition of the present invention can further optionally add an additive (H). Specific examples of the additive (H) include a surfactant, a filler, and a polymer (referred to as the above-mentioned alkali-soluble resin (A) Polymers other than), adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerants, or other colorants.

The surfactant helps to improve the coatability of the photosensitive resin composition. Specific examples of the surfactant include a cationic surfactant, an anionic surfactant, a non-ionic surfactant, an amphoteric surfactant, a polysiloxane surfactant, a fluorine-based surfactant, or the above-mentioned surfactant. Agent combination.

Specifically, the surfactant is, for example, polyethoxyalkyl ethers such as polyethoxydodecyl ether, polyethoxystearyl ether, and polyethoxy oleyl ether; Polyethoxyalkyl phenyl ethers such as ethoxy octyl phenyl ether, polyethoxy nonyl phenyl ether; polyethylene glycols such as polyethylene glycol dilaurate, polyethylene glycol distearate Diesters; sorbitan fatty acid esters; fatty acid modified polyesters; or tertiary amine modified polyurethanes. The aforementioned surfactants can be used alone or in combination.

Specific examples of the surfactant include KP products manufactured by Shin-Etsu Chemical Industry, SF-8427 products manufactured by Dow Corning Toray Co., Ltd., and general-purpose products manufactured by Kyoeisha Oil Chemical Industry Polyflow products, F-Top products manufactured by Tochem Products Co., Ltd., and Mekafke manufactured by Dainippon Ink Chemical Industry (Megafac) products, Fluorade products manufactured by Sumitomo 3M, Asahi Guard products manufactured by Asahi Glass, or Surflon products manufactured by Asahi Glass.

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

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

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxy Propanolpropyltrimethoxysilane, 3-glycidylpropylmethyldiethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropoxypropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or a combination thereof.

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

Specific examples of the ultraviolet absorber include 2- (3-third butyl-5-methyl-2-hydroxyphenyl) -5-chlorophenyl azide, alkoxy phenone, or the compound combination.

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

Other colorants include inorganic pigments, organic pigments, or a combination of the two.

Specific examples of the inorganic pigment include metal compounds such as metal oxides and metal salts (e.g., metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, antimony, etc.) or the above. List metal composite oxides.

Specific examples of the organic pigment include CI Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81 , 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139 , 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17 , 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2 , 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1 , 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170 , 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 1 90, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 19, 23, 29 , 32, 36, 38, 39; CI Pigment Blue 1, 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 66; CI Pigment Green 7, 36, 37; CI Pigment Brown 23, 25, 28 or a combination of these pigments.

<Manufacturing method of photosensitive resin composition for black matrix>

A method for preparing a photosensitive resin composition for a black matrix, for example, an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), and a photoinitiator The agent (C), the solvent (D), the black pigment (E), and the compound (F) containing an epoxy group structure represented by the formula (FI) are placed in a stirrer and stirred to uniformly mix into a solution state. If necessary, inorganic oxide fine particles (G) and additives (H) may be added and uniformly mixed to obtain a photosensitive resin composition in a solution state.

The method for preparing the photosensitive resin composition is not particularly limited. A method for preparing a photosensitive resin composition for a black matrix is, for example, first dispersing a part of the alkali-soluble resin (A) and the ethylenically unsaturated group-containing compound (B) in a part of the solvent (D) to form a dispersion solution; And then the remaining alkali-soluble resin (A), ethylenically unsaturated group-containing compound (B), photoinitiator (C), solvent (D), black pigment (E), and The compound (F) having the epoxy structure shown below was prepared.

Alternatively, the photosensitive resin composition may be formed by first dispersing a part of the black pigment (E) in a mixture of a part of the alkali-soluble resin (A) and a part of the solvent (D) to form a black pigment dispersion liquid; and Add an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D), a black pigment (E), and a ring containing a ring represented by formula (FI). Compound (F) having an oxo structure. The dispersing step of the black pigment (E) can be performed by mixing with a mixer such as a beads mill or a roll mill.

<Manufacturing Method of Black Matrix>

The black matrix is manufactured by sequentially applying pre-baking, exposure, development, and post-exposure baking treatments on the substrate to the above-mentioned photosensitive resin composition. Also, the resulting black matrix When the film thickness is 1 μm, the optical density range may be 3.0 or more, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The method of preparing the black matrix is detailed below.

First, a photosensitive resin composition for a black matrix in a solution state is uniformly coated on a substrate by a coating method such as spin coating or cast coating to form a coating film. Specific examples of the above substrate include: alkali-free glass, soda-lime glass, hard glass (Pales glass), quartz glass used for liquid crystal display devices and the like, and those with a transparent conductive film attached to the glass; or used for solid-state photography The substrate of a photoelectric conversion device (such as a silicon substrate) and the like.

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 in a pre-bake manner to form a pre-baking coating film. It is important to note that the conditions for reduced-pressure drying and pre-baking vary depending on the type and ratio of each component. Generally speaking, reduced-pressure drying is performed at a pressure of less than 200 mmHg for 1 second to 20 seconds, and pre-baking is a heat treatment of the coating film at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes.

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

Then, immersing the exposed pre-baking coating film in a developing solution at a temperature of 23 ± 2 ° C to remove the pre-baking coating film of the unexposed portion, so that the substrate can be placed on the substrate. Form a specific pattern.

The developing solution is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, diethylamine, Dimethylethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5,4,0] -7-undecene, etc. Basic compounds, etc. The concentration of the developing solution is generally 0.001 wt% to 10 wt%, preferably 0.005 wt% to 5 wt%, and more preferably 0.01 wt% to 1 wt%.

After the pre-baking coating film is developed, the substrate having the specific pattern is washed with water, and then the specific pattern is air-dried with compressed air or compressed nitrogen. Then, a post-bake process is performed using a heating device such as a hot plate or an oven. The post-baking temperature is usually 150 to 250 ° C., wherein the heating time using a hot plate is 5 minutes to 60 minutes, and the heating time using an oven is 15 minutes to 150 minutes. After the above processing steps, a black matrix can be formed on the substrate.

<Manufacturing Method of Color Filter>

The manufacturing method of the color filter is similar to the manufacturing method of the black matrix. Specifically, the photosensitive composition for a color filter is coated on a substrate on which a black matrix has been formed, and then sequentially subjected to pre-baking, exposure, development, and post-baking processes. However, under the conditions of reduced pressure drying, reduced pressure drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds. After the above processing steps, a specific pattern can be fixed, thereby forming a pixel layer. In addition, by repeating the above steps, sequentially forming pixel layers such as red, green, and blue on the substrate, a substrate (ie, a color filter having a pixel layer) on which a black matrix and a pixel layer are formed can be obtained.

<Method for Manufacturing Liquid Crystal Display Element>

First, a color filter formed by the above-mentioned color filter manufacturing method and a substrate provided with a thin film transistor (TFT) are arranged to face each other, and a gap (crystal) is provided between the two. Cell gap). Next, the color filter and a peripheral portion of the substrate are bonded with an adhesive, and an injection hole is left. Then, liquid crystal is injected through the injection hole in the substrate surface and the gap separated by the adhesive, and finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a polarizing plate is provided by providing a polarizing plate on the other side of the color filter that contacts the liquid crystal layer and the other side of the substrate that contacts the liquid crystal layer. The liquid crystal used above, that is, a liquid crystal compound or a liquid crystal composition is not particularly limited here. However, any liquid crystal compound and liquid crystal composition can be used.

In addition, the liquid crystal alignment film used in making the color filter is used to restrict the alignment of liquid crystal molecules, and there is no particular limitation. Any inorganic or organic substance can be used, and the present invention is not limited thereto.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to the contents disclosed in these examples.

<Example> Preparation example of polymerizable unsaturated diol compound (a-1-1)

Preparation Examples 1 to 3 of the diol compound (a-1-1) containing a polymerizable unsaturated group will be described below:

Preparation Example 1

First, 100 parts by weight of a rhenium epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, and 0.1 part by weight Parts of 2,6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added to a 500-ml four-necked flask in a continuous manner. The feeding speed is controlled at 25 parts by weight / minute, and the temperature of the reaction process is maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a light yellow transparent mixed solution with a solid content concentration of 50% by weight can be obtained. Next, subjecting the light yellow transparent mixed liquid to the steps of extraction, filtration, and heating and drying, to obtain a polymerizable unsaturated group-containing diol compound (a-1- in Preparation Example 1 having a solid content of 99.9% by weight) 1-a).

Preparation Example 2

First, 100 parts by weight of a fluorene 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, and 0.1 part by weight Parts of 2,6-di-tert-butyl-p-cresol and 135 parts by weight of propylene glycol monomethyl ether acetate were added to a 500-ml four-necked flask in a continuous addition manner. The feeding speed is controlled at 25 parts by weight / minute, and the temperature during the reaction is maintained at 100 ° C to 110 ° C. After the reaction for 15 hours, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heating and drying to obtain a polymerizable unsaturated group-containing diol compound (a-1-1- b).

Preparation Example 3

100 parts by weight of a fluorene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 100 parts by weight of 2-methacrylic acid, ethoxysuccinate, and 0.3 parts by weight of chlorine Benzyltriethylammonium, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol, and 200 parts by weight of propylene glycol monomethyl ether acetate were continuously added to a 500-ml four-necked flask. The feeding speed is controlled at 25 parts by weight / minute, and the temperature of the reaction process is maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heating and drying to obtain a polymerizable unsaturated group-containing diol compound (a-1-1-c) in Preparation Example 3 having a solid content of 99.9% by weight. ).

Synthesis example of unsaturated resin (A-1)

The following describes Synthesis Example A-1-1 to Synthesis Example A-1-3 of the resin (A-1) having an unsaturated group:

Synthesis Example A-1-1

First, 1.0 mol of the diol compound (a-1-1-a) having a polymerizable unsaturated group in Preparation Example 1 and 0.3 mol of biphenyltetracarboxylic acid (abbreviated as a-1-2-a) ), 1.4 moles of succinic acid (abbreviated a-1-3-c), 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2,6-di-tert-butyl-p-cresol, 700 G of propylene glycol monomethyl ether acetate and 100 g of ethyl 3-ethoxypropionate were added simultaneously to 500 ml Bottle to form a reaction solution. Here, "simultaneous addition" means adding a tetracarboxylic acid or its acid dianhydride (a-1-2) and a dicarboxylic acid or its anhydride (a-1-3) at the same reaction time. Next, the reaction solution is heated to 110 ° C. and reacted for 2 hours to obtain a resin A-1-1 having an unsaturated group.

Synthesis Example A-1-2

1.0 mol of the diol compound (a-1-1-a) having a polymerizable unsaturated group, 2.9 g of benzyltriethylammonium chloride, and 950 g of propylene glycol methyl ether acetate were added to A 500 ml four-necked flask to form a reaction solution. Next, 0.6 mol of benzophenonetetracarboxylic dianhydride (a-1-2-b) was added and reacted at 90 ° C for 2 hours. Then, 0.8 mol of maleic acid (a-1-3-a) was added and reacted at 90 ° C for 4 hours. Through the above synthetic steps, a resin A-1-2 having an unsaturated group can be obtained.

Synthesis Example A-1-3

The resin having an unsaturated group in Synthesis Example A-1-3 was prepared by the same procedure as in Synthesis Example A-1-2, and the difference was that the component types of the resin having unsaturated groups and the amount of use were changed , Reaction time, reaction temperature, and reactant addition time (as shown in Table 1). Here, "addition in stages" means that tetracarboxylic acid or its acid dianhydride (a-1-2) and dicarboxylic acid or its anhydride (a-1-3) are added separately at different reaction times, that is, first Tetracarboxylic acid or its acid dianhydride (a-1-2) is added, followed by dicarboxylic acid or its anhydride (a-1-3).

The compounds corresponding to the abbreviations in Table 1 are shown below.

Examples of synthesis of other alkali-soluble resins (A-2)

The following describes Synthesis Examples A-2-1 to A-2-2 of other alkali-soluble resins (A-2):

Synthesis Example A-2-1

A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. After introducing nitrogen, 40 parts by weight of methacrylic acid, 30 parts by weight of methyl methacrylate, 30 Parts by weight of styrene, 2 parts by weight of 2,2'-azobis (isobutyronitrile) (2,2'-Azobis (isobutyronitrile), AIBN), and 100 parts by weight of isopropanol. Next, the above mixture was slowly stirred and the solution was warmed to 80 ° C. Next, polycondensation was performed at 80 ° C. for 4 hours, and then hydroquinone monomethyl ether was added in parts by weight, and then polymerization was performed while slowly returning to room temperature. Then, after adding 40 parts by weight of Glycidyl methacrylate (GMA), the product was precipitated with ultrapure water, filtered, and dried to obtain other products having an average molecular weight Mw of 40,000 and an acid value of 110 mgKOH / g. Alkali soluble resin A-2-1.

Synthesis Example A-2-2

In a 500 ml three-necked flask, add 0.1 mol of 3- (triethoxysilyl) propylsuccinic anhydride and 0.1 mol of 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, 0.50 mole of methyltrimethoxysilane, 0.30 mole of diphenyldimethoxysilane, and 200 grams of 4-hydroxy-4-methyl-2-pentanone, An aqueous oxalic acid solution (0.35 g of oxalic acid / 75 g of water) was added over 30 minutes while stirring at a warm temperature. Next, the flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes. Then, the oil bath was heated to 120 ° C within 30 minutes. When the temperature of the solution is reduced to 110 ° C. (that is, the reaction temperature), the polymerization is continued by heating and stirring for 5 hours (that is, the polycondensation time). Then, the solvent is removed by distillation to obtain other alkali-soluble resin A-2-2.

Examples and comparative examples of photosensitive resin composition for black matrix

Examples 1 to 15 and Comparative Examples 1 to 6 of the photosensitive resin composition for a black matrix are described below:

Example 1

100 parts by weight of other alkali-soluble resin A-2-1, 30 parts by weight of dipentaerythritol hexaacrylate (abbreviated as B-1), and 80 parts by weight of ethylene glycol dimethacrylate (abbreviated as B-2) ), 10 parts by weight of a photoinitiator represented by formula (CI-4) (abbreviated as C-1-1), 10 parts by weight of IRGACURE OXE-02 (abbreviated as C-2-1), 150 parts by weight Parts of black pigment MA100 (abbreviated as E-1) and 20 parts by weight of TECHMORE VG3101H (abbreviated as F-1) were added to 2500 parts by weight of propylene glycol monomethyl ether acetate (abbreviated as D-1), and the After the agitator is uniformly stirred, a photosensitive resin composition for a black matrix of Example 1 can be obtained.

Examples 2 to 15

The photosensitive resin composition for a black matrix of Examples 2 to 15 was prepared by the same procedure as in Example 1, and the difference was that the component types of the photosensitive resin composition for a black matrix and the amount of use thereof were changed. (As shown in table 2).

Comparative Examples 1 to 6

The photosensitive resin compositions of Comparative Examples 1 to 6 were prepared by the same procedure as in Example 1, and the difference was that the component types of the photosensitive resin composition and their amounts of use were changed (as shown in Table 3). ).

The compounds corresponding to the reference numerals in Tables 2 and 3 are shown below.

Evaluation method

Bluishness

The photosensitive resin composition for a black matrix prepared in each of the above examples and comparative examples was applied by a coater (model: MS-A150, purchased from Shinko Trading) in a length and width manner by spin coating. A coating film having a thickness of 3 μm was obtained on a 100-mm (mm) glass substrate. Then, the glass substrate was pre-baked at 100 ° C for 100 seconds to form a pre-baked coating film.

Then, the above pre-baked coating film was placed under a line and space mask (manufactured by Nibbon Filcon, Japan), and 100 mJ / cm ² of ultraviolet light (exposure machine model AG500- 4N; manufactured by M & R Nano Technology). Next, it was developed with 0.04538% potassium hydroxide aqueous solution at 23 ° C. for 1 minute to remove the coating film on the unexposed portion of the substrate and obtain a specific pattern. Then, the glass substrate with a specific pattern was washed with water and air-dried, and then baked at 235 ° C for 10 minutes to obtain a black matrix. Finally, the colorimeter (L *, a *, b *), where b * is evaluated as follows:

◎: b * ≦ -0.1

○: -0.1 <b * ≦ 0.05

△: 0.05 <b * ≦ 0.2

╳: b *> 0.2

<Evaluation Results>

As can be seen from Tables 2 and 3, it is composed of a photosensitive resin for a black matrix containing both a specific photoinitiator (C-1) and a compound (F) having an epoxy group structure represented by formula (FI). Compared with the black matrices (Examples 1 to 15) produced by the object, the black matrix of Comparative Examples 1 to 6 had poor blueness evaluation.

In addition, the black matrix (Examples 3, 4, 7, 8, 10 to 13) formed by the photosensitive resin composition for a black matrix using the alkali-soluble resin (A-1) was evaluated for better bluishness.

In addition, when the inorganic resin fine particles (G) are further contained in the photosensitive resin composition for a black matrix (Examples 5 to 7, 9 to 13), the evaluation of the bluishness of the black matrix is also favorable.

In summary, the photosensitive resin composition for a black matrix of the present invention contains a specific photoinitiator (C-1) and a compound (F) having an epoxy group structure represented by formula (FI). A proper bluish chromaticity can be obtained without increasing the amount of black pigment used.

On the other hand, if the photosensitive resin composition for a black matrix of the present invention further contains a resin (A-1) having an unsaturated group and fine particles of inorganic oxides (G), the obtained black matrix can be further obtained. More appropriate bluishness.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

Claims (12)

A photosensitive resin composition for a black matrix, comprising: an alkali-soluble resin (A); an ethylenically unsaturated group-containing compound (B); a photoinitiator (C); a solvent (D); a black pigment (E); And a compound (F) having an epoxy group structure represented by formula (FI), wherein the photoinitiator (C) includes a photoinitiator (C-1) having a structure of formula (CI); In Formula (CI), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R _7, and R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, COR ₁₆ , OR ₁₇ , a halogen atom, NO ₂ , a group represented by the formula (C-II) or a group represented by the formula (C-III); Or any two of R ₁ to R ₈ whose relative positional relationship is adjacent to each other independently represent an alkenyl group substituted by a group represented by formula (C-IV) and having a carbon number of 2 to 10; ₁ ~ R ₈ or the relative positional relationship of both R ortho to one another independently of any common is _{- (CH 2) p -Y- (} CH 2) q - , or a group represented by the formula (CV) represents; However, the condition is that at least one of any two of R ₁ to R ₈ whose relative positional relationship is adjacent is a group represented by the formula (CV); each of R ₉ , R ₁₀ , R _11, and R ₁₂ Independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: a halogen atom, a phenyl group, a CN, an OH, SH, alkoxy, COOH or COOR ^X having 1 to 4 carbons; R ^X represents an alkyl group having 1 to 4 carbons; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently unsubstituted Phenyl or phenyl substituted with more than one of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OR ₁₇ , SR _18, or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a halogen atom, 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 are} optionally passed The groups R ₁₇ , R ₁₈ , R ₁₉ and / or R ₂₀ form a 5- or 6-membered ring with one carbon atom in the naphthyl ring; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently COR _16, NO ₂ or a group represented by the formula (C-II); Y represents O, S NR ₂₆ or a single bond; p represents an integer of 0 to 3; Q represents an integer of 1 to 3; X is CO or represents a single bond; R ₁₃ represents alkyl having 1 to 20, which is unsubstituted or substituted with one or more Substituted with the following groups: halogen atom, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ or the formula (C-VI) Represented groups; Or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms, interspersed with more than one O, S, SO, SO ₂ , NR ₂₆ or CO, or an alkenyl group having 2 to 12 carbon atoms, which is not interspersed Or interspersed with more than one O, NR ₂₆ or CO, wherein the alkyl group having 2 to 20 carbon atoms and the alkenyl group having 2 to 12 carbon atoms Substituted or substituted with more than one halogen atom; or R ₁₃ represents a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or one or more O, S, and NR ₂₆ not interspersed or interspersed Or a cycloalkyl group having a carbon number of 3 to 10; or R ₁₃ represents a phenyl group or a 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 atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, carbon number having 2 or more O, S, NR ₂₆ or CO interspersed with 2 An alkyl group to 20, or a group represented by formula (C-VII); Or each of them is substituted with a cycloalkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms interspersed with more than one O, S, NR ₂₆ or CO; k represents an integer from 1 to 10; R ₁₄ represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. Substituted or substituted with more than one of the following: a halogen atom, a phenyl group, an alkylphenyl group having 1 to 20 carbon atoms or CN; or R ₁₄ represents a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with one The following groups are substituted: an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, CN, OR ₁₇ , SR _18, and / or NR ₁₉ R ₂₀ ; or R ₁₄ represents carbon Heteroaryl groups of 3 to 20, alkoxy, benzyloxy or phenoxy groups of 1 to 8 carbon atoms, said benzyloxy and phenoxy groups being unsubstituted or having more than one of the following groups Substitution: an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms and / or a halogen atom; R ₁₅ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms , Each of which is unsubstituted or substituted with more than one of the following groups: benzene , A halogen atom, a haloalkyl group having a carbon number of 1 to _{4, CN, NO 2, OR 17} , SR 18, NR 19 R 20, PO (OC k H 2k + 1) 2, SO- ( 1 to 10 carbon atoms Alkyl groups), SO _2- (alkyl groups having 1 to 10 carbons), alkyl groups having 2 to 20 carbons interspersed with more than one O, S or NR ₂₆ ; or each having a carbon number of 1 To 20 alkyl substitutions, the 1 to 20 carbons are unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, carbon 3 to 8 cycloalkyls, 3 to 20 carbons heteroaryl, 6 to 20 carbons aryloxycarbonyl, 3 to 20 carbons heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms which is not interspersed or interspersed with more than one O, CO, or NR ₂₆ ; Or R ₁₅ is an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: a halogen atom, OR ₁₇ , SR ₁₈ , a cycloalkyl group having 3 to 8 carbon atoms, Heteroaryl group having 3 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms, heteroaryloxycarbonyl group having 3 to 20 carbon atoms , NR ₁₉ R ₂₀ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , phenyl, a group represented by the formula (C-VI) or formula (C-VIII) ); Or the alkyl group having 1 to 20 carbon atoms is substituted by a phenyl group, the phenyl group is substituted by a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ substitution; or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms, interspersed with more than one O, SO or SO ₂ , and the alkyl group having 2 to 20 carbon atoms interspersed A radical is unsubstituted or substituted with more than one of the following groups: halogen atom, OR ₁₇ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; Or R ₁₅ represents an alkyl or benzamyl group having 2 to 20 carbon atoms, which is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, benzene OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is a naphthylmethyl group which is unsubstituted or substituted with more than one OR ₁₇ or a heteroarylcarbonyl group having 3 to 14 carbons; or R ₁₅ Represents an alkoxycarbonyl group having a carbon number of 2 to 12, which is an unsubstituted or unsubstituted one, and the alkoxycarbonyl group having an unsubstituted or unsubstituted carbon number of 2 to 12 is unsubstituted. Or substituted with more than one hydroxyl group Or R ₁₅ represents a phenoxycarbonyl group, which is unsubstituted or substituted with one or more of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , haloalkyl having 1 to 4 carbon atoms, S (O) _m- (carbon having 1 to 6 Alkyl), unsubstituted or S (O) _m- (phenyl) substituted with alkyl having 1 to 12 carbon atoms or SO _2- (alkyl having 1 to 6 carbon atoms); or R ₁₅ represents S (O ₂ ) O- (phenyl), which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms; or a diphenylphosphinofluorenyl group or a di- (carbon group having 1 to 4 carbon atoms) (Oxy) -phosphinofluorenyl; m represents 1 or 2; R _'14 has one of the meanings given for R ₁₄ ; R' ₁₅ has one of the meanings given for R ₁₅ ; X ₁ represents O , S, SO or SO ₂ ; X ₂ represents O, CO, S or a single bond; R ₁₆ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted Or substituted with more than one of the following groups: phenyl, halogen atom, haloalkyl having 1 to 4 carbons, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or interspersed One or more O, S or NR ₂₆ having 1 to 20 carbons; or each substituted with one or more carbons having 1 to 20 carbons, the 1 to 20 alkyls being Unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, heteroaromatic having 3 to 20 carbons Group, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents a hydrogen atom and a carbon number of 1 to 20 alkyl group, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with more than one of the following groups: halogen atom, phenyl group, OH, SH, CN, olefin group having 3 to 6 carbon atoms Oxygen, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl group with 1 to 4 carbons), O (CO)-(alkyl group with 1 to 4 carbons), O (CO ) -Phenyl, (CO) OH or (CO) O- (alkyl group having 1 to 4 carbons); or R ₁₆ represents an alkyl group having 2 to 12 carbons, with more than one O, S interposed therebetween Or NR ₂₆ ; or R ₁₆ represents (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbons), and carbon number 2 to 12 Alkenyl or 3 to 8 carbon rings Group; or R ₁₆ represents the phenyl group substituted by SR _18, wherein R ₁₈ represents a group bonded to which is attached a single bond or a naphthyl ring azole carbazol portion ₁₆ of the COR phenyl group; n-represents An integer of 1 to 20; R ₁₇ represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 3 carbon atoms), and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or have one or more of the following groups Substitution: halogen atom, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms), O (CO)-(alkyl group with 1 to 4 carbons), O (CO)-(alkenyl group with 2 to 4 carbons), O (CO)-(phenyl), (CO) OH, (CO ) O- (alkyl group with 1 to 4 carbons), cycloalkyl group with 3 to 20 carbons, SO _2- (haloalkyl group with 1 to 4 carbons), O- (carbon number from 1 to 4 Haloalkyl) or a cycloalkyl group having 3 to 20 carbon atoms interspersed with more than one oxygen atom; or R ₁₇ represents an alkyl group with 2 to 20 carbon atoms interspersed with more than one O, S, or NR ₂₆ Or R ₁₇ represents (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(alkyl group having 1 to 8 carbon atoms), and alkyl group having 1 to 8 carbon atoms Radicals, alkenyl radicals having 2 to 12 carbon atoms, alkenyl radicals having 3 to 6 carbon atoms or Interrupted by one or more interrupted by O, S, CO or NR ₂₆ carbon atoms of the cycloalkyl group having 3 to 20; or R ₁₇ represents alkyl having 1 to 8 - (carbon number of 3 to 10 (Cycloalkyl), which is unsaturated or interspersed with more than one oxygen atom; or R ₁₇ represents benzamidine, which is unsubstituted or substituted with one or more alkyl groups having 1 to 6 carbon atoms and halogen atoms , OH, or an alkoxy group having 1 to 3 carbon atoms; or R ₁₇ represents a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups Substitution: halogen atom, OH, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, CN, NO ₂ , phenyl- (alkoxy group having 1 to 3 carbon atoms), benzene An oxygen group, an alkylthio group having 1 to 12 carbon atoms, a phenylthio group, N (an alkyl group having 1 to 12 carbon atoms) ₂ , a diphenyl-amino group, or the group represented by the formula (C-VII) Represented by the group; or R ₁₇ forms a bond to a phenyl group or a naphthalene having a group represented by the formula (C-II) or a group represented by the formula (C-VII) Single bond of one of the carbon atoms of the radical; R ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, and a carbon atom having 3 to 20 carbon atoms Cycloalkyl or phenyl- (alkyl having 1 to 3 carbons), wherein the alkenyl having 2 to 12 carbons, cycloalkyl or phenyl-(carbon having 1 to 3 alkyl) is unsubstituted or has more than one O, S, NR ₂₆ , CO, or (CO) OR ₁₇ ; or R ₁₈ is an alkyl having 1 to 20 carbons, which is unsubstituted Substituted or substituted by more than one of the following groups: OH, SH, CN, alkenyloxy groups having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O- (carbon numbers 1 to 4 Alkyl), O (CO)-(alkenyl having 2 to 4 carbons), O (CO)-(alkyl having 1 to 4 carbons), O (CO)-(phenyl), or ( CO) OR ₁₇ ; or R ₁₈ represents an alkyl group having 2 to 20 carbon atoms, with one or more O, S, NR ₂₆ , CO, or (CO) OR ₁₇ intermingled therebetween; or R ₁₈ represents (CH ₂ CH ₂ O ) _n H, (CH ₂ CH ₂ O) _n (CO)-(alkyl groups having 1 to 8 carbons), alkyl groups having 2 to 8 carbons, or alkenyl groups having 3 to 6 carbons; Or R ₁₈ represents a benzamidine group, which is unsubstituted or substituted with one or more of the following groups: an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH, an alkoxy group having 1 to 4 carbon atoms, or carbon number of 1 to 4 alkylthio; or R ₁₈ represents a phenyl group, a naphthyl group or a C Heteroaryl groups of 3 to 20, each of which is unsubstituted or substituted with one or more of the following: a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, 1 to 12 alkoxy, CN, NO ₂ , phenyl- (alkoxy having 1 to 3 carbons), phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N (alkyl group having 1 to 12 carbons) ₂ , diphenylamino group, (CO) O- (alkyl group having 1 to 8 carbons), C (O)-(carbon group having 1 to 8 carbons) (Alkyl), C (O) N- (alkyl having 1 to 8 carbons) ₂ or a group represented by the formula (C-VII); R ₁₉ and R ₂₀ each independently represent a hydrogen atom and a carbon number Alkyl group of 1 to 20, hydroxyalkyl group of 2 to 4 carbons, alkoxyalkyl group of 2 to 10 carbons, alkenyl group of 2 to 5 carbons, ring of 3 to 20 carbons Alkyl, phenyl- (alkyl having 1 to 3 carbons), alkyl fluorenyl having 1 to 8 carbons, alkyl fluorenyloxy having 1 to 8 carbons, alkenyl having 3 to 12 carbons Fluorenyl, SO _2- (haloalkyl having 1 to 4 carbons) or benzamidine; or R ₁₉ and R ₂₀ represent phenyl, naphthyl, or heteroaryl having 3 to 20 carbons, each of which is Unsubstituted or substituted with more than one of the following groups: A prime atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a benzamidine group, or an alkoxy group having 1 to 12 carbon atoms; Or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S, or NR ₁₇ , and the 5 or 6 members are saturated or unsaturated A saturated ring is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 20 carbons, an alkoxy group having 1 to 20 carbons, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , C (O) R ₂₃ , NO ₂ , a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, phenyl group, and one or more O, S, CO or NR ₁₇ carbon atoms, A cycloalkyl group of 3 to 20, or a group represented by the formula (C-VII); or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a heteroaromatic ring system, the heteroaromatic ring system Is unsubstituted or substituted with more than one of the following groups: alkyl having 1 to 20 carbons, haloalkyl having 1 to 4 carbons, alkoxy having 1 to 20 carbons, = O, OR _{17 , SR 18, NR 21 R 22} , COR 23, halogen atom, NO _2, CN Phenyl or interrupted or not interrupted by more than one O, S, CO or NR ₁₇ carbon atoms of the cycloalkyl group having 3 to 20, or the formula (C-VII) represents a group; and R _{21 is} R ₂₂ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; or R ₂₁ and R ₂₂ with which they are attached The nitrogen atoms connected together form a saturated or unsaturated ring without 5 or 6 members of O, S or NR ₂₆ , which are uncondensed or unsaturated with benzene Ring condensation; R ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and 2 to 20 carbon atoms having one or more O, CO, or NR ₂₆ interspersed therebetween Alkyl, cycloalkyl having 3 to 20 carbon atoms without or without hetero, O, S, CO, or NR ₂₆ , or R ₂₃ represents phenyl, naphthyl, or phenyl-(carbon having 1 to 4 (Alkyl), OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ means (CO) OR ₁₇ , (CO) R ₁₇ , (CO) NR ₁₉ R ₂₀ , or has the meaning given for R ₁₉ and R ₂₀ One of: R ₂₅ means (CO) OR ₁₇ , (CO) R ₁₇ , (CO) NR ₁₉ R ₂₀ , or has the content given for R ₁₇ One of the meanings; R ₂₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, COR ₁₉ , and an alkyl group having 2 to 20 carbon atoms, with more than one intervening in between O or CO; or phenyl-alkyl having 1 to 4 carbons and cycloalkyl having 3 to 8 carbons, which are not interspersed or interspersed with more than one O or CO; or phenyl , Which is unsubstituted or substituted with more than one of the following groups: an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or A group represented by the formula (C-VII); provided that at least one group is present in the photoinitiator (C-1) having the structure of the formula (CI) by the formula (C-II) or A group represented by the formula (C-VII), In Formula (FI), each of Z independently represents a halogen atom or an alkyl group having 1 to 5 carbon atoms; each of W ₁ independently represents a single bond or an alkylene group having 1 to 10 carbon atoms; multiple W ₂ Each independently represents a single bond, O, or an alkylene group having 1 to 10 carbon atoms; multiple W ₃ each independently represents a hydrogen atom, a group represented by formula (F-II) or formula (F-III), where W At least one of ₃ is a group represented by formula (F-II) or formula (F-III); a plurality of L ₁ each independently represent a hydrogen atom or a methyl group; i each independently represents an integer of 0 to 4; j represents 0 An integer to 2 In formula (F-II) and formula (F-III), each of a plurality of L ₂ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; L ₃ represents a single bond or an alkylene group having 1 to 10 carbon atoms * Indicates a bonding site. Among the alkylene groups having 1 to 10 carbon atoms in the W ₁ , W _2, and L ₃ , any -CH ₂ -can be replaced with -O- , -CH = CH- or -C≡C-, and an arbitrary hydrogen atom may be replaced with a halogen atom. The photosensitive resin composition for a black matrix according to item 1 of the patent application scope, wherein the alkali-soluble resin (A) includes a resin (A-1) having an unsaturated group, and the resin (A-1) having an unsaturated group ( A-1) is obtained by polymerizing a mixture including a diol compound (a-1-1) containing a polymerizable unsaturated group; a tetracarboxylic acid or an acid dianhydride (a-1-2) thereof; and Dicarboxylic acid or its anhydride (a-1-3); the polymerizable unsaturated diol compound (a-1-1) comprises an epoxy compound having at least two epoxy groups and at least one carboxyl group An acidic group and at least one ethylenically unsaturated compound are reacted; the epoxy compound having at least two epoxy groups includes a compound of formula (a-1-I), formula (a-1-II) or formula a compound having a structure represented by (a-1-III) or a combination thereof, In the formula (a-1-I), A ¹ , A ² , A ^3, and A ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. , An aryl group having 6 to 12 carbons or an aralkyl group having 6 to 12 carbons, In the formula (a-1-II), A ⁵ to A ¹⁸ each 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 0 to 10 Integer In the formula (a-1-III), Ar ₃ represents a naphthalene ring, A ¹⁹ represents a cyano group, a halogen or a hydrocarbon group, and A ²⁰ represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkoxy group, or an alkane group. Thio, cycloalkylthio, arylthio, aralkylthio, fluorenyl, halogen, nitro, cyano, or substituted amino, A ²¹ represents an alkylene group, a represents an integer from 0 to 4, and b And c represents an integer of 0 or more. The photosensitive resin composition for a black matrix according to item 1 of the scope of patent application, wherein in the photoinitiator (C-1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the formula (C-II), COR ₁₆ or NO ₂ ; or R ₁ to R ₈ Any of the two in which the relative positional relationship is adjacent to each other independently is a group represented by the formula (CV), provided that the relative positional relationship in R ₁ to R ₈ is any of the two in which the relative positional relationship is adjacent. At least one pair is a group represented by the formula (CV); X represents CO or a single bond; R ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups : A halogen atom, (CO) OR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms with one interposed therebetween The above O, S, NR ₂₆ or CO; or R ₁₃ represents a phenyl group or a naphthyl group, both of which are unsubstituted or substituted with one or more COR ₁₆ or a group represented by the formula (C-VII); R ₁₄ represents alkyl having from 1 to 20, a phenyl group or an alkoxy group having a carbon number of 1 to 8 R ₁₅ represents a phenyl group, a naphthyl group, a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, a halogen atom, a haloalkyl group having a carbon number of 1 to 4 OR ₁₇ , SR _18, or an alkyl group having 2 to 20 carbon atoms, intermixed with more than one O or S; or each of them substituted with one or more alkyl groups having 1 to 20 carbon atoms, the carbon number is The alkyl group of 1 to 20 is unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, carbon having 3 to 20 heteroaryl, 6 to 20 carbon aryloxycarbonyl, 4 to 20 carbon heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO (OC _k H _{2k +1} ) ₂ ; or R ₁₅ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , a cycloalkyl group having 3 to 8 carbon atoms, Heteroaryl having 3 to 20 carbon atoms, NR ₁₉ R ₂₀ , (CO) OR ₁₇ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; R _'14 has the meaning given for R ₁₄ one person; R _'15 has one of the meanings R ₁₅ Suo those given for; R ₁₆ represents phenyl, Unsubstituted or substituted by one or more of the following _{groups: OR 17, SR 18, NR} 19 R 20 or interrupted by one or more carbon O, S or NR ₂₆ atoms of alkyl group having 2 to 20; or R ₁₆ represents Phenyl, which is substituted with one or more alkyl groups having 1 to 20 carbons, the alkyl groups having 1 to 20 carbons being unsubstituted or substituted with more than one of the following groups: halogen atom, (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aryloxycarbonyl having 6 to 20 carbons, 4 to 20 carbons Heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with the following groups: halogen atom, phenyl, OH , SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ (CO) O- (alkyl group having 1 to 4 carbon atoms), O (CO)-(carbon group having 1 to 4 carbon atoms) Alkyl) or (CO) O- (alkyl having 1 to 4 carbons); R ₁₇ represents an alkyl having 1 to 20 carbons, which is unsubstituted or substituted with more than one of the following groups: halogen atom _{, OCH 2 CH 2 (CO)} O- ( alkyl having 1 to 4), O- (carbon number of 1 to 4 alkyl), (CO) O- (1 to 4 carbon atoms Alkyl group), a cycloalkyl group having a carbon number of 3 to 20 carbons, or interrupted by one or more oxygen atoms atoms cycloalkyl group having 3 to 20; or R ₁₇ represents an alkyl group having a carbon number of 2 to 20, therebetween heteroaryl Has more than one oxygen atom; R ₁₈ represents a methyl group substituted with (CO) OR ₁₇ ; R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 to An alkyl alkynyl group of 8 or an alkyl alkoxy group having a carbon number of 1 to 8; or R ₁₉ and R ₂₀ and the nitrogen atom to which they are attached form a heteroaromatic ring system, the heteroaromatic ring system is Substituted or substituted via a group represented by the formula (C-VII); provided that at least one of the photoinitiator (C-1) having the structure of the formula (CI) is present by the formula (C The group represented by -II) or the group represented by the formula (C-VII). The photosensitive resin composition for a black matrix according to item 1 of the scope of patent application, wherein in the photoinitiator (C-1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom; 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 (CV), provided 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 (CV); or the R ₂ represents a group represented by the formula (C-II ), COR ₁₆ , NO ₂ or a group represented by the formula (C-III); or R ₇ represents a group or COR represented by the formula (C-II) ₁₆ ; R ₉ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom; R ₁₀ represents a hydrogen atom, OR ₁₇ or COR ₁₆ ; X represents CO or a single bond; R ₁₃ represents a phenyl group; or R ₁₃ represents a carbon number of 1 to Alkyl group of 20, which is unsubstituted or substituted with more than one of the following groups: a halogen atom, R ₁₇ , OR ₁₇ , SR ₁₈ or PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₃ represents a carbon number of 2 alkyl to 20, during which more than one oxygen hetero atom; K represents 2; R ₁₄ represents an alkyl group having a carbon number or a thienyl group having 1 to 20 R ₁₅ represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more OR ₁₇ carbon atoms or a substituted alkyl group of 1 to 20; or R ₁₅ represents a thiophene group, a hydrogen atom, a carbon number of 1 to 20 Alkyl, the alkyl having 1 to 20 carbons is unsubstituted or substituted with more than one of the following groups: OR ₁₇ , SR ₁₈ , cycloalkyl having 3 to 8 carbons, NR ₁₉ R ₂₀ or ( CO) OR ₁₇ ; or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms, intermingled with SO ₂ ; R ₁₆ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or an alkyl group having 1 to 20 carbons; or R ₁₆ represents a thienyl group; R ₁₇ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 1 to 20 carbon atoms Alkyl group, which is unsubstituted or substituted by more than one of the following groups: halogen atom, O (CO)-(alkyl group of 1 to 4 carbons), O (CO)-(carbon number of 2 to 4 Alkenyl) or a cycloalkyl group having 3 to 20 carbon atoms interspersed with one or more oxygen atoms; or R ₁₇ represents an alkyl group with 2 to 20 carbon atoms interspersed with more than one oxygen atom; R ₁₈ represents carbon 3 to 20 cycloalkyl, 1 to 20 carbon, unsubstituted Or substituted with more than one OH, O (CO)-(alkenyl group having 2 to 4 carbons) or (CO) OR ₁₇ ; or R ₁₈ represents a phenyl group, which is unsubstituted or substituted with more than one halogen atom ; R ₁₉ and R ₂₀ each independently represent an alkyl fluorenyl group having 1 to 8 carbons or an alkyl fluorenyloxy group having 1 to 8 carbons; or R ₁₉ and R ₂₀ together with the nitrogen atom to which they are attached form a hetero A 5- or 6-membered saturated ring of an oxygen atom; provided that at least one group represented by the formula (C-II) is present in the photoinitiator (C-1) having the structure of the formula (CI) group. The photosensitive resin composition for a black matrix according to item 1 of the patent application scope, further comprising inorganic oxide fine particles (G), wherein the inorganic oxide fine particles (G) include silicon compound particles, aluminum compound particles, and tin compounds. Particles, titanium compound particles, zirconium compound particles, barium compound particles, or composite particles thereof. The photosensitive resin composition for a black matrix according to item 1 of the patent application scope, wherein the amount of the alkali-soluble resin (A) is 100 parts by weight, and the ethylenically unsaturated group-containing compound (B) 15 to 150 parts by weight, the photoinitiator (C) is used in an amount of 10 to 100 parts by weight, the solvent (D) is used in an amount of 1000 to 6000 parts by weight, and the black pigment ( E) is used in an amount of 100 to 600 parts by weight, and the use amount of the compound (F) containing an epoxy group structure represented by formula (FI) is 10 to 180 parts by weight. The photosensitive resin composition for a black matrix according to item 2 of the scope of patent application, wherein the resin (A-1) having an unsaturated group is based on 100 parts by weight of the alkali-soluble resin (A) used. The amount used is 30 to 100 parts by weight. The photosensitive resin composition for a black matrix according to item 1 of the scope of patent application, wherein the amount of the alkali-soluble resin (A) is 100 parts by weight, and the photoinitiator having the structure of the formula (CI) (C-1) is used in an amount of 5 to 100 parts by weight. The photosensitive resin composition for a black matrix according to item 5 of the scope of patent application, wherein the used amount of the alkali-soluble resin (A) is 100 parts by weight, and the used amount of the inorganic oxide fine particles (G) is 2 to 10 parts by weight. A black matrix, which is sequentially subjected to a pre-baking process, an exposure process, a development process, and a post-baking process by using the photosensitive resin composition for a black matrix according to any one of claims 1 to 9 of the scope of patent application. Formed. A color filter includes a black matrix as described in item 10 of the patent application scope. A liquid crystal display device includes the color filter according to item 11 of the scope of patent application.