TWI664500B - Black photosensitive resin composition and uses thereof - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition and a black matrix and / or a black gap formed using the black photosensitive resin composition to manufacture a color filter and a liquid crystal display element. The photosensitive resin composition includes an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a black pigment (E). The black matrix and / or black gap formed by the black photosensitive resin composition according to the present invention has the advantage of having no development residue.

Description

Black photosensitive resin composition and application thereof

The invention relates to a black photosensitive resin composition and a black matrix and / or a black gap formed by using the black photosensitive resin composition to manufacture a color filter and a liquid crystal display element; in particular, to provide a black photosensitive property. The resin composition and its application, and the black matrix and / or black gap formed by the black photosensitive resin composition have the advantage of no development residue.

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 addition, in order to ensure a certain distance (cell gap) between two substrates (such as a color filter and a TFT substrate), a spacer is used in a display device such as a liquid crystal display device or an organic EL display device. .

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 general, a method for forming a gap body is to disperse a granular gap body over the entire surface of a substrate. However, the gap body formed by the above method cannot reach a good position Setting accuracy. In addition, granular spacers also adhere to the pixel display portion, resulting in a decrease in pattern contrast and image quality.

The methods listed in the previous case to solve the black matrix and the black interstitial body are listed below, as well as the problems they have not overcome.

First, in terms of the black matrix, 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.

Next, Japanese Patent Laid-Open No. 2008-268854 discloses a photosensitive resin composition for a black matrix. This photosensitive resin composition contains an alkali-soluble resin having a carboxylic acid group and an unsaturated group, a photopolymerizable monomer having an ethylenically unsaturated group, a photopolymerization initiator, and a high-use black pigment. The aforementioned alkali-soluble resin having a carboxylic acid group and an unsaturated group can improve the resolution of the photosensitive resin composition.

On the other hand, in order to solve the problems encountered by the black gap body, various methods for forming the gap body with a photosensitive resin composition have been proposed. In this method, a photosensitive resin composition is coated on a substrate, and exposed and developed with a photomask having a predetermined pattern to form a strip-shaped gap body. In addition to the pixel display portion, a gap body may be formed in other predetermined regions. In addition, in Japanese Patent Application Laid-Open No. 2011-170075, it is proposed that a light-shielding agent such as carbon black can be added to the gap body to obtain a black gap body having light-shielding properties.

Various substrates such as a TFT substrate in which an element is formed on a substrate are often used in display devices such as a liquid crystal display device. When using a TFT substrate, the black stripe gap must be The body is formed on an element of the substrate to which it corresponds, or on an element of another substrate opposite to the substrate. In such a case, in order to consider the height of the element, the height of the black strip-shaped gap body needs to be changed in the part formed by the element or other parts.

In the above case, changing the exposure amount for forming the black stripe gap body can form black stripe gap bodies with different heights at one time. Preferably, the above method is performed with a half-tone mask.

However, the industry today has increased requirements for the development residues of black matrices and black gap bodies, so that the black gap bodies and black matrices produced by the aforementioned photosensitive resin composition are prone to the problem of residue generation under different development conditions, and cannot be caused. Accepted by the industry.

Therefore, how to make the black matrix and the black interstitial body produced by the black photosensitive resin composition free of developing residues so as to meet the requirements of the current industry is the goal of hard research in the technical field to which the present invention belongs.

In the present invention, by providing a black photosensitive resin composition containing a special alkali-soluble resin and a black pigment, a black matrix and a black gap body without developing residues formed from the black photosensitive resin composition are obtained.

Therefore, the present invention provides a black photosensitive resin comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment ( E), wherein the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), wherein the first first alkali-soluble resin (A-1) has a structure as shown in formula (I):

In formula (I), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent; and the black pigment (E) includes a first black pigment (E-1), wherein the first black pigment (E-1) comprises a compound having the formula (EI), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof:

In formula (EI), R ^1e and R ^6e are each independently a hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ^2e , R ^3e , R ^4e , R ^5e , R ^7e , R ^8e , R ^9e And R ^10e series and all others are hydrogen atom, halogen atom, R ^11e , COOH, COOR ^11e , COO-, CONH ₂ , CONHR ^11e , CONR ^11e R ^12e , CN, OH, OR ^11e , COCR ^11e , OOCNH ₂ , OOCNHR ^11e , OOCNR ^11e R ^12e , NO ₂ , NH ₂ , NHR ^11e , NR ^11e R ^12e , NHCOR ^12e , NR ^11e COR ^12e , N = CH ₂ , N = CHR ^11e , N = CR ^11e R ^12e , SH, SR ^11e , SOR ^11e , SO ₂ R ^11e , SO ₃ R ^11e , SO ₃ H, SO _3- , SO ₂ NH ₂ , SO ₂ NHR ^11e, or SO ₂ NR ^11e R ^12e ; and selected from R ^2e and R ^3e , At least one combination of the group consisting of R ^3e and R ^4e , R ^4e and R ^5e , R ^7e and R ^8e , R ^8e and R ^9e , and R ^9e and R ^10e , is directly bonded to each other, or ^Bonded to each other by bridging with oxygen atom, sulfur atom, NH or NR ^11e ; R ^11e and R ^12e are independently of each other alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, and 2 to 12 carbon atoms Alkenyl, cycloalkenyl having 3 to 12 carbons, or alkynyl having 2 to 12 carbons.

The present invention also provides a black matrix and a black gap body, which are formed by the aforementioned black photosensitive resin composition being subjected to a pre-baking process, an exposure process, a developing process, and a post-baking process.

The present invention also provides a color filter, which includes the aforementioned black matrix and / or black gap body.

The present invention further provides a liquid crystal display device, which includes the aforementioned color filter.

The present invention provides a black photosensitive resin comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment (E) Wherein, the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), wherein the first first alkali-soluble resin (A-1) has a structure as shown in formula (I):

In formula (I), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent; and the black pigment (E) includes a first black pigment (E-1), wherein the first black pigment (E-1) comprises a compound having the formula (EI), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof:

In formula (EI), R ^1e and R ^6e are each independently a hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ^2e , R ^3e , R ^4e , R ^5e , R ^7e , R ^8e , R ^9e And R ^10e series and all others are hydrogen atom, halogen atom, R ^11e , COOH, COOR ^11e , COO-, CONH ₂ , CONHR ^11e , CONR ^11e R ^12e , CN, OH, OR ^11e , COCR ^11e , OOCNH ₂ , OOCNHR ^11e , OOCNR ^11e R ^12e , NO ₂ , NH ₂ , NHR ^11e , NR ^11e R ^12e , NHCOR ^12e , NR ^11e COR ^12e , N = CH ₂ , N = CHR ^11e , N = CR ^11e R ^12e , SH, SR ^11e , SOR ^11e , SO ₂ R ^11e , SO ₃ R ^11e , SO ₃ H, SO _3- , SO ₂ NH ₂ , SO ₂ NHR ^11e, or SO ₂ NR ^11e R ^12e ; and selected from R ^2e and R ^3e , At least one combination of the group consisting of R ^3e and R ^4e , R ^4e and R ^5e , R ^7e and R ^8e , R ^8e and R ^9e , and R ^9e and R ^10e , is directly bonded to each other, or ^Bonded to each other by bridging with oxygen atom, sulfur atom, NH or NR ^11e ; R ^11e and R ^12e are independently of each other alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, and 2 to 12 carbon atoms Alkenyl, cycloalkenyl having 3 to 12 carbons, or alkynyl having 2 to 12 carbons.

The alkali-soluble resin (A) according to the present invention may include the first alkali-soluble resin (A-1). Secondly, the alkali-soluble resin (A) may optionally include a second alkali-soluble resin (A-2), and may optionally include other alkali-soluble resin (A-3).

The first alkali-soluble resin (A-1) has a structure represented by the following formula (I):

In the formula (I), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent.

In one embodiment, the first alkali-soluble resin (A-1) has at least one ethylenically unsaturated group.

When the black photosensitive resin composition of the present invention contains a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) has at least one ethylenically unsaturated group, the black photosensitive property The black matrix and black gap body made of the resin composition can further improve the non-developing residue.

The first alkali-soluble resin (A-1) can be prepared by reacting a first mixture, and the first mixture is made of an ethylenically unsaturated monomer (a-1) having a structure represented by the formula (I-1) -1), copolymerized by ethylenically unsaturated monomer (a-1-2) with at least one carboxylic acid or carboxylic anhydride and other copolymerizable ethylenically unsaturated monomer (a-1-3) Copolymer.

The ethylenically unsaturated monomer has a structure represented by the following formula (I-1):

In the formula (I-1), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent.

The ethylenically unsaturated monomer may have a structure represented by the following formula (I-2-1) and formula (I-2-2):

In the formula (I-2-1) and the formula (I-2-2), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent. The ethylenically unsaturated monomer may be an ether dimer having α-hydroxymethacrylic acid or an esterified product thereof by ether dimerization, that is, the ethylenically unsaturated monomer has at least one ether group.

The aforementioned ether dimer can be formed into a polymer having a structure represented by the following formula (I-3-1) or formula (I-3-2) through a cyclization polymerization reaction:

In the formula (I-3-1) or (I-3-2), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent.

The polymer having a structure represented by Formula (I-3-1) or Formula (I-3-2) has a tetrahydropyran ring structure derived from an ether dimer.

In the structure represented by formula (I-1), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent, and A ₁ and A ₂ are There is no particular limitation, and A ₁ and A ₂ may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, third pentyl, stearyl, Linear or branched alkyl such as lauryl or 2-ethylhexyl; aromatic groups such as phenyl; cyclohexyl, third butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl Cycloaliphatic groups such as alkyl, adamantyl, or 2-methyl-2-adamantyl; alkoxy substituted alkyls such as 1-methoxyethyl or 1-ethoxyethyl; benzyl, etc. Alkyl substituted alkyl. The A ₁ and A ₂ may preferably be a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, or the like. The A ₁ and A _{2 are more} preferably a methyl group or an ethyl group.

The aforementioned A ₁ and A ₂ may be the same substituent or different substituents. From the viewpoint of improving the transparency and heat resistance of the polymer, A ₁ and A _{2 are} preferably the same substituents to form a symmetrical ether dimer. From the standpoint of storage stability, A ₁ and A _{2 are} preferably different substituents to form an asymmetric ether dimer. The ether dimer may preferably be, for example: 2,2 '-[oxybis (methylene)] bis-acrylic acid or dialkyl-2,2' [oxybis (methylene)] bis-2-acrylic acid ester.

Specific examples of the symmetric ether dimer may be 2,2 '-[oxybis (methylene)] bis-acrylic acid, dimethyl-2,2'-[oxybis (methylene)] bis- 2-acrylate, diethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (n-propyl) -2,2'-[oxybis (methylene) ] Bis-2-acrylate, bis (isopropyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (n-butyl) -2,2'-[oxy Bis (methylene)] bis-2-acrylate, bis (isobutyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (third butyl)- 2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (third pentyl) -2,2'-[oxybis (methylene)] bis-2-acrylate, Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (dodecyl) -2,2'-[oxybis (methylene)] Bis-2-acrylic acid, bis (2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (1-methoxy-ethyl) -2, 2 '-[oxybis (methylene)] bis-2-acrylate, bis (1-ethoxyethyl) -2,2'-[oxybis (methylene)] bis-2-acrylate , Dibenzyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diphenyl-2,2'-[oxybis (methylene )] Bis-2-acrylate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (third butylcyclohexyl) -2,2'-[ Oxybis (methylene)] bis-2-acrylate, bis (dicyclopentadienyl) 2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (tricyclodecane Group) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (isobornyl) -2,2'-[oxybis (methylene)] bis-2-acrylic acid Ester, diadamantyl-2,2 '-[oxybis (methylene)] bis-2-acrylate or bis (2-methyl-2-adamantyl) -2,2'-[oxybis (Methylene)] bis-2-acrylate and the like.

Preferably, the symmetrical ether dimer may be dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diethyl-2,2'-[oxybis ( Methylene)] bis-2-acrylate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, dibenzyl-2,2'-[oxybis ( Methylene)) Bis-2-acrylate, diphenyl-2,2 '-[oxybis (methylene)] bis-2-acrylate or bis (dicyclopentadienyl) 2,2'-[oxybis ( Methylene)] bis-2-acrylate and the like.

More preferably, the symmetric ether dimer may be dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diphenyl-2,2'-[oxybis ( Methylene)] bis-2-acrylate or dibenzyl-2,2 '-[oxybis (methylene)] bis-2-acrylate and the like.

The aforementioned ethylenically unsaturated monomer (a-1-1) having a structure represented by the formula (I-1) may be used singly or in combination.

Based on an ethylenically unsaturated monomer (a-1-1) having a structure represented by the formula (I-1), and an ethylenically unsaturated monomer (a-1-) having at least one carboxylic acid or carboxylic anhydride described later 2) The total amount of the copolymerizable ethylenically unsaturated monomer (a-1-3) is 100 parts by weight, and the ethylenically unsaturated monomer having a structure represented by the formula (I-1) The amount of (a-1-1) used is 5 to 50 parts by weight, preferably 10 to 45 parts by weight, and more preferably 15 to 40 parts by weight.

The ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid may include, but is not limited to, an unsaturated monocarboxylic acid compound, an unsaturated polycarboxylic acid compound, an unsaturated group and as many as one carboxylic acid group. A cyclic compound or a polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups.

The aforementioned unsaturated monocarboxylic acid compound may include, but is not limited to, (meth) acrylic acid, butenoic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2- (meth) acrylic acid and ethoxysuccinate (2-methacryloyloxyethyl succinate monoester), 2- (meth) acrylic acid ethoxy hexahydrophthalate, 2- (meth) acrylic acid ethoxy phthalate or omega-carboxylic acid polymer Caprolactone polyol monoacrylate and the like. The omega-carboxylic acid-based polycaprolactone polyol monoacrylate can be a product manufactured by East Asia Synthetic and model ARONIX M-5300.

The aforementioned unsaturated polycarboxylic acid compound may include, but is not limited to, maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid, and the like.

The aforementioned polycyclic compound having an unsaturated group and one carboxylic acid group may include, but is not limited to, 5-carboxylic acid bicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-5-methylbicyclo [2.2. 1] hept-2-ene, 5-carboxylic acid-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-6-methylbicyclo [2.2.1] hept-2-ene Ene or 5-carboxylic acid-6-ethylbicyclo [2.2.1] hept-2-ene and the like.

Examples of the polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups include 5,6-dicarboxylic acid bicyclo [2.2.1] hept-2-ene and the like.

Preferably, the ethylenically unsaturated monomer having at least one carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, 2-methacrylic acid, ethoxysuccinate, and 2-methacrylic acid. Hexahydrophthalate or any combination thereof.

The ethylenically unsaturated monomer having at least one carboxylic anhydride may include, but is not limited to, an unsaturated carboxylic anhydride compound or a polycyclic compound having an unsaturated group and a carboxylic anhydride.

The aforementioned unsaturated carboxylic anhydride compound may include, but is not limited to, maleic anhydride, fumaric anhydride, methyl fumaric anhydride, itaconic anhydride, citraconic anhydride, and the like, and the aforementioned polycyclic compound having an unsaturated group and a carboxylic anhydride may include but It is not limited to 5,6-dicarboxylic anhydride bicyclo [2.2.1] hept-2-ene and the like.

Preferably, the ethylenically unsaturated monomer having at least one carboxylic anhydride may be maleic anhydride or methyl fumaric anhydride.

The aforementioned ethylenically unsaturated monomers (a-1-2) having at least one carboxylic acid or carboxylic anhydride may be used alone or in combination.

Based on an ethylenically unsaturated monomer (a-1-1) having a structure represented by the formula (I-1) and an ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid or carboxylic anhydride And the total amount of other copolymerizable ethylenically unsaturated monomers (a-1-3) mentioned later is 100 parts by weight, and the ethylenically unsaturated monomer (a-1) having at least one carboxylic acid or carboxylic anhydride -2) is used in an amount of 5 to 40 parts by weight, preferably 10 to 35 parts by weight, and more preferably 15 to 30 parts by weight.

The other copolymerizable ethylenically unsaturated monomer (a-1-3) may include but not Limited to alkyl (meth) acrylate, alicyclic (meth) acrylate, aryl (meth) acrylate, unsaturated dicarboxylic acid ester, alkyl (meth) acrylate, having (meth) Acrylate-based polyethers, styrene compounds, or unsaturated compounds other than the above.

The aforementioned alkyl (meth) acrylate may include, but is not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl methacrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, and the like.

The aforementioned alicyclic (meth) acrylate may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and dicyclopentyl (meth) acrylate {or, Tricyclo [5.2.1.02,6] dec-8-yl (meth) acrylate}, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate or tetrahydrofuran (meth) acrylate Esters, etc.

The aforementioned aryl (meth) acrylate may include, but is not limited to, phenyl (meth) acrylate, benzyl methacrylate, and the like.

The aforementioned unsaturated dicarboxylic acid ester may include, but is not limited to, diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like.

The aforementioned hydroxyalkyl (meth) acrylate may include, but is not limited to, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, and the like.

The aforementioned polyether having a (meth) acrylate group may include, but is not limited to, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like.

The aforementioned styrenic compound may include, but is not limited to, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, or p-methoxystyrene.

Unsaturated compounds other than the aforementioned compounds may include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, Isoprene, 2,3-dimethyl 1,3-butadiene, N-butanediimino-3-maleimide benzoate, N-butadiene imino- 4-maleimidoimidobutyrate, N-butadiimidoimino-6-maleimidoiminohexanoate, N-butadiimidoimido-3-male N-imine propionate, N- (9-acridyl) maleimide, N-octylmaleimide, N-cyclohexylmaleimide ) Or N-phenylmaleimide.

The other copolymerizable ethylenically unsaturated monomers (a-1-3) may be used singly or in combination.

Preferably, the other copolymerizable ethylenically unsaturated monomer (a-1-3) is selected from methyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2- Hydroxyethyl ester, third butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, isobornyl methacrylate, dicyclopentyloxy (meth) acrylate Ethyl ester, styrene, p-methoxystyrene, or any combination thereof.

Based on an ethylenically unsaturated monomer (a-1-1) having a structure represented by formula (I-1), an ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid or carboxylic anhydride And other copolymerizable ethylenically unsaturated monomers (a-1-3) are used in a total amount of 100 parts by weight, and the other copolymerizable ethylenically unsaturated monomers (a-1-3) are used in amounts It is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight.

In another embodiment of the present invention, the first alkali-soluble resin (A-1) is an ethylenically unsaturated monomer (a-1-1) having a structure represented by formula (I-1). 2. The ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid or carboxylic anhydride undergoes a double bond copolymerization reaction with other copolymerizable ethylenically unsaturated monomer (a-1-3) to A polymer is formed in which the side chains of the polymer have carboxylic acid groups. Then, the carboxylic acid group in the side chain of the polymer is subjected to an addition reaction with the ethylenically unsaturated monomer (a-1-4) having an epoxy group to prepare the first alkali-soluble resin (A-1 ), The first alkali-soluble resin (A-1) has at least one ethylenically unsaturated group.

The ethylenically unsaturated monomer (a-1-4) having an epoxy group may include, but is not limited to, a (meth) acrylate compound having an epoxy group, an α-alkylacrylate compound having an epoxy group, or Glycidyl ether compounds and the like.

The aforementioned (meth) acrylate compound having an epoxy group may include, but is not limited to, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and (meth) acrylic acid 3,4 -Butylene oxide, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexyl methyl (meth) acrylate Wait.

The aforementioned α-alkyl acrylate compound having an epoxy group may include, but is not limited to, α-ethyl acrylate, α-n-propyl propylene acrylate, α-n-butyl propylene acrylate, or α-ethylacrylic acid-6,7-epoxyheptyl ester and the like.

The aforementioned glycidyl ether compound may include, but is not limited to, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidylether, or p-vinylbenzyl glycidylether. Vinyl benzylglycidyl ether and the like.

The ethylenically unsaturated monomer (a-1-4) having an epoxy group may be used alone or in combination.

Preferably, the ethylenically unsaturated monomer (a-1-4) having an epoxy group is selected from the group consisting of glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid 3,4-epoxycyclohexyl methyl ester, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-ethylene Benzyl Glycidyl Ether or any combination thereof.

Based on an ethylenically unsaturated monomer (a-1-1) having a structure represented by formula (I-1), an ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid or carboxylic anhydride And other copolymerizable ethylenically unsaturated monomers (a-1-3) are used in a total amount of 100 parts by weight, and the amount of the epoxy-based ethylenically unsaturated monomers (a-1-4) is used It is 1 to 35 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 25 parts by weight.

In another embodiment, the first alkali-soluble resin (A-1) is an ethylenically unsaturated monomer (a-1-1) having a structure as shown in Formula (I-1), other The copolymerized ethylenically unsaturated monomer (a-1-3) and the ethylenically unsaturated monomer (a-1-4) having an epoxy group A double bond copolymerization reaction is performed to form a polymer in which a side chain of the polymer has an epoxy group. Then, an epoxy group in a side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid or carboxylic anhydride to obtain the first alkali-soluble resin. (A-1).

In yet another embodiment, the first alkali-soluble resin (A-1) is an ethylenically unsaturated monomer (a-1-1) having a structure as shown in Formula (I-1), other The copolymerized ethylenically unsaturated monomer (a-1-3) and the ethylenically unsaturated monomer (a-1-4) having an epoxy group undergo a double bond copolymerization reaction to form a polymer, wherein The side chain of the polymer has an epoxy group. Then, an epoxy group in a side chain of the polymer is subjected to addition reaction with an ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid or carboxylic anhydride, and then further half-ester with an acid anhydride compound Chemical reaction to obtain the first alkali-soluble resin (A-1).

The polystyrene-equivalent weight average molecular weight of the prepared first alkali-soluble resin (A-1) measured by a Gel Permeation Chromatography (GPC) is generally 1,000 to 35,000, preferably 3,000 to 30,000 , And more preferably 5,000 to 25,000.

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the first alkali-soluble resin (A-1) is 45 to 100 parts by weight, preferably 50 to 90 parts by weight, And more preferably, it is 55 to 80 parts by weight.

The alkali-soluble resin (A) according to the present invention may optionally include a second alkali-soluble resin (A-2). The second alkali-soluble resin (A-2) can be obtained by polymerizing a second mixture, and the second mixture includes an epoxy compound (a-2-1) having at least two epoxy groups and at least one carboxyl group. Compound (a-2-2) having an acid group and at least one ethylenically unsaturated group. In addition, the second mixture may optionally include a carboxylic anhydride compound (a-2-3) and / or a compound (a-2-4) having an epoxy group.

The epoxy compound (a-2-1) having at least two epoxy groups may have a structure represented by the following formula (III) or formula (IV). Among them, the description of "the epoxy compound (a-2-1) may have a structure represented by the following formula (III) or formula (IV)" also covers compounds having a structure represented by the following formula (III) and compounds having the following When the compound of the structure shown by Formula (IV) exists simultaneously, and it is set as an epoxy compound (a-2-1). Specifically, the aforementioned epoxy compound (a-2-1) having at least two epoxy groups has a structure represented by the following formula (III), for example:

In formula (III), B ₁ , B ₂ , B _3, and B ₄ are the same or different, and B ₁ , B ₂ , B _3, and B ₄ each represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 5 An alkyl group, an alkoxy group having 1 to 5 carbons, an aromatic group having 6 to 12 carbons, or an aralkyl group having 6 to 12 carbons.

The epoxy compound (a-2-1) having at least two epoxy groups having a structure as shown in formula (III) may include reacting a bisphenol fluorene compound with an epihalohydrin The obtained epoxy-containing bisphenol amidine type compound is not limited thereto.

Specific examples of the bisphenol hydrazone compound may include, but are not limited to, 9,9-bis (4-hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (4-hydroxy -3-methylphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene], 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene [9,9-bis (4-hydroxy-3-chlorophenyl) fluorene], 9,9-bis (4-hydroxy-3-bromophenyl) fluorene [9,9-bis (4-hydroxy-3-bromophenyl) fluorene], 9,9 -Bis (4-hydroxy-3-fluorophenyl) fluorene [9,9-bis (4-hydroxy-3-fluorophenyl) fluorene], 9,9-bis (4-hydroxy-3-methoxyphenyl)芴 [9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene], 9,9-bis (4-hydroxy-3,5-dimethylphenyl) 芴 [9,9-bis (4-hydroxy -3,5-dimethylphenyl) fluorene], 9,9-bis (4-hydroxy-3,5-dichlorophenyl) 芴 [9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene] or 9,9-bis (4-hydroxy-3,5-dibromophenyl) 芴 [9,9-bis (4- hydroxy-3,5-dibromophenyl) fluorene].

Specific examples of the aforementioned halogenated propylene oxide (epihalohydrin) may include, but are not limited to, 3-chloro-1,2-propylene oxide (epichlorohydrin) or 3-bromo-1,2-propylene oxide (epibromohydrin).

The epoxy-containing bisphenol fluorene type compound prepared by the reaction of a bisphenol fluorene type compound and a halogenated propylene oxide may include, but is not limited to: (1) Nippon Steel Chemical Co., Ltd. Manufactured goods, and its model is ESF-300, etc .; (2) Goods manufactured by Osaka Gas Co., Ltd, and its model is PG-100 or EG-210, etc .; (3) SMS technology ( SMS Technology Co., Ltd), and its model is SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.

In formula (IV), B ₅ to B ₁₈ are the same or different, B ₅ to B ₁₈ are 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 a represents an integer from 0 to 10.

The epoxy compound (a-2-1) having at least two epoxy groups as shown in the formula (IV) can be obtained, for example, by having the following formula (IV-1) in the presence of an alkali metal hydroxide. The compound of the structure shown is reacted with a halogenated propylene oxide to obtain:

In formula (IV-1), the definitions of B ₅ to B ₁₈ are as described above, and are not repeated here.

Furthermore, the aforementioned epoxy compound (a-2-1) having at least two epoxy groups as shown in the formula (IV) may be, for example, in the presence of an acid catalyst, a compound having the following formula (IV-2) The compound having the structure shown is subjected to a condensation reaction with phenols to form a compound having a structure represented by the formula (IV-1). Next, an excess of halogenated propylene oxide is added to perform a dehydrohalogenation reaction to obtain an epoxy compound (a-2-1) having at least two epoxy groups in a structure shown in formula (IV). :

In formula (IV-2), the definitions of B ₇ to B ₁₀ are as described above, and are not repeated here. B ₁₉ and B ₂₀ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

Preferably, the halogen atom may be, for example, a chlorine atom or a bromine atom; the alkyl group may be, for example, a methyl group, an ethyl group, or a third butyl group; and the alkoxy group may be, for example, a methoxy group or an ethoxy group.

Specific examples of the aforementioned phenols may include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, and t-butylphenol ( t-butylphenol, octylphenol, nonylphenol, xylenol, methyl butylphenol, di-t-butylphenol, vinylphenol (vinylphenol), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol, cyclohexyl cresol and the like. These phenols may be used alone or in combination.

The amount of the compound based on the aforementioned structure having the formula (IV-2) is 1 mole, the amount of phenols is 0.5 to 20 moles, and preferably 2 to 15 moles. ear.

Specific examples of the acid catalyst may include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous, or chlorine. Zinc chloride, etc. The acid catalyst may preferably be p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, or any combination thereof. The acid catalyst may be used alone or in combination.

Although the use amount of the acid catalyst is not particularly limited, based on the use amount of the compound having the structure represented by the formula (IV-2) is 100% by weight, the use amount of the acid catalyst is preferably 0.1% by weight. Percent to 30 weight percent.

The aforementioned condensation reaction can be performed without a solvent or in the presence of an organic solvent. Specific examples of the organic solvent may include, but are not limited to, toluene, xylene, methyl isobutyl ketone, and the like. These organic solvents may be used singly or in combination.

Based on the foregoing, the total amount of the compound and phenols having the structure represented by the formula (IV-2) is 100% by weight, and the amount of the organic solvent is 50% to 300% by weight, and preferably 100% by weight To 250 weight percent. The operation temperature of the aforementioned condensation reaction may be 40 ° C to 180 ° C, and the operation time may be 1 hour to 8 hours.

After the condensation reaction is performed, a neutralization treatment or a water washing treatment may be further performed.

The neutralization treatment adjusts the pH value of the solution after the reaction to 3 to 7, and preferably 5 to 7.

The water washing treatment can be performed using a neutralizing agent, and the neutralizing agent is an alkaline substance. Specific examples of the neutralizing agent may include, but are not limited to, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; calcium hydroxide or magnesium hydroxide Alkaline earth metals Hydroxides; organic amines such as diethylene triamine, triethylenetetramine, aniline, or phenylene diamine; ammonia (ammonia), sodium dihydrogen phosphate ( sodium dihydrogen phosphate) or any combination thereof. This neutralizing agent can be used individually or in mixture of multiple types.

This water washing treatment can be performed by a conventional method. For example, an aqueous solution with a neutralizing agent is added to the solution after the reaction, and extraction is performed repeatedly. After the neutralization treatment or the water washing treatment, unreacted phenols and solvents can be removed by heating under reduced pressure, and concentrated to obtain a compound having a structure represented by formula (IV-1).

Specific examples of the halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane (3- bromo-1,2-epoxypropane) or any combination thereof.

Before carrying out the above-mentioned dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction.

The operation temperature of the above-mentioned dehydrohalogenation reaction may be 20 ° C to 120 ° C, and the operation time thereof may be 1 hour to 10 hours.

The alkali metal hydroxide added in the dehydrohalogenation reaction may be an alkali metal hydroxide aqueous solution. In this embodiment, the alkali metal hydroxide aqueous solution is continuously added to the dehydrohalogenation reaction system, and water and halogenated propylene oxide are continuously distilled off under reduced or normal pressure to separate and remove water. The halogenated propylene oxide system was continuously refluxed into the reaction system.

Before carrying out the above-mentioned dehydrohalogenation reaction, tetramethyl ammonium chloride, tetramethyl ammonium bromide or trimethyl benzyl ammonium chloride can be added to the reaction system. The quaternary ammonium salt acts as a catalyst. After reacting at 50 ° C to 150 ° C for 1 hour to 5 hours, an alkali metal hydroxide or an aqueous solution thereof is added. Next, at 20 ° C to 120 ° C The dehydrohalogenation reaction is performed at the temperature for 1 hour to 10 hours.

Based on the total equivalents of hydroxyl groups in the aforementioned compound having the structure represented by formula (IV-1) is 1 equivalent, the amount of the halogenated propylene oxide used may be 1 to 20 equivalents, and preferably 2 to 10 equivalents equivalent.

Based on the total equivalents of the hydroxyl groups in the aforementioned compound having the structure represented by the formula (IV-1) is 1 equivalent, the use amount of the alkali metal hydroxide added in the dehydrohalogenation reaction may be 0.8 equivalent to 15 equivalents, and It may preferably be 0.9 to 11 equivalents.

In addition, in order to make the dehydrohalogenation reaction proceed smoothly, an alcohol such as methanol or ethanol may be added to the reaction system. Second, the reaction system can also add aprotic polar solvents such as dimethyl sulfone or dimethyl sulfoxide for reaction.

In the case of using alcohols, based on the total usage of the aforementioned halogenated propylene oxide is 100% by weight, the usage of the alcohols may be 2 to 20% by weight, and preferably 4 to 15% by weight percentage.

In the case of using an aprotic polar solvent, based on the total amount of halogenated propylene oxide used, 100% by weight, the amount of aprotic polar solvent used is 5 to 100% by weight, and preferably 10 to 100% by weight 90 weight percent.

After the dehydrohalogenation reaction, the product can be optionally washed with water, and halogenated propylene oxide, alcohols, and aprotic polar solvents can be removed by distillation under reduced pressure. This vacuum distillation can be performed at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa [10 millimeters of mercury (mmHg)] or less.

In order to avoid the hydrolyzable halogen of the prepared epoxy resin, the solution after the dehydrohalogenation reaction can be added to a solvent such as toluene or methyl isobutyl ketone, and sodium hydroxide or hydroxide In an aqueous alkali metal hydroxide solution such as potassium, dehydrohalogenation is performed again.

In this dehydrohalogenation reaction, it has the following formula (IV-1) based on the foregoing. The total equivalents of the hydroxyl groups in the structured compound are 1 equivalent, and the amount of the alkali metal hydroxide used may be 0.01 mol to 0.3 mol, and preferably 0.05 mol to 0.2 mol. Secondly, the operation temperature of the aforementioned dehydrohalogenation reaction may be 50 ° C to 120 ° C, and the operation time thereof may be 0.5 hour to 2 hours.

After the dehydrohalogenation reaction is completed, the salts can be removed by steps such as filtration and water washing, and the solvent such as toluene or methyl isobutyl ketone can be removed by means of distillation under reduced pressure to obtain a compound having the formula (IV) The compound of the structure shown.

The aforementioned epoxy compound (a-2-1) having at least two epoxy groups as shown in the formula (IV) may include, but is not limited to, products manufactured by Nippon Kayaku Co. Ltd., and Models are NC-3000, NC-3000H, NC-3000S or NC-3000P.

The aforementioned compound (a-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group may be selected from the group consisting of (1) to (3): (1) acrylic acid, methyl Acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylacrylic acid Acrylic acid oxybutyl adipic acid, 2-methacrylic acid oxyethyl hexahydrophthalic acid, 2-methacrylic acid oxyethyl maleic acid, 2-methacrylic acid oxypropyl maleate Acid, 2-methacrylic acid oxybutyl maleic acid, 2-methacrylic acid oxypropyl succinic acid, 2-methacrylic acid oxypropyl adipate, 2-methacrylic acid oxypropyl Tetrahydrophthalic acid, 2-methacrylic acid oxypropyl phthalic acid, 2-methacrylic acid oxybutyl phthalic acid, or 2-methacrylic acid oxybutyl phthalic acid ; (2) A compound prepared by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein the dicarboxylic acid compound may include, but is not limited to, adipic acid, succinic acid, maleic acid, or Phthalic acid; (3) by A half-ester compound prepared by reacting a hydroxy (meth) acrylate with a carboxylic anhydride compound. The (meth) acrylate having a hydroxy group may include, but is not limited to, 2- (hydroxyethyl) acrylate. ], 2-hydroxyethyl methacrylate [(2-hydroxyethyl) methacrylate], 2-hydroxypropyl acrylate [(2-hydroxypropyl) acrylate], 2-hydroxypropyl methacrylate [(2-hydroxypropyl) methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl) acrylate], 4-hydroxybutyl methacrylate [(4-hydroxybutyl) methacrylate] or pentaerythritol trimethacrylate and the like. The carboxylic acid anhydride compound may be the same as the carboxylic acid anhydride compound (a-2-3) contained in the second mixture described later, so it will not be repeated here.

The aforementioned second mixture may optionally include a carboxylic anhydride compound (a-2-3) and / or a compound (a-2-4) having an epoxy group.

The above carboxylic acid anhydride compound (a-2-3) can be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, clothing Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride, or trimellitic acid Acid anhydrides (1,3-dioxoisobenzofuran-5-carboxylic anhydride) and other dicarboxylic anhydride compounds; and (2) benzophenone tetracarboxylic dianhydride (BTDA), bistetracarboxylic dianhydride or bisbenzene Tetracarboxylic acid anhydride compounds such as ether tetracarboxylic dianhydride.

The compound (a-2-4) having an epoxy group may be, for example, selected from glycidyl methacrylate, 3,4-epoxy cyclohexyl methacrylate, and glycidyl ether having an unsaturated group. A group of compounds, unsaturated compounds having epoxy groups, or any combination of the foregoing.

The aforementioned glycidyl ether compound having an unsaturated group may include, but is not limited to, products manufactured by Nagase Chemical Industry Co., Ltd. and the models are Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171 or Denacol EX-192, etc.

In one embodiment, the second alkali-soluble resin (A-2) may be an epoxy compound (a-2-1) having at least two epoxy groups and at least one carboxylic acid as shown in formula (III). Group and at least one ethylenically unsaturated compound (a-2-2) are polymerized to form a reaction product having a hydroxyl group. Next, a carboxylic anhydride compound (a-2-3) was added and reacted. The total hydroxyl equivalent of the reaction product having a hydroxyl group is 1 equivalent, and the equivalent of the acid anhydride group contained in the carboxylic anhydride compound (a-2-3) is preferably 0.4 equivalent to 1 equivalent, and more preferably 0.75 equivalent to 1 equivalent. . When a plurality of carboxylic anhydride compounds (a-2-3) are used, they may be added sequentially or simultaneously during the reaction. When a dicarboxylic acid anhydride compound and a tetracarboxylic acid anhydride compound are used as the carboxylic acid anhydride compound (a-2-3), the molar ratio of the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound is preferably 1/99 to 90 / 10, and more preferably 5/95 to 80/20. Second, the operating temperature of the above reaction may be, for example, 50 ° C to 130 ° C.

In another embodiment, the second alkali-soluble resin (A-2) may be an epoxy compound (a-2-1) having at least two epoxy groups and at least one carboxyl group as shown in formula (IV). The acid group and at least one ethylenically unsaturated compound (a-2-2) are reacted to form a hydroxyl-containing reaction product. Next, a carboxylic anhydride compound (a-2-3) and / or an epoxy group-containing compound (a-2-4) are added to perform a polymerization reaction. Based on the total epoxy group equivalent of the epoxy compound (a-2-1) having at least two epoxy groups as shown in formula (IV) is 1 equivalent, the epoxy compound (a-2-1) has at least one carboxylic acid group and at least one ethylenic compound. The acid value equivalent of the saturated compound (a-2-2) is preferably 0.8 equivalents to 1.5 equivalents, and more preferably 0.9 equivalents to 1.1 equivalents. The total amount of hydroxyl groups based on the above-mentioned reaction product having hydroxyl groups is 100 mole% (mol%), and the amount of carboxylic anhydride compound (a-2-3) used is 10 mole% to 100 mole%, preferably 20 Molar% to 100 Molar%, and more preferably 30 Molar% to 100 Molar%.

When the second alkali-soluble resin (A-2) is prepared, in order to accelerate the reaction, a basic compound is usually added to the reaction solution as a reaction catalyst. The reaction catalyst may be used singly or in combination. The reaction catalyst may include, but is not limited to, triphenyl phosphine, triphenyl stibine, and triethylamine. (triethylamine), triethanolamine, tetramethylammonium chloride, benzyltriethylammonium chloride, and the like. The total amount of the epoxy compound (a-2-1) having at least two epoxy groups and the compound (a-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. The use amount of the reaction catalyst is preferably 0.01 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight.

In addition, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol (2,6-di- t-butyl-p-cresol) or phenothiazine. In general, the above-mentioned polymerization inhibitors can be used singly or in combination. Based on the total amount of the above-mentioned epoxy compound (a-2-1) having at least two epoxy groups and the compound (a-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group, 100 The use amount of the polymerization inhibitor is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.

When the second alkali-soluble resin (A-2) is prepared, a polymerization reaction solvent may be added if necessary. Specific examples of the polymerization reaction solvent may include, but are not limited to, alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, or ethylene glycol; methyl ethyl ketone or cyclohexanone, and the like Ketones; aromatic hydrocarbons such as toluene or xylene; cellosolve or butyl cellosolve; carbitol or butyl carbitol (butyl carbitol) and other carbitol compounds; propylene glycol monomethyl ether (propylene glycol monomethyl ether) and other propylene glycol alkyl ether compounds; dipropylene glycol monomethyl ether [di (propylene glycol) methyl ether] and other propylene glycol alkyl ethers [ poly (propylene glycol) alkyl ether]; acetate compounds such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, or propylene glycol methyl ether acetate Substances; alkyl lactate compounds such as ethyl lactate or butyl lactate; or dialkyl glycol ethers. This polymerization reaction solvent may be used individually or in mixture of multiple types. In addition, the acid value of the second alkali-soluble resin (A-2) is preferably 50 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 150 mgKOH / g.

The polystyrene-equivalent number average molecular weight of the aforementioned second alkali-soluble resin (A-2) measured by a colloidal permeation chromatography is generally 500 to 10,000, preferably 800 to 8000, and more preferably 1000 to 6000.

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the second alkali-soluble resin (A-2) is 0 to 55 parts by weight, preferably 10 to 50 parts by weight, And more preferably, it is 20 parts by weight to 45 parts by weight.

When the alkali-soluble resin (A) of the present invention contains the second alkali-soluble resin (A-2), the black matrix and the black interspacer produced from the black photosensitive resin composition can further improve the non-developing residue.

In the black photosensitive resin composition of the present invention, other alkali-soluble resins (A-3) can be optionally added.

The aforementioned other alkali-soluble resin (A-3) may include, 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-3) may be alkali-soluble resins such as acrylic resins, urethane resins, and novolac resins other than the unsaturated resin (A-1). .

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the other alkali-soluble resin (A-3) is 0 to 55 parts by weight, preferably 10 to 50 parts by weight, and More preferably, it is 20 to 45 parts by weight.

The compound (B) having an ethylenically unsaturated group according to the present invention may include an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.

Specific examples of the unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, acrylamidomorpholine, methacrylamidomorpholine, acrylic-7-amino-3,7-dimethyl Octyl ester, methacrylic acid 7-amino-3,7-dimethyloctyl ester, isobutoxymethacrylamide, isobutoxymethylmethacrylamide, isobornyl acrylate Ethyl ester, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyldiethylene glycol Acrylate, Ethyl Diethylene Glycol Methacrylate, Third Octyl Acrylamidoxamine, Third Octyl Methacrylamidine, Diacetone Acrylamidine, Diacetone Methacrylamidine, Dimethylamine Acrylate Ester, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl ethyl methacrylate, dicyclopentyl acrylate Pentenyl ester, dicyclopentenyl methacrylate, nitrogen, nitrogen-dimethyl acrylamide, nitrogen, nitrogen-dimethyl acrylamide Tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetramethacrylate methacrylate Hydrofurfuryl ester, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichloroacrylate Phenoxyethyl, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, methacrylic acid- 2-tribromophenoxyethyl, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinyl caprolactone Phenylamine, nitrogen-vinyl skintyrone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, methyl Pentabromophenyl acrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, acrylic acid Sheet ester, bornyl acrylate or methacrylate and the like. The unsaturated compound having at least one ethylenically unsaturated group may be used alone or in combination.

Specifics of the unsaturated compound having at least two ethylenically unsaturated groups Examples may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, dicyclopentenyl dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol Diacrylate, tetraethylene glycol dimethacrylate, tri (2-hydroxyethyl) isocyanate diacrylate, tri (2-hydroxyethyl) isocyanate dimethacrylate, tri (2-hydroxyethyl) isocyanate Triacrylate, tri (2-hydroxyethyl) isocyanate trimethacrylate, caprolactone modified tri (2-hydroxyethyl) isocyanate triacrylate, caprolactone modified tri (2-hydroxyethyl) Base) isocyanate trimethacrylate, trimethylol propyl triacrylate, trimethylol propyl trimethacrylate, trimethylol propyl triacrylate modified by ethylene oxide (hereinafter referred to as EO), EO modified trimethylol propyl trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylol propyl triacrylate, PO modified trimethylol propyl trimethacrylate, Triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate , 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate Methacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethyl Acrylate, caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexamethacrylate, caprolactone-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol five Methacrylate, ditrimethylol propyl tetraacrylate, ditrimethylol propyl tetramethacrylate, bisphenol A diacrylate modified by EO, bisphenol A di modified by EO Acrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO modified bisphenol A diacrylate, EO modified hydrogenated bisphenol A dimethyl ester Acrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethyl propane Enoate, PO modified glycerol tripropionate, EO modified bisphenol F diacrylate, EO modified bisphenol F dimethacrylate, novolac polyglycidyl ether acrylate, novolac polyglycidyl Ether methacrylate, a product of TO-1382 manufactured by Toa Kosei Co., Ltd., or a model of KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, or KAYARAD manufactured by Nippon Kayaku Co., Ltd. DPCA-120 products. The unsaturated compound having at least two ethylenically unsaturated groups may be used alone or in combination.

Preferably, the compound (B) having an ethylenically unsaturated group is selected from the group consisting of trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified by EO, and trihydroxymethyltriacrylate modified by PO. Methylpropyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetraacrylate ditrihydroxyol Methylpropyl ester, PO modified glycerol tripropionate, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 or any combination of the above compounds.

The compound (B) having an ethylenically unsaturated group may be used alone or in combination.

Based on the total used amount of the alkali-soluble resin (A) being 100 parts by weight, the used amount of the compound (B) having an ethylenically unsaturated group is 40 to 200 parts by weight, preferably 50 to 180 parts by weight Parts, and more preferably 60 parts by weight to 160 parts by weight.

The photoinitiator (C) of the present invention may be a substance that generates free radicals by irradiating light, and the aforementioned substance having a free radical may trigger a polymer to a polymer, a polymer to an oligomer, or a polymer to The cross-linking reaction between monomers can form a pattern with good mechanical strength (for example: black matrix or black interstitial body).

The photoinitiator (C) according to the present invention includes a photoinitiator (C-1) having a structure represented by the formula (CI). Second, the photoinitiator (C) may optionally include other photoinitiators. beginning Agent (C-2) is described below.

The photoinitiator (C) according to the present invention includes a photoinitiator (C-1) having a structure represented by the formula (CI):

Among them, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, , COR ₁₆ , OR ₁₇ , halogen, NO ₂ or , Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independent of each other. Substituted C ₂ -C ₁₀ alkenyl or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of one another are -(CH ₂ ) _P -Y- (CH ₂ ) _q- ; or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other is But provided that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ ; R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen, Phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, (CO) OH or (CO) O (C ₁ -C ₄ alkyl); or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ Independently of each other are unsubstituted phenyl or phenyl substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring with one 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 independent of each other for , COR ₁₆ or NO ₂ ; Y is O, S, NR ₂₆ or direct bond; p is integer 0, 1, 2 or 3; q is integer 1, 2 or 3; X is CO or direct bond; R ₁₃ is C _1- C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ or ; Or R ₁₃ is a C ₂ -C ₂₀ alkyl group, which is interspersed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO, or C ₂ -C ₁₂ alkenyl, which is not interspersed or interspersed with one Or more O, CO or NR ₂₆ in which the interspersed C ₂ -C ₂₀ alkyl and unsaturated or interspersed C ₂ -C ₁₂ alkenyl are unsubstituted or substituted with one or more halogens; or R ₁₃ series C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl or C ₃ -C ₁₀ cycloalkyl without one or more O, S, CO or NR ₂₆ ; or R ₁₃ series Phenyl or naphthyl, each unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , _{, COR 16, CN, NO 2} , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, interrupted by one or more O, S, CO or NR C ₂₆ of ₂ -C ₂₀ alkyl group; or via their respective C ₃ -C ₁₀ cycloalkyl, or interrupted by one or more O, S, CO or NR ₂₆ of the C ₃ -C ₁₀ cycloalkyl; based integer k 1 to 10; R ₁₄ type hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy, or C ₁ -C ₂₀ alkyl, which are unsubstituted or substituted by one or more halogen, phenyl, C _1- C ₂₀ alkylphenyl or CN substituted; or R ₁₄ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkane Group, halogen, CN, OR ₁₇ , SR ₁₈ and / or NR ₁₉ R ₂₀ ; or R ₁₄ is a C ₃ -C ₂₀ heteroaryl group, C ₁ -C ₈ alkoxy group, benzyloxy group or phenoxy group, the Benzyloxy and phenoxy are unsubstituted or substituted with one or more C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and / or halogen; R ₁₅ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ 、 PO (OC _k H _{2k + 1} ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, S or NR ₂₆ ; or each C _1- C ₂₀ alkyl substitution, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is hydrogen, C _2- C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl without one or more O, CO or NR ₂₆ ; or R ₁₅ is C ₁ -C ₂₀ alkyl, which is unsubstituted or Multiple substitutions of the following groups: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl Oxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , , , Phenyl; or the C ₁ -C ₂₀ alkyl group is substituted with a phenyl group, the phenyl group is halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₄ haloalkyl group, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ Substituted; or R ₁₅ is a C ₂ -C ₂₀ alkyl group, in which one or more O, SO, or SO ₂ is interspersed, and the interspersed C ₂ -C ₂₀ alkyl group is unsubstituted or substituted by one or more of the following groups Group substitution: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is a C ₂ -C ₂₀ alkylfluorenyl or benzyl Fluorenyl, which is unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is unsubstituted or A naphthylmethyl group substituted with one or more OR ₁₇ or a C ₃ -C ₁₄ heteroarylcarbonyl group; or R ₁₅ is a C ₂ -C ₁₂ alkoxycarbonyl group, which is not interspersed or interspersed with one or more O And the C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R ₁₅ is a phenoxycarbonyl group which is unsubstituted or substituted with one or more Group substitution: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S (O) _m -C ₁ -C ₆ alkyl, unsubstituted or C ₁ -C ₁₂ alkyl or SO ₂ -C ₁ -C ₆ alkyl substituted S (O) _m -phenyl; or R ₁₅ is SO ₂ O-phenyl, which is unsubstituted or substituted by C ₁ -C ₁₂ Group substitution; or diphenylphosphinofluorenyl or bis (C ₁ -C ₄ alkoxy) -phosphinofluorenyl; m is 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 is O, S, SO or SO ₂ ; X ₂ is O, CO, S or a direct bond; R ₁₆ is C ₆ -C ₂₀ aryl Or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or one or more C ₁ -C ₂₀ alkyl groups with one or more O, S or NR ₂₆ ; or each substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group Unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ Aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ is hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl , OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C ₁ -C ₄ alkyl); or R ₁₆ is C ₂ -C ₁₂ alkyl, with one or more intervening in between O, S or NR ₂₆ ; or R ₁₆ series (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ Alkenyl or C ₃ -C ₈ cycloalkyl; or R ₁₆ is a phenyl substituted with SR ₁₈ , where the group R ₁₈ represents a phenyl or naphthyl ring bonded to the carbazole moiety to which COR ₁₆ is attached N is 1 to 20; R ₁₇ is hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen , OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), OCO)-(C ₂ -C ₄ ) alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C ₁ -C ₄ alkyl), C ₃ -C ₂₀ Cycloalkyl, SO _2- (C ₁ -C ₄ haloalkyl), O (C ₁ -C ₄ haloalkyl) or a C ₃ -C ₂₀ cycloalkyl group interspersed with one or more O; or R ₁₇ is a C ₂ -C ₂₀ alkyl group interspersed with one or more O, S or NR ₂₆ ; or R ₁₇ series (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl, C ₂ -C ₁₂ Alkenyl, C ₃ -C ₆ alkenyl or C ₃ -C ₂₀ cycloalkyl without one or more O, S, CO or NR ₂₆ ; or R ₁₇ is C ₁ -C ₈ alkyl -C ₃ -C ₁₀ cycloalkyl, which has one or more O unsubstituted or interspersed; or R ₁₇ is benzamyl, which is unsubstituted or has one or more C ₁ -C ₆ alkyl, halogen , OH or C ₁ -C ₃ alkoxy substitution; or R ₁₇ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, Phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenyl-amino or Or R ₁₇ forms a bond to or Direct bond of one carbon atom of phenyl or naphthyl ring; R ₁₈ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, where C _2- C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl without one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; or R ₁₈ Is a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ ( CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl Or (CO) OR ₁₇ ; or R ₁₈ is a C ₂ -C ₂₀ alkyl group, which is interspersed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; or R ₁₈ (CH ₂ CH ₂ O) _n H , (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkylfluorenyl or C ₃ -C ₆ alkenyl; or R ₁₈ benzamyl, It is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy, or C ₁ -C ₄ alkylthio; or R ₁₈ series Phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ Haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N ( C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO) O (C ₁ -C ₈ alkyl), (CO) -C ₁ -C ₈ alkyl, (CO) N (C _1- C ₈ alkyl) ₂ or ; R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkylfluorenyl, C ₁ -C ₈ alkylfluorenyloxy, C ₃ -C ₁₂ alkenyl, SO _2- (C ₁ -C ₄ haloalkyl) or benzamyl; or R ₁₉ and R ₂₀ are phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted by one or more of the following groups Group substitution: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzamidine or C ₁ -C ₁₂ alkoxy; or R ₁₉ and R ₂₀ With its attached N atom to 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-membered saturated or unsaturated ring is unsubstituted or One or more of the following groups substituted: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO) R ₂₃ , NO ₂ , halogen , C ₁ -C ₄ -haloalkyl, CN, phenyl, Or C ₃ -C ₂₀ cycloalkyl, the C ₃ -C ₂₀ cycloalkyl has one or more O, S, CO, or NR ₁₇ without interspersed or interspersed; or R ₁₉ and R ₂₀ with the N atom to which it is attached Together form a heteroaromatic ring system that is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO) R ₂₃ , , Halogen, NO ₂ , CN, phenyl, or C ₃ -C ₂₀ cycloalkyl, the C ₃ -C ₂₀ cycloalkyl has one or more O, S, CO, or NR ₁₇ uninterspersed or interspersed; R ₂₁ and R _{22 is} independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ₂₁ and R ₂₂ together with the N atom to which they are attached Forms a 5- or 6-membered saturated or unsaturated ring without interspersed or interspersed O, S, or NR ₂₆ , and the 5- or 6-membered saturated or unsaturated ring is not fused or the 5- or 6-membered saturated or unsaturated ring saturated ring system is fused with a benzene ring; R ₂₃ type hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, interrupted by one or more O, cO or NR C ₂₆ alkoxy of ₂ -C ₂₀ , C ₃ -C ₂₀ cycloalkyl without meta or hetero, O, S, CO or NR ₂₆ , or R ₂₃ phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ is (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , (CO) R ₁₇ ; or R ₂₄ has one of the meanings given for R ₁₉ and R ₂₀ ; R ₂₅ is COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO) R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ ; R ₂₆ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl ,between C ₂ -C ₂₀ alkyl with one or more O or CO; or phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkane without one or more O or CO Or (CO) R ₁₉ ; or phenyl, which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or ; Provided that at least one group is present in the molecule or

The photoinitiator (C-1) having a structure represented by the formula (CI) is characterized in that it contains one or more annelated unsaturated rings on a carbazole moiety. In other words, at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈

In one embodiment, the photo-initiator (C-1) having a structure represented by formula (CI), the C ₁ -C ₂₀ alkyl is linear or branched and is, for example, C ₁ -C ₁₈ -, C ₁ -C _4- , C ₁ -C _12- , C ₁ -C _8- , C ₁ -C ₈ -or C ₁ -C ₄ alkyl or C ₄ -C ₁₂ -or C ₄ -C ₈ alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, 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. C ₁ -C ₆ alkyl has the same meaning as given above for C ₁ -C ₂₀ alkyl and has the highest corresponding number of C atoms.

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

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

The interrupted by one or more O, S, NR ₂₆ or CO of C ₂ -C ₂₀ alkyl is O, S, NR ₂₆ or CO interrupted (e.g.) 1-9 times, 1-5 times, 1-3 times or 1 or 2 times. If more than one mesohetero group is present, they are the same kind or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylidene). These alkyl groups are straight 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 .

The C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkyl, and C ₃ -C ₈ cycloalkyl are understood in the context of this application as alkyl groups containing at least one ring. It is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. C ₃ -C ₁₀ cycloalkyl is also intended to encompass bicyclics 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 Isostructure, and bridged or fused ring systems, the term is also intended to cover, for example , Wait.

The C ₃ -C ₂₀ cycloalkyl group interspersed with O, S, CO, NR ₂₆ has the meaning given above, wherein at least one CH ₂ -group in the alkyl group is replaced with O, S, CO or NR ₂₆ . Examples are such as , , (E.g

), , , , , or And other structures.

The C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl is a C ₃ -C ₁₀ cycloalkyl group, as defined above, substituted with one or more alkyl groups having up to 8 carbon atoms. Instance system , Wait.

The C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl having one or more O heterocycles is substituted with one or more alkyl groups having up to 8 carbon atoms, as defined above, O O C ₃ -C ₁₀ cycloalkyl. Instance system , Wait.

The C ₁ -C ₁₂ alkoxy substituted with the system via a O atom C ₁ -C ₁₂ alkyl. C ₁ -C ₁₂ alkyl has the same meaning as given above for C ₁ -C ₂₀ alkyl and has the highest corresponding number of C atoms. The C ₁ -C ₄ alkoxy is linear or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy or Third butoxy. C ₁ -C ₈ alkoxy and C ₁ -C ₄ -alkoxy have the same meaning as described above and have the highest corresponding number of C atoms.

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

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

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

The C ₂ -C ₁₂ alkenyl is mono- or polyunsaturated and is, for example, C ₂ -C _10- , C ₂ -C _8- , C ₂ -C ₅ -alkenyl, such as vinyl, allyl , Methylallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl , 7-octenyl or dodecenyl, especially allyl. C ₂ -C ₅ alkenyl has the same meaning as given above for C ₂ -C ₁₂ alkenyl and has the highest corresponding number of C atoms.

The interspersed one or more C ₂ -C ₁₂ alkenyl groups of O, CO or NR ₂₆ are interspersed with O, S, NR ₂₆ or CO (for example) 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 time. Or 2 times. If more than one mesohetero group is present, they are the same kind or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylidene). The 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.

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

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

The C ₂ -C ₁₂ alkynyl is a mono- or polyunsaturated straight or branched chain and is, for example, a C ₂ -C _8- , C ₂ -C ₆ -or C ₂ -C ₄ alkynyl. Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, Octynyl and others.

The C ₂ -C ₂₀ alkylfluorenyl is linear or branched and is, for example, C ₂ -C _18- , C ₂ -C _14- , C ₂ -C _12- , C ₂ -C _8- , C ₂ -C ₆ -or C ₂ -C ₄ alkylfluorenyl or C ₄ -C ₁₂ -or C ₄ -C ₈ alkylfluorenyl. Examples are ethenyl, propionyl, butyryl, isobutyryl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl Base, hexadecanoyl, octadecyl, and icosyl, preferably ethenyl. C ₁ -C ₈ alkylfluorenyl has the same meaning as given above for C ₂ -C ₂₀ alkylfluorenyl and has the highest corresponding number of C atoms.

The C ₂ -C ₁₂ alkoxycarbonyl is linear or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonoxycarbonyl, decoxycarbonyl or dodecyloxycarbonyl, especially methoxy A carbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, or an isobutoxycarbonyl group, preferably a methoxycarbonyl group.

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

The C ₃ -C ₁₀ cycloalkylcarbonyl group is C ₃ -C ₁₀ cycloalkyl-CO-, wherein the cycloalkyl group has one of the meanings shown above and has the highest corresponding number of C atoms. The C ₃ -C ₁₀ cycloalkylcarbonyl group interspersed with one or more O, S, CO, NR ₂₆ refers to metacycloalkyl-CO-, wherein the metacycloalkyl group is as defined above.

The C ₃ -C ₁₀ cycloalkoxycarbonyl group is C ₃ -C ₁₀ cycloalkyl-O- (CO)-, wherein the cycloalkyl group has one of the meanings shown above and has the highest corresponding number of C atoms. A C ₃ -C ₁₀ cycloalkoxycarbonyl group interspersed with one or more O, S, CO, NR ₂₆ refers to metacycloalkyl-O- (CO)-, wherein the metacycloalkyl group is as described above As defined.

The C ₁ -C ₂₀ alkylphenyl group refers to a phenyl group substituted with one or more alkyl groups, wherein the total of C atoms is at most 20.

The C ₆ -C ₂₀ aryl system is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, And the like, especially tetraphenyl, naphthyl, and the like are phenyl or naphthyl, and phenyl is preferred. Naphthyl is 1-naphthyl or 2-naphthyl.

In the context of the present invention, the C ₃ -C ₂₀ heteroaryl is intended to include a monocyclic or polycyclic system, such as a fused ring system. Examples are thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furanyl, dibenzofuranyl, Fluorenyl, xanthenyl, thioxanthenyl, phenoxathiol, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, midindenyl, isoindolyl, indolyl , Indazolyl, purinyl, quinazinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, Porphyrinyl, pyridinyl, carbazolyl, β-pyridinyl, phenanthridyl, acridinyl, naphthylazine, phenanthroline, phenazinyl, isothiazolyl, phenothiazinyl , Isoxazolyl, furfuryl, 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-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl -7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxanthenyl, 2,7-phenoxanthenyl, 2 -Pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4 -Imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl , 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindole , 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-purine , 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 group, 2,3-dimethoxy-6-quinoxaline group, 2-quinazolinyl group, 7-quinazolinyl group, 2-dimethylamino group -6-quinazolinyl, 3- Phenyl, 6- Phenyl, 7- Phenyl, 3-methoxy-7- Phenyl, 2-pyridinyl, 6-pyridinyl, 7-pyridinyl, 6,7-dimethoxy-2-pyridinyl, 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- Perylene-6-yl, 3-phenanthridyl, 2-acridyl, 3-acridyl, 2-naphthylazine, 1-methyl-5-naphthylazine, 5-phenanthroline, 6-phenanthroline, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenthiazinyl , 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 4-methyl-3-furanyl Group, 2-phenoxa group, 10-methyl-2-phenoxa group and the like.

The C ₃ -C ₂₀ heteroaryl group is especially thienyl, benzo [b] thienyl, thiathranyl, thioxanthenyl, 1-methyl-2-indolyl or 1-methyl-3-indole Radical; especially thienyl.

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

The substituted aryl (phenyl, naphthyl, C ₆ -C ₂₀ aryl or C ₅ -C ₂₀ heteroaryl) is 1 to 7 times, 1 to 6 times or 1 to 4 times, especially 1 Substitutions, 2 or 3 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 the 3,4-, 3,4,5-, 2,6-, 2,4-, or 2,4,6-group. state.

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

The group substituted with one or more defined substituents is intended to have one substituent or multiple substituents with the same or different definitions as given. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, and fluorine and chlorine are preferred. If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ are independently common to each other as ; Then, for example, the following structures (Ia) -I (i) are formed: Or (for example)

Structures such as (Id)-(Ih):

The better one is structure (Ia).

The photoinitiator (C-1) having a structure represented by the formula (C-I) is characterized in that at least one phenyl ring is fused with a carbazole moiety to form a "naphthyl" ring. That is, one of the above structures is given by the structure shown by formula (C-I).

If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R _7, or R ₇ and R ₈ independently of each other are-(CH ₂ ) _P -Y- (CH ₂ ) _q- , then forming (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.

Instance system Wait.

If R ₁₇ forms a bond to a group or A direct bond to a carbon atom of a phenyl or naphthyl ring forms, for example, such as And other structures.

If R ₁₆ is a phenyl substituted with SR ₁₈ , where the group R ₁₉ 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 N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S or NR ₁₇ , 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 N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S, or NR ₁₇ , then an uninterrupted or mixed O is formed. Or NR ₁₇ , especially O-5 or 6-membered saturated rings.

If R ₂₁ and R _{22 together} with the attached N atom form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S or NR ₂₆ , and the benzene ring is fused 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 Ring (e.g. )Wait.

If R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, the ring system is intended to include more than one ring (e.g., 2 or 3 rings) and one or one from the same species or different species Above heteroatoms. Suitable heteroatom systems 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 Step or integer group or step group, but does not exclude any other integer or step or integer group or step group. The term "(meth) acrylate" in the context of this application is intended to mean acrylate and corresponding Methacrylate.

The preferred ones shown in the text used for the compounds of the present invention in the context of the present invention are intended to refer to all categories of patent application scope, that is, to the patent application scope of compositions, uses, methods, color filters, and the like.

The oxime ester having the structure represented by the formula (CI) is prepared by a method described in the literature, for example, by reacting a corresponding oxime with a halogen, especially a chloride or an acid anhydride, under the following conditions: Tributylmethyl 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 a compound of formula Ia is illustrated, in which R ₇ is an oxime ester group and X is a direct bond system [the reaction of compounds (Ib)-(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 is CO, the corresponding oxime is obtained by separating the methylene methylene group with 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 the formula (CI) having the formula (CI) as defined above by reacting the corresponding oxime compound with the halogen halide of formula (a) or the anhydride of formula (b) in the presence of a base or a mixture of bases Method of photoinitiator (C-1) of the structure shown.

Wherein Hal is halogen, 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), aqueous DMA, ethanol or aqueous ethanol. 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 intermediates are prepared, for example, by methods described in the literature (e.g. standard chemistry textbooks, e.g. 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 for them Those skilled in the art are familiar.

Another convenient synthesis of oximes is the use of nitrous acid or alkyl nitrite to "active" methylene nitrite. Basic conditions (as described in Organic Syntheses coll. Vol. VI (J. Wiley & Sons, New York, 1988), pages 199 and 840) and acidic conditions (as in Organic Synthesis coll. Vol. V, p. 32 and 373, coll. Vol. III, 191 and 513, coll. Vol. II, 202, 204, and 363) Both are suitable for preparation in the present invention Oxime used as starting material. 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 light initiator (C-1) having a structure represented by the free formula (IA):

Among them, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, , COR ₁₆ , OR ₁₇ , halogen, NO ₂ or ; Or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independent of each other. Substituted C ₂ -C ₁₀ alkenyl; or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R _7, or R ₇ and R ₈ are independently common with each other Is-(CH ₂ ) _P -Y- (CH ₂ ) _q- ; or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ And R ₈ independently of each other are ; Provided that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen, Phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, (CO) OH or (CO) O (C ₁ -C ₄ alkyl); or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ Independently of each other are unsubstituted phenyl or phenyl substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring with one 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 independent of each other for , COR ₁₆ or NO ₂ ; Y is O, S, NR ₂₆ or direct bond; p is integer 0, 1, 2 or 3; q is integer 1, 2 or 3; X is CO or direct bond; R ₁₃ is C _1- C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ or ; Or R ₁₃ is a C ₂ -C ₂₀ alkyl group, which is interspersed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO, or C ₂ -C ₁₂ alkenyl, which is not interspersed or interspersed with Or more O, CO or NR ₂₆ in which the interspersed C ₂ -C ₂₀ alkyl and unsaturated or interspersed C ₂ -C ₁₂ alkenyl are unsubstituted or substituted with one or more halogens; or R ₁₃ is a C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl, or C ₃ -C ₁₀ cycloalkyl group, which is not interspersed or interspersed with one or more O, S, CO or NR ₂₆ ; or R ₁₃ Phenyl or naphthyl, each unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , CN, NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, interposed with one or more O, S, CO or NR ₂₆ ; each warp or C ₃ -C ₁₀ cycloalkyl, or interrupted by one or more O, S, CO or NR ₂₆ of the C ₃ -C ₁₀ cycloalkyl; K-based integer from 1 to 10; R ₁₅ lines C ₆ - C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, interspersed with one or more O, S or C ₂ -C ₂₀ alkyl group of NR ₂₆ ; or each C ₁ -C ₂₀ alkyl group substituted, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl, which is not interspersed or interspersed with one or more O, CO or NR ₂₆ ; or R ₁₅ C ₁ -C ₂₀ alkyl-based, which was used without A substituted or by one or more of the following groups: _{halo, OR 17, SR 18, C} 3 -C 8 cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl group, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , , , Phenyl; or the C ₁ -C ₂₀ alkyl group is substituted with a phenyl group, the phenyl group is halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₄ haloalkyl group, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ Substituted; or R ₁₅ is a C ₂ -C ₂₀ alkyl group, in which one or more O, SO, or SO ₂ is interspersed, and the interspersed C ₂ -C ₂₀ alkyl group is unsubstituted or substituted by one or more of the following groups Group substitution: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is a C ₂ -C ₂₀ alkylfluorenyl or benzyl Fluorenyl, which is unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is unsubstituted or A naphthylmethyl group substituted with one or more OR ₁₇ or a C ₃ -C ₁₄ heteroarylcarbonyl group; or R ₁₅ is a C ₂ -C ₁₂ alkoxycarbonyl group, which is not interspersed or interspersed with one or more O And the C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R ₁₅ is a phenoxycarbonyl group which is unsubstituted or substituted with one or more Group substitution: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S (O) _m -C ₁ -C ₆ alkyl, unsubstituted or C ₁ -C ₁₂ alkyl or SO ₂ -C ₁ -C ₆ alkyl substituted S (O) _m -phenyl; or R ₁₅ is SO ₂ O-phenyl, which is unsubstituted or substituted by C ₁ -C ₁₂ Group substitution; or is diphenylphosphinofluorenyl or bis (C ₁ -C ₄ alkoxy) -phosphinofluorenyl; m is 1 or 2; R _'15 has one of the meanings given for R ₁₅ ; X ₁ is O, S, SO or SO ₂ ; X ₂ is O, CO, S or direct bond; R ₁₆ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is not Substituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or interspersed with one or more O, S or C ₁ -C ₂₀ alkyl of NR ₂₆ ; or each of them is substituted by one or more C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted by one or more of the following Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl butoxycarbonyl, oR _17, SR ₁₈ or NR ₁₉ R _20; or R ₁₆ lines , Unsubstituted or substituted with one or more of the following radicals C ₁ -C ₂₀ alkyl group: halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl, (CO) OH or (CO) O ( (C ₁ -C ₄ alkyl); or R ₁₆ is a C ₂ -C ₁₂ alkyl mixed with one or more O, S or NR ₂₆ ; or R ₁₆ is (CH ₂ CH ₂ O) _{n + 1} H, ( CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl; or R ₁₆ is 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; n is 1 to 20; R ₁₇ is hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O ( CO) -phenyl, (CO) OH, (CO) O (C ₁ -C ₄ alkyl), SO _2- (C ₁ -C ₄ haloalkyl), O (C ₁ -C ₄ haloalkyl), C or ₃ -C ₂₀ cycloalkyl interrupted by one or more of C ₃ -C ₂₀ O Alkyl group; R _17, or C ₂ -C ₂₀ alkyl-based, have therebetween one or more heteroatoms O, S or NR _26; or R ₁₇ lines _{(CH 2 CH 2 O) n} + 1 H, (CH 2 CH 2 O ) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenyl or C ₃ -C ₂₀ cycloalkyl , Which is not interspersed or interspersed with one or more O, S, CO or NR ₂₆ ; or R ₁₇ is a C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl, which is unstrained or interspersed with one or more O; or R ₁₇ is benzamyl, which is unsubstituted or substituted with one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or R ₁₇ is phenyl , Naphthyl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenyl Amino-amino Or R ₁₇ forms a bond to or Direct bond of one carbon atom of phenyl or naphthyl ring; R ₁₈ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, where C _2- C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl without one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; or R ₁₈ Is a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ ( CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl Or (CO) OR ₁₇ ; or R ₁₈ is a C ₂ -C ₂₀ alkyl group, which is interspersed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; or R ₁₈ (CH ₂ CH ₂ O) _n H , (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkylfluorenyl or C ₃ -C ₆ alkenyl; or R ₁₈ benzamyl, It is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy, or C ₁ -C ₄ alkylthio; or R ₁₈ series Phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ Haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N ( C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO) O (C ₁ -C ₈ alkyl), (CO) -C ₁ -C ₈ alkyl, (CO) N (C _1- C ₈ alkyl) ₂ or ; R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, SO _2- (C ₁ -C ₄ haloalkyl), C ₁ -C ₈ alkylfluorenyl, C ₁ -C ₈ alkylfluorenyloxy , C ₃ -C ₁₂ alkenyl or benzamyl; or R ₁₉ and R ₂₀ are phenyl, naphthyl, or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or has one or more of the following groups Group substitution: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzamidine or C ₁ -C ₁₂ alkoxy; or R ₁₉ and R ₂₀ With its attached N atom to 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-membered saturated or unsaturated ring is unsubstituted or One or more of the following groups substituted: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO) R ₂₃ , NO ₂ , halogen , C ₁ -C ₄ -haloalkyl, CN, phenyl, Or C ₃ -C ₂₀ cycloalkyl, the C ₃ -C ₂₀ cycloalkyl has one or more O, S, CO, or NR ₁₇ without interspersed or interspersed; or R ₁₉ and R ₂₀ with the N atom to which it is attached Together form a heteroaromatic ring system that is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO) R ₂₃ , , Halogen, NO ₂ , CN, phenyl, or C ₃ -C ₂₀ cycloalkyl, the C ₃ -C ₂₀ cycloalkyl is not interspersed or interspersed with one or more O, S, CO, or NR ₁₇ ; R ₂₁ and R _{22 is} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ₂₁ and R ₂₂ together with the N atom to which they are attached Forms a 5- or 6-membered saturated or unsaturated ring without interspersed or interspersed O, S or NR ₂₆ , and the 5- or 6-membered saturated or unsaturated ring is not fused or the 5- or 6-membered saturated or unsaturated Saturated ring systems are fused with benzene rings; R ₂₃ is hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkanes interspersed with one or more O, CO or NR ₂₆ , C ₃ -C ₂₀ cycloalkyl without meta or hetero, O, S, CO or NR ₂₆ , or R ₂₃ phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ is (CO) OR ₁₇ , CONR ₁₉ R ₂₀ , (CO) R ₁₇ ; or R ₂₄ has one of the meanings given for R ₁₉ and R ₂₀ ; R ₂₅ is COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO) R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ ; R ₂₆ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl , C ₂ -C ₂₀ alkyl, with one or more O or CO interspersed between them; or phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl, without interspersed or interspersed with one or more O Or CO; or (CO) R ₁₉ ; or phenyl, which is unsubstituted or substituted with one or more of the following: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or ; Provided that at least one group is present in the molecule or

The preferred group defined for the photoinitiator (C-1) of the structure represented by formula (IA) corresponds to the photoinitiator (C- 1) given, just for 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 the photoinitiator (C-1) of the structure represented by the formula (C-I).

The preferred one is the photoinitiator (C-1) of the structure shown by the formula (CI) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 is} independently of each other hydrogen, C ₁ -C ₂₀ alkyl, , COR ₁₆ or NO ₂ , or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of one another are Provided that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ ; X is CO or a direct bond; R ₁₃ is C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₃ is a C ₂ -C ₂₀ alkyl group with one or more O, S, NR ₂₆ or CO interposed therebetween; or R ₁₃ is phenyl or naphthyl, both Unsubstituted or one or more Or COR ₁₆ substitution; R ₁₄ is C ₁ -C ₂₀ alkyl, phenyl or C ₁ -C ₈ alkoxy; R ₁₅ is phenyl, naphthyl, C ₃ -C ₂₀ heteroaryl, each without Substituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or C ₂ -C ₂₀ alkyl with one or more O or S interposed therebetween; or They are each substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group being unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ Or PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₅ is a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ Cycloalkyl, C ₃ -C ₂₀ heteroaryl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; R _'14 has one of the meanings given for R ₁₄ one; R _'15 has the meanings for R ₁₅ Suo one of those given; R ₁₆ lines phenyl, which is unsubstituted or substituted with one or more of the following _{groups: oR 17, SR 18, NR} 19 R 20 Interrupted by one or more O, S or NR C ₂₆ of ₂ -C ₂₀ alkyl, phenyl or R ₁₆ lines, which is substituted by one or more C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl group which Unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ Aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ is C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with: Halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkane) Group) or (CO) O (C ₁ -C ₄ alkyl); R ₁₇ is a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, OCH ₂ CH ₂ ( CO) O (C ₁ -C ₄ alkyl), O (C ₁ -C ₄ alkyl), (CO) O (C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl or interspersed with one or A C ₃ -C ₂₀ cycloalkyl group of multiple O; or R ₁₇ is a C ₂ -C ₂₀ alkyl group with one or more O interposed therebetween; R ₁₈ is a methyl group substituted with (CO) OR ₁₇ ; R ₁₉ and R _{20 is} independently of each other hydrogen, phenyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₈ alkylfluorenyl, or C ₁ -C ₈ alkylfluorenyloxy ; Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, which ring system is unsubstituted or Substitution; provided that at least one group is present in the molecule or

Attention must be paid to the photoinitiator (C-1) of the structure shown in the formula (CI) as defined above, wherein R ₁ , R ₂ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen, COR ₁₆ or NO ₂ , R ₃ and R ₄ together are ; R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are hydrogen; X is a direct bond; R ₁₃ is C ₁ -C ₂₀ alkyl; R ₁₄ is C ₁ -C ₂₀ alkyl; R ₁₅ is C ₁ -C ₂₀ Alkyl or phenyl substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl; R ₁₆ is phenyl substituted with one or more C ₁ -C ₂₀ alkyl or OR ₁₇ ; and R ₁₇ based unsubstituted or substituted with one or more of halogen or C ₁ -C ₂₀ alkyl interrupted by one or more lines of C ₂ -C ₂₀ O-alkyl; with the proviso that there is in the molecule at least one group .

The subject matter of the present invention is further a photoinitiator (C-1) having a structure shown by the 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 hydrogen, or R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ are independently common to each other as Provided that at least one of R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ is Or R ₂ series , COR ₁₆ , NO ₂ or ; Or R ₇ series Or COR ₁₆ ; R ₉ , R ₁₁ and R ₁₂ are hydrogen; R ₁₀ is hydrogen, OR ₁₇ or COR ₁₆ ; X is CO or a direct bond; R ₁₃ is C ₁ -C ₂₀ alkyl, which is unsubstituted or One or more of the following groups are substituted: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO (OC _k H _{2k + 1} ) ₂ ; or R ₁₃ is a C ₂ -C ₂₀ alkyl group with one or more O interposed therebetween Or R ₁₃ is phenyl; k is an integer 2; R ₁₄ is C ₁ -C ₂₀ alkyl or thienyl; R ₁₅ is phenyl or naphthyl, each of which is unsubstituted or via one or more OR ₁₇ or C ₁ -C ₂₀ alkyl substitution; or R ₁₅ is thienyl, hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ is a C ₂ -C ₂₀ alkyl with SO ₂ interposed therebetween; R ₁₆ is phenyl or naphthyl, each Unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ is thienyl; R ₁₇ is hydrogen, C ₁ -C ₈ Alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or via one or more of the following groups: halogen, O (CO)-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄₎ alkenyl group or interrupted by one or O of a C ₃ -C ₂₀ cycloalkyl; R _17, or C ₂ -C ₂₀ alkyl-based, have therebetween one or more heteroatoms O; R ₁₈ lines C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl Group, which is unsubstituted or substituted with one or more OH, O (CO)-(C ₂ -C ₄ ) alkenyl or (CO) OR ₁₇ ; or R ₁₈ is phenyl, which is unsubstituted or substituted Or more than one halogen substitution; R ₁₉ and R ₂₀ are independently C ₁ -C ₈ alkylfluorenyl or C ₁ -C ₈ alkylfluorenyloxy; or R ₁₉ and R ₂₀ are formed together with the N atom to which they are attached There are 5 or 6-membered saturated rings in between; provided that at least one group is present in the molecule .

Examples of compounds of the invention are compounds of formula (Ia)-(Ig) as defined above. Compounds of formula (Ia), (Ib), (Ic), especially formula (Ia) or (Ic), or formula (Ia), (Ic) or (Id), especially formula (Ia) are of interest.

For example, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen, Or COR ₁₆ or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ independently of one another are .

For example, R ₃ and R ₄ or R ₁ and R ₂ together are Or R ₃ and R ₄ and R ₅ and R ₆ together are ; R ₃ and R _{4 are} particularly common .

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

R _{7 is} especially hydrogen, Or COR ₁₆ . Or R ₇ series Or COR ₁₆ , especially .

R _{2 is} especially , COR ₁₆ or Or R ₂ together with R ₁ is . R _{2 is} especially COR ₁₆ .

X is preferably a direct bond.

For example, R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups: C _1- C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ , wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring with one 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 independent of each other Or COR ₁₆ .

Specifically, for example, R ₉ , R ₁₀ , R _11, and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or one substituted with one or more of the following groups Phenyl: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other Or COR ₁₆ .

For example, R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or one substituted with one or more C ₁ -C ₆ alkyl. Phenyl; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently Or COR ₁₆ .

In another embodiment, for example, R ₉ , R ₁₀ , R _11, and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or via one or more of the following groups Group substituted phenyl: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently halogen, 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 .

In addition, for example, R ₉ , R ₁₀ , R _11, and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups : C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or COR ₁₆ .

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

Preferably, R ₉ , R ₁₁ and R ₁₂ are hydrogen and R ₁₀ is hydrogen, OR ₁₇ or COR ₁₆ .

R ₁₃ is, for example, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following: halogen, COOR ₁₇ or CONR ₁₉ R ₂₀ ; or R ₁₃ is C ₂ -C ₂₀ alkyl , Interspersed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO, or C ₂ -C ₁₂ alkenyl, optionally interspersed with one or more O, CO or NR ₂₆ , or R ₁₃ series C ₃ -C ₁₀ cycloalkyl, optionally mixed with one or more O, S, CO, NR ₂₆ , or R ₁₃ phenyl or naphthyl, both of which are unsubstituted or have one or more of the following groups Group substitution: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , , COR ₁₆ , NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl with one or more O interposed therebetween; or C ₁ -C ₂₀ alkyl , Which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or C ₂ -C ₂₀ alkyl with one or more O interposed therebetween.

In addition, R ₁₃ is, for example, a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or a C ₂ -C ₂₀ alkyl group with one or more O interposed therebetween; or a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₁₀ cycloalkyl group; or R ₁₃ is phenyl or naphthyl, 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 , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, with one or more O interposed therebetween.

In another embodiment, R ₁₃ is, for example, a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , OR ₁₇ , SR _18, or PO (OC _k H _{2k + 1} ) ₂ ; or C ₂ -C ₂₀ alkyl with one or more O interposed therebetween; or C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₀ cycloalkyl, phenyl or naphthyl .

Or R ₁₃ is, for example, a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR _18, or PO (OC _k H2 _{k + 1} ) ₂ ; or a C ₂ -C ₂₀ alkyl group with one or more O interposed therebetween; or a phenyl group, a C ₂ -C ₁₂ alkenyl group or a C ₃ -C ₁₀ cycloalkyl group.

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

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

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

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

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

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

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

R ₁₅ is, for example, a C ₆ -C ₂₀ aryl group or a C ₅ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkane Group, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , C ₁ -C ₂₀ alkyl group; or R ₁₅ series hydrogen, C ₃ -C ₈ cycloalkyl group, the C ₃ -C ₈ cycloalkyl group Optionally mixed with one or more O, CO or NR ₂₆ ; or R ₁₅ is a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , C ₃ -C ₈ cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₈ -C ₂₀ phenoxycarbonyl, C ₅ -C ₂₀ heteroaryloxy-carbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , , Phenyl or phenyl substituted by: halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ or NR ₁₉ R ₂₀ ; or R ₁₅ is C ₂ -C ₂₀ alkyl , Interspersed with one or more O, S or SO ₂ , or R ₁₅ is C ₂ -C ₂₀ alkylfluorenyl, benzamidine, C ₂ -C ₁₂ alkoxycarbonyl, phenoxycarbonyl, CONR ₁₉ R ₂₀ , NO ₂ or C ₁ -C ₄ haloalkyl.

In addition, R ₁₅ is, for example, hydrogen, C ₆ -C ₂₀ aryl, especially phenyl or naphthyl, each of which is unsubstituted or substituted with C ₁ -C ₁₂ alkyl; or is C ₃ -C ₅ hetero Aryl, such as thienyl; or C ₃ -C ₈ cycloalkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₇ , C _3- C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ is a C ₂ -C ₂₀ alkyl with one or more O or SO ₂ interspersed therebetween.

The photoinitiator (C-1) having a structure represented by formula (CI) is of interest, in which R ₁₅ is (for example) hydrogen, phenyl, or naphthyl, each of which is unsubstituted or is C ₁ -C ₈ Alkyl substitution; or R ₁₅ is thienyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₇ , C ₃ -C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ is a C ₂ -C ₂₀ alkyl group with one or more O or SO ₂ interspersed therebetween.

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

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

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

R ₁₆ is, for example, a C ₆ -C ₂₀ aryl group (especially phenyl or naphthyl group, especially phenyl group) or a C ₅ -C ₂₀ heteroaryl group (especially thienyl group), each of which is unsubstituted or substituted by one or more Substituted with the following groups: phenyl, halogen, C ₁ -G ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl interspersed with one or more O; Or each of them is substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , benzene , C ₃ -C ₈ cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₅ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ is hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, C _3- C ₆ alkenyloxy, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C ₁ -C ₄ alkyl); or R ₁₆ is a C ₂ -C ₁₂ alkyl group with one or more O interposed therebetween; or (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkane And n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

In addition, R ₁₆ is, 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, C ₁ -C _4- haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ is C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: Halogen, phenyl, OH, SH, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl) , O (CO) -phenyl, (CO) OH or (CO) O (C ₁ -C ₄ alkyl); or R ₁₆ is a C ₂ -C ₁₂ alkyl group with one or more O interposed therebetween; or (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl And n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

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

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

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

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

R ₁₇ is, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkyl), O (CO)-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO) -benzene group, (CO) OH, (CO ) O (C 1 -C 4 alkyl), C ₃ -C ₂₀ cycloalkyl interrupted by one or more O or of C ₃ -C ₂₀ cycloalkyl; or R ₁₇ lines C ₂ -C ₂₀ alkyl with one or more O interposed between it; (CH ₂ CH ₂ O) _{n + 1} H, (GH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl) , C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenyl, or C ₃ -C ₂₀ cycloalkyl, optionally mixed with one or more O; or R ₁₇ series Benzamidine, which is unsubstituted or substituted with one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or R ₁₇ is phenyl, naphthyl or C5-C ₂₀ heteroaryl groups, each unsubstituted or substituted with one or more of the following groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl- C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenyl-amino or .

In another embodiment, R ₁₇ is, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen , O (CO)-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ alkenyl), or C ₂ -C ₂₀ alkyl interspersed with one or more O; or C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, C ₃ optionally interspersed with one or more O -C ₂₀ cycloalkyl; or benzamidine, which is unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; Or is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, or C ₁ -C ₁₂ alkoxy.

R ₁₇ is also, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or via one or more of the following groups Substitution: halogen, C ₃ -C ₂₀ cycloalkyl, O (CO)-(C ₁ -C ₄ alkyl), O (CO)-(C ₂ -C ₄ alkenyl) or one or more O C ₂ -C ₂₀ alkyl, or R ₁₇ is C ₂ -C ₂₀ alkyl, with one or more O interposed therebetween.

R _{17 is} especially hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₂₀ alkyl, which are unsubstituted or substituted with one or more of the following groups: O (CO)-(C ₁ -C ₄ alkyl Group), O (CO)-(C ₂ -C ₄ alkenyl), or C ₂ -C ₂₀ alkyl group with one or more O, or R ₁₇ C ₂ -C ₂₀ alkyl group with one or more A O.

R ₁₈ is, for example, a C ₃ -C ₂₀ cycloalkyl group, which is unsaturated or has one or more O; or R ₁₈ is a C ₁ -C ₂₀ alkyl group, which is unsubstituted or after one or more Group substitution: OH, O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO)-(C ₁ -C ₄ alkyl) or (CO) OR ₁₇ ; or R ₁₈ is C ₂ -C ₂₀ alkyl with one or more O, S, CO, NR ₂₆ or COOR ₁₇ interposed therebetween; or R ₁₈ is a C ₂ -C ₈ alkylfluorenyl or C ₃ -C ₆ alkenyl, benzamidine; or R ₁₈ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkane Radical, C ₁ -C ₁₂ alkoxy or NO ₂ .

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

R _18- based (for example) C ₁ -C ₂₀ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₂ -C ₈ alkyl , Benzamidine, phenyl or naphthyl.

For example, R ₁₈ is C ₁ -C ₂₀ alkyl, which is substituted with one or more of the following groups: OH, O (CO)-(C ₂ -C ₄ ) alkenyl, O (CO)-(C _1- C ₄ alkyl) or (CO) OR ₁₇ , or R ₁₈ is phenyl, which is substituted with one or more halogens.

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

For example, R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl Phenyl, or naphthyl, C ₁ -C ₈ alkylfluorenyl, C ₁ -C ₈ alkylfluorenyloxy, C ₃ -C ₁₂ alkenyl or benzamyl; or R ₁₉ and R ₂₀ The attached N atoms together 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 attached N atom form a heteroaromatic ring system, The ring system is unsubstituted or substituted with one or more of the following: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, or .

In addition, for example, R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkylfluorenyl, C ₁ -C ₈ alkylfluorenyloxy, C ₃ -C ₁₂ alkenyl or benzamyl; or R ₁₉ and R ₂₀ with the N to which they are attached Atoms together form a 5- or 6-membered saturated ring optionally mixed with O or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a carbazole ring.

For example, R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl , C ₁ -C ₈ alkylfluorenyl, C ₁ -C ₈ alkylfluorenyloxy, C ₃ -C ₁₂ alkenyl or benzamyl; or R ₁₉ and R ₂₀ together with the N atom to which they are attached A 5 or 6 member saturated ring with O or NR ₁₇ interspersed as appropriate.

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

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

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

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

R ₂₆ is, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, interposed with one or more O or CO; or phenyl-C _1- C ₄ alkyl, C ₃ -C ₈ cycloalkyl, optionally mixed with one or more O or CO; or (CO) R ₁₉ or phenyl, unsubstituted or through one or more of the following groups Substitution: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ .

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

Examples of the photoinitiator (C-1) having the structure represented by the formula (C-I) in the present invention are shown by the following formulae (1) to (86).

The use of the photoinitiator (C-1) having a structure represented by the formula (C-I) for photopolymerizing a composition containing at least one ethylenically unsaturated photopolymerizable compound.

Based on the used amount of the alkali-soluble resin (A) being 100 parts by weight, the used amount of the photoinitiator (C-1) having the structure represented by the formula (CI) is 2 to 20 parts by weight, preferably 3 to 18 parts by weight, more preferably 4 to 16 parts by weight.

When the black photosensitive resin composition of the present invention contains the light initiator (C-1) having the structure represented by the formula (CI), the black matrix and the black gap prepared from the black photosensitive resin composition The body can be further improved without developing residue.

In the black photosensitive resin composition of the present invention, other photoinitiators (C-2) can be optionally added.

Specific examples of the other photoinitiator (C-2) may include O-fluorenyl oxime compounds, triazabenzene compounds, acetophenone compounds, and diimidazoles other than the aforementioned photoinitiator (C-1). Compound, benzophenone compound, α -diketone compound, keto alcohol compound, keto alcohol ether compound, phosphonium oxide, quinone compound, halogen-containing compound, peroxide, or any combination thereof.

Specific examples of the O-fluorenyl oxime compound other than the photoinitiator (C-1) may include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-phenylfluorenyl oxime), 1- [4- (phenylthio) phenyl] -octane-1,2-dione-2- (O-phenylfluorenyl oxime), 1- [4- (Phenylphenyl) phenyl] -heptane-1,2-dione-2- (O-phenylfluorenyloxime), 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3-substituent] -ethanone-1- (O-ethylfluorenyloxime), 1- [9-ethyl-6- (3-methylphenylfluorenyl) -9H-carb Azole-3-substituent] -ethanone-1- (O-acetamidooxime), 1- (9-ethyl-6-phenylamidino-9H-carbazole-3-substituent) -ethane Keto-1- (O-ethylammonium oxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylphenylfluorenyl) -9H-carbazole-3-substituted Yl] -1- (O-ethylamidoxime), acetone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylphenylfluorenyl) -9H-carbazole -3-Substituent] -1- (O-ethylammonium oxime), acetone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofurylphenylfluorenyl) -9H-carb Azole-3-substituent] -1- (O-acetamidooxime), acetone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-acetylamoxime), acetone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuran) (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) phenylfluorenyl] -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) and the like, or any combination thereof.

Preferably, the O-fluorenyl oxime compound other than the photoinitiator (C-1) may be 1- [4- (phenylthio) phenyl] -octane-1,2-dione-2 -(O-benzyl oxime), which can be a product manufactured by Ciba Refining Co., Ltd., and the model is OXE-01; 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazole-3-substituent] -ethanone-1- (O-acetylamoxime), which can be a product manufactured by Ciba Refining Co., Ltd., and the model number is OXE-02; -1- [9-ethyl-6- (2-methyl- 4-tetrahydrofuranmethoxyphenylfluorenyl) -9H-carbazole-3-substituent] -1- (O-ethylfluorenyloxime); acetone-1- {9-ethyl-6- [2- Methyl-4- (2,2-dimethyl-1,3-dioxapentyl) methoxyphenylfluorenyl] -9H-carbazole-3-substituent} -1- (O-ethyl Fluorenyl oxime) or any combination thereof. These O-fluorenyl oxime compounds may be used alone or in combination.

Specific examples of the above-mentioned triazabenzene compound may include, but are not limited to, vinyl-halomethyl-s-triazabenzene compound, 2- (naphtho-1-substituted) -4,6-bis-halo Methyl-s-triazabenzene compound, 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazabenzene compound, etc., or any combination thereof .

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

Specific examples of the aforementioned 2- (naphtho-1-substituted) -4,6-bis-halomethyl-s-triazabenzene compound may include 2- (naphtho-1-substituted) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (4-methoxy-naphtho-1-substituted) -4,6-bis-trichloromethyl-s-triaza Benzene, 2- (4-ethoxy-naphtho-1-substituted) -4,6-bis-trichloromethyl-s-triazabenzene, 2- (4-butoxy-naphtho- 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-substituent] -4,6-bis-trichloromethyl-s-triazabenzene, 2- (2-methoxy-naphtho-1-substituted) -4,6-bis-trichloromethyl-s-triazabenzene, 2- (6-methoxy-5-methyl- Naphtho-2-substituted) -4,6-bis-trichloromethyl-s-triazabenzene, 2- (6-methoxy-naphtho-2-substituted) -4,6-bis -Trichloromethyl-s-triazabenzene, 2- (5-methoxy-naphtho-1-substituted) -4,6-bis-trichloromethyl-s-triazabenzene, 2 -(4,7-dimethoxy-naphtho-1-substituted) -4,6-bis-trichloromethyl-s-triazabenzene 2- (6-ethoxy - 2-substituted naphtho-yl) -4,6-bis - trichloromethyl -s- triazine or 2- (4,5-dimethoxy-naphtho-1-substituted) compounds such as 4,6-bis-trichloromethyl-s-triazabenzene, or any combination thereof.

Specific examples of the aforementioned 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazabenzene compound may include 4- [p-N, N-bis (ethoxycarbonyl) (Methyl) aminophenyl] -2,6-bis (trichloromethyl) -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-bis (chloroethyl) aminophenyl] -2,6-bis (trichloro (Methyl) -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) amino Phenyl] -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) aminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-bromo -P-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6- (Trichloromethyl) -s-triazabenzene, 4- [m-chloro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloro (Methyl) -s-triazabenzene, 4- [m-fluoro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [o-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s- Triazabenzene, 4- [o-chloro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triaza Benzene, 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-triazabenzene, 4- [m-bromo-p-N, N-bis (chloroethyl) Aminophenyl] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-chloro-p-N, N-bis (chloroethyl) aminophenyl]- 2,6-bis (trichloromethyl) -s-triazabenzene, 4- [m-fluoro-p-N, N-bis (chloroethyl) aminobenzene Group] -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (m-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazabenzene, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s -Triazabenzene, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (O-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-chloro-p-N -Ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-fluoro-p-N-ethoxycarbonylmethylamine Phenyl) -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-triaza Benzene, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-bromo-p-- N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-chloro-p-N-chloroethylaminophenyl)- 2,6-bis (trichloromethyl) -s-triazabenzene, 4- (o-fluoro-p- N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazabenzene or 2,4-bis (trichloromethyl) -6- {3-bromo-4 -A compound of [N, N-bis (ethoxycarbonylmethyl) amino] phenyl} -1,3,5-triazabenzene, or any combination thereof.

The above triazabenzene compound is preferably 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. These triazabenzene compounds may be used alone or in combination.

Specific examples of the acetophenone compound may include p-dimethylamine acetophenone, α , α' -dimethoxyoxy azoacetophenone, 2,2'-dimethyl-2-phenyl Acetophenone, p-methoxyacetophenone, 2-benzyl-2-N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone or 2-methyl Compounds such as -1- [4- (methylthio) phenyl] -2- (4-morpholino) -1-acetone, or any combination thereof. The acetophenone compound may preferably be 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholino) -1-acetone, 2-benzyl-2- N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone. These acetophenone compounds may be used alone or in combination.

Specific examples of the above diimidazole compound may include 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole, 2,2'-bis (o-fluorobenzene) ) -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 or 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyldiimidazole, etc. Compound, or any combination of the above. These diimidazole compounds may be used alone or in combination. The diimidazole compound may preferably be 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole.

Specific examples of the benzophenone compound may include compounds such as benzophenone, 4,4'-bis (dimethylamine) benzophenone or 4,4'-bis (diethylamine) benzophenone. Or any combination of the above compounds. These benzophenone compounds may be used alone or in combination. The benzophenone compound is preferably 4,4'-bis (diethylamine) benzophenone.

Specific examples of the α -diketone compound may include benzodiazone, acetamido, and the like.

Specific examples of the keto alcohol compound may include benzophenone.

Specific examples of the ketol ether compound may include compounds such as bisphenethyl ketone methyl ether, benzophenone diethyl ether, benzophenone isopropyl ether, or any combination thereof.

Specific examples of the above phosphonium oxide may include 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide or bis- (2,6-dimethoxyphenylphosphonium) -2,4,4-tri A compound such as methylphenylphosphine oxide, or any combination thereof.

Specific examples of the quinone compound may include compounds such as anthraquinone, 1,4-naphthoquinone, and the like, or any combination thereof.

Specific examples of the halogen-containing compound may include compounds such as benzamidine chloride, tribromomethyl benzamidine, and tris (trichloromethyl) -s-triazabenzene, or any combination of the foregoing compounds.

Specific examples of the peroxide may include compounds such as di-third butyl peroxide.

Preferably, the other photoinitiator (C-2) may be 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3-substituent] -ethane Keto-1- (O-acetylamoxime), which can be a product manufactured by Ciba Refining Co., Ltd., and the model is OXE-02; 1- [4- (phenylthio) phenyl] -octane -1,2-dione-2- (O-phenylhydrazine oxime), which can be a product manufactured by Ciba Refining Co., Ltd., and the model is OXE-01; 2-methyl-1- (4-methyl Thiophenyl) -2-morpholino-1-acetone, which can be a product manufactured by Ciba Refining Co., Ltd., and the model number is IRGACURE 907 or any combination of the above compounds.

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the photoinitiator (C) is 5 parts by weight to 50 parts by weight, preferably 8 parts by weight to 45 parts by weight, and more preferably 11 parts by weight to 40 parts by weight.

The solvent (D) of the present invention can dissolve the aforementioned alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, and the photoinitiator (C), but it does not generate with the black pigment (E) described later. Reaction, and preferably has appropriate volatility.

Specific examples of the solvent (D) may include alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, diethylene glycol alkyl ethers, other ether compounds, ketone compounds, and alkyl lactate Compounds, other ester compounds, aromatic hydrocarbon compounds, carboxylic acid amine compounds, or any combination thereof. The above-mentioned solvents (D) can be used singly or in combination.

Specific examples of the alkyl glycol monoalkyl ether compound may 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 Compounds such as alcohol 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 any combination thereof.

Specific examples of the alkyl glycol monoalkyl ether acetate compound may include compounds such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, or propylene glycol ethyl ether acetate, or any of the above compounds. combination.

Specific examples of the diethylene glycol alkyl ether may include compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, or diethylene glycol diethyl ether, or any combination of the foregoing compounds.

Specific examples of the other ether compounds may include compounds such as tetrahydrofuran.

Specific examples of the aforementioned ketone compounds may include compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol, or any combination of the foregoing compounds.

Specific examples of the alkyl lactate compound may include compounds such as methyl lactate or ethyl lactate, or any combination of the aforementioned compounds.

Specific examples of the other ester compounds may include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, and 3-methoxy Ethyl propionate, 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 , Isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Compounds such as ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, or ethyl 2-oxybutyrate, or any combination thereof.

Specific examples of the aromatic hydrocarbon compound may include a compound such as toluene, xylene, or any combination thereof.

Specific examples of the carboxylic acid amine compound may be compounds such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, or any combination thereof.

Preferably, the solvent (D) may be propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate.

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the solvent (D) is 1000 parts by weight to 3500 parts by weight, preferably 1200 parts by weight to 3200 parts by weight, and more preferably 1500 parts by weight Parts to 3000 parts by weight.

The black pigment (E) according to the present invention contains a first black pigment (E-1) and may optionally contain a second black pigment component (E-2), which will be described below.

The first black pigment (E-1) is a compound represented by the following formula (E-I), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof.

In formula (EI), R ^1e and R ^6e are each independently a hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ^2e , R ^3e , R ^4e , R ^5e , R ^7e , R ^8e , R ^9e And R ^10e series and all others are hydrogen atom, halogen atom, R ^11e , COOH, COOR ^11e , COO-, CONH ₂ , CONHR ^11e , CONR ^11e R ^12e , CN, OH, OR ^11e , COCR ^11e , OOCNH ₂ , OOCNHR ^11e , OOCNR ^11e R ^12e , NO ₂ , NH ₂ , NHR ^11e , NR ^11e R ^12e , NHCOR ^12e , NR ^11e COR ^12e , N = CH ₂ , N = CHR ^11e , N = CR ^11e R ^12e , SH, SR ^11e , SOR ^11e , SO ₂ R ^11e , SO ₃ R ^11e , SO ₃ H, SO _3- , SO ₂ NH ₂ , SO ₂ NHR ^11e, or SO ₂ NR ^11e R ^12e ; and selected from R ^2e and R ^3e , At least one combination of the group consisting of R ^3e and R ^4e , R ^4e and R ^5e , R ^7e and R ^8e , R ^8e and R ^9e , and R ^9e and R ^10e , is directly bonded to each other, or ^Bonded to each other by bridging with oxygen atom, sulfur atom, NH or NR ^11e ; R ^11e and R ^12e are independently of each other alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, and 2 to 12 carbon atoms Alkenyl, cycloalkenyl having 3 to 12 carbons, or alkynyl having 2 to 12 carbons.

The geometric isomer of the compound represented by the above formula (E-I) has the following core structure (but the substituents in the structural formula are omitted), and the trans-trans isomer may be the most stable.

In the case where the compound represented by the above formula (EI) is anionic, it is preferred to use any known appropriate cation, such as a metal, organic, inorganic, or metal organic cation, specifically, an alkali metal, an alkaline earth metal , Transition metal, primary ammonium, secondary ammonium, trialkylammonium and other tertiary ammonium, tetraalkylammonium and other quaternary ammonium or organometallic complexes to compensate their charges. When the geometric isomer of the compound represented by the formula (E-I) is anionic, the same salt is preferred.

Among the substituents of the above formula (EI) and the definitions of these, the following are preferred in terms of the tendency of the shielding ratio to increase. The reason for this is that the following substituents are considered to have no absorption and do not affect the hue of the pigment. R ^2e , R ^4e , R ^5e , R ^7e , R ^9e, and R ^10e are independent of each other, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom. R ^3e and R ^8e are independent of each other, preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH _{3 ) (C 2 H 5),} N (C 2 H 5) 2, α- naphthyl, β- naphthyl group, SO ₃ H or SO ₃ ^-, more preferably a hydrogen atom or SO ₃ H.

R ^1e and R ^6e are independent of each other, preferably a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom. Preferably, at least one combination selected from the group consisting of R ^1e and R ^6e , R ^2e and R ^7e , R ^3e and R ^8e , R ^4e and R ^9e , and R ^5e and R ^10e is the same, more preferably R ^1e is the same as R ^6e , R ^2e is the same as R ^7e , R ^3e is the same as R ^8e , R ^4e is the same as R ^9e , and R ^5e is the same as R ^10e .

Examples of the alkyl group having 1 to 12 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, 2-methylbutyl, N-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2- Ethylhexyl, nonyl, decyl, undecyl or dodecyl.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, norbornel base, , Norcaryl, caryl, Group, norpinyl, pinyl, 1-adamantyl or 2-adamantyl.

The alkenyl group having 2 to 12 carbon atoms is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butane Alken-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2- 1-butene-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl , Hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexene-1- Radical, 2,4-cyclohexadien-1-yl, 1-pair Ene-8-yl, 4 (10) -thuberene-10-yl, 2-nor En-1-yl, 2,5-nor Dien-1-yl, 7,7-dimethyl-2,4-norbornadien-3-yl or camphenyl.

Examples of the alkynyl group having 2 to 12 carbon atoms are 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, and 2-methyl-3-butyn-2- , 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyne-6-yl, cis-3-methyl-2-pentene-4-yne -1-yl, trans-3-methyl-2-pentene-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyne -9-yl, 1-decyne-10-yl or 1-dodecyne-12-yl.

The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

In a preferred embodiment of the present invention, R ^2e , R ^4e , R ^5e , R ^7e , R ^9e, and R ^{10e of} formula (EI) are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, and R ^3e and R ^8e Independent of each other are hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH ₃ ) (C ₂ H ₅ ), N (C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO _3- , R ^1e is the same as R ^6e , R ^2e is the same as R ^7e , R ^3e is the same as R ^8e , and R ^4e Like R ^9e , R ^5e is the same as R ^10e .

The first black pigment (E-1) is preferably a compound represented by the following formula (E-I-1).

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the first black pigment (E-1) is 40 parts by weight to 180 parts by weight, preferably 45 parts by weight to 160 parts by weight, and More preferably, it is 50 to 140 parts by weight.

When the black photosensitive resin composition of the present invention does not use the first alkali-soluble resin (A-1) and the first black pigment (E-1) at the same time, the black photosensitive resin composition is obtained from the black photosensitive resin composition. The black matrix and the black gap body have defects of development residue.

The second black pigment (E-2) includes but is not limited to (1) black organic pigments: perylene black, cyanine black, aniline black, and the like; (2) From red, blue, green, purple, yellow, cyanine, magenta and other pigments, select two or more pigments to mix to make it a black-colored mixed color organic pigment; (3 ) Shading materials: carbon black, chrome oxide, Iron oxide, titanium black, graphite, and the like.

Specific examples of the carbon black include, but are not limited to, C.I. Pigment black 7, or a product manufactured by Mitsubishi Chemical Corporation, and its model number is MA100, MA220, MA230, MA8, # 970, # 1000, # 2350, or # 2650. The black pigment (E) may be used alone or in combination.

Preferably, the second black pigment (E-2) may be carbon black, or the aforementioned product is MA100 or MA230.

Based on the use amount of the alkali-soluble resin (A) being 100 parts by weight, the use amount of the black pigment (E) is 50 parts by weight to 180 parts by weight, preferably 55 parts by weight to 160 parts by weight, and more preferably 60 parts by weight Parts to 140 parts by weight.

Before the effects of the present invention are not affected, the black photosensitive resin composition of the present invention may be further optionally added with an additive (F). Specific examples of the additive (F) may include a surfactant, a filler, an adhesion promoter, an antioxidant, an anti-agglomerating agent, or a polymerization agent that can increase various properties (for example, mechanical properties) other than the alkali-soluble resin (A). Thing.

Specific examples of the aforementioned surfactant may include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polysiloxane surfactant, a fluorine surfactant, or the above-mentioned surfactant. Any combination of agents.

Specific examples of the surfactant may include, but are not limited to, polyethoxyalkyl ethers such as polyethoxydodecyl ether, polyethoxystearyl ether, or polyethoxy oleyl ether; and polyethylene Polyethoxyalkylphenyl ethers, such as oxyoctylphenyl ether or polyethoxynonylphenyl ether; Polyethylene glycol dilaurate or polyethylene glycol distearate Ethylene glycol diesters; sorbitan fatty acid ester compounds; fatty acid modified polyester compounds; tertiary amine modified polyurethane compounds; or commercially available products. Among them, the commercial product can be a product manufactured by Shin-Etsu Chemical Industry Co., Ltd. and its model is KP; Dow Corning Toray Co., Ltd. The product manufactured by Dow Corning Toray Co., Ltd. and its model is SF-8427; the product manufactured by Gongrongshe Oil Chemical Industry and its model is Polyflow; Tochem Products Co., Ltd. , Ltd.), and its model is F-Top; Dainippon Ink Chemical Industry, and its model is Megafac; Sumitomo 3M, and its model is Fluorade; or Asahi Glass Co., Ltd. , And its model is Asahi Guard or Surflon. These surfactants can be used singly or in combination.

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

Specific examples of the adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane (a product manufactured by Shin-Etsu Chemical Co., Ltd. and its model number is KBM-403), EPPN501H (manufactured by Nippon Kayaku Co., Ltd.), EPIKOTE 152 (manufactured by Shell Chemical Co., Ltd.), 3-epoxypropylene Oxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Compounds such as oxysilane, 3-methylpropionyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane, or any combination thereof.

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

Specific examples of the anti-coagulation agent may include compounds such as sodium polyacrylate.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of fillers, adhesion promoters, antioxidants, anticoagulants, or polymers other than the alkali-soluble resin (A) in the additive (F) It is not more than 10 parts by weight, and preferably not more than 6 parts by weight.

<Preparation of black photosensitive resin composition>

The black photosensitive resin composition is prepared by placing the aforementioned alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the solvent (D), and the black pigment (E). Stir in a stirrer to uniformly mix it into a solution state, and if necessary, add an additive (F). After uniformly mixing, a black photosensitive resin composition in a solution state can be obtained.

Second, the method for preparing the black photosensitive resin composition is not particularly limited. The black pigment (E) can be directly added to a mixture composed of an alkali-soluble resin (A), an ethylenically unsaturated compound (B), a photoinitiator (C), and a solvent (D), and can be dispersed. The photosensitive resin composition in the solution state is formed. Alternatively, a part of the black pigment (E) is first added to a mixture consisting of a part of the alkali-soluble resin (A) and a part of the solvent (D) to form a pigment dispersion. Then, the remaining alkali-soluble resin (A), the ethylenically unsaturated compound (B), the photoinitiator (C), the remaining solvent (D), and the remaining black pigment (E) are added to the foregoing. In the pigment dispersion, a photosensitive resin composition in a solution state is obtained.

The dispersing step of the black pigment (E) can be performed by a mixer such as a beads mill or a roll mill.

<Preparation of Black Matrix / Black Interstitial Body>

The black matrix is obtained by coating the above-mentioned black photosensitive resin composition on a thin film transistor (TFT) substrate or a transparent substrate, and sequentially performing pre-baking treatment, exposure processing, development processing, and post-baking processing. It can be made, the method can be (1) an integrated color filter method, which is a color filter including a black matrix and a pixel layer on the TFT element substrate side; or (2) an integrated black matrix method, The system is only provided with a black matrix on the TFT element substrate side, and the above-mentioned method is not particularly limited. When the film thickness of the obtained black matrix is 2 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.

In addition, the black matrix of the present invention is formed on a TFT substrate, and the method thereof may be (1) an integrated color filter method in which a color filter including a black matrix and a pixel layer is disposed on a TFT element substrate side; Or (2) the integrated black matrix method, in which the black matrix is provided only on the TFT element substrate side, and the above method is not particularly limited.

When the black photosensitive resin composition described above is used to produce a black gap body, it is formed in the same manner as described above, and the thickness of the black gap body is 3 μm. The method for preparing the black matrix / black gap body of the present invention is described in detail below.

First, a black photosensitive resin composition 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 substrates may include thin film transistor (TFT) substrates or transparent substrates for liquid crystal display devices and the like: alkali-free glass, soda lime glass, hard glass (Pales glass), quartz glass, and A transparent conductive film is adhered to the aforementioned glass; or a substrate (for example, a silicon substrate) of a photoelectric conversion device used for a solid-state imaging device or the like.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure. Then, the remaining solvent is removed in a pre-bake manner to form a pre-bake coating film. According to the different types and proportions of the ingredients, the aforementioned conditions for reduced-pressure drying and pre-baking change accordingly. Drying under reduced pressure is generally performed at a pressure of less than 200 mmHg for 1 second to 20 seconds, and the pre-baking system heat-treats the coating film at 70 ° C to 110 ° C for 1 minute to 15 minutes.

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

After the exposure process, the pre-baking coating film after the exposure is immersed in a developing solution at 21 ° C to 25 ° C to remove the pre-baking coating film of the unexposed part, and it can be formed on a substrate. Specific patterns.

The aforementioned developing solution may be sodium hydroxide, potassium hydroxide, sodium carbonate, carbon Sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, Basic compounds such as pyrrole, piperidine or 1,8-diazabicyclo- [5,4,0] -7-undecene. The concentration of the developing solution is generally 0.001 to 10 weight percent, preferably 0.005 to 5 weight percent, and more preferably 0.01 to 1 weight percent.

After the development process, the substrate having a specific pattern is washed with water, and the above substrate is air-dried with compressed air or compressed nitrogen. Then, a post-baking process is performed with a heating device such as a hot plate or an oven to form a black matrix on the substrate. The post-baking temperature is generally 150 ° C to 250 ° C. When the heating device is a hot plate, the heating time is 5 minutes to 60 minutes; when the heating device is an oven, the heating time is 15 minutes to 150 minutes.

<Preparation method of color filter>

The color filter of the present invention is prepared by firstly applying a photosensitive resin composition for a color filter in a solution state by a coating method such as spin coating, cast coating, or roll coating. A coating film is formed on the aforementioned substrate having a black matrix and / or a black spacer.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and the remaining solvent is removed by pre-baking to form a pre-baking coating film. Among them, the conditions for reduced-pressure drying and pre-baking vary according to the type or ratio of each component. Drying under reduced pressure is generally performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the pre-baking system heat-treats the coating film at 70 ° C to 110 ° C for 1 to 15 minutes.

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

After the exposure process, the pre-baking coating film after the exposure is immersed in a developing solution at 21 ° C to 25 ° C to remove the unexposed portions. Pre-baking coating film can be divided into specific patterns on the substrate.

After the development process, the substrate having a specific pattern is washed with water, and the above substrate is air-dried with compressed air or compressed nitrogen. Then, post-baking treatment is performed with a heating device such as a hot plate or an oven. The conditions of the post-bake treatment are as described above, and are not repeated here. Repeat the above steps to form red, green and blue pixel color layers on the substrate.

Next, in a vacuum environment of 220 ° C. to 250 ° C., an ITO protective film (evaporated film) is formed on the surface of the pixel-colored layer by sputtering. If necessary, the ITO protective film is etched and wired, and a liquid crystal alignment film (polyimide for liquid crystal alignment film) is coated on the surface of the ITO protective film to form a color filter having a pixel layer.

<Preparation method of liquid crystal display>

The color filter and the substrate provided with a thin film transistor (TFT) are arranged opposite to each other, and a gap (cell gap) is provided between the two. Then, 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 gap between the substrate surface and the adhesive, and the injection hole is sealed to form a liquid crystal layer. After that, the polarizing plate is disposed 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, so that a liquid crystal display can be manufactured.

The above liquid crystal may be a liquid crystal compound or a liquid crystal composition, which is not particularly limited here, but any liquid crystal compound and liquid crystal composition may be used.

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

In addition to the methods described above, the liquid crystal display device having the resin black matrix of the present invention can also be disclosed in, for example, Japanese Patent Laid-Open No. 4-253028, Japanese Patent Laid-Open No. 7-159772, Japanese Patent Laid-Open No. 9-311348, and the like. It is manufactured by a well-known method. The resin black matrix of the present invention is particularly preferably installed in Willem Den Boer, "Active Matrix Liquid Crystal Displays" (Newnes, 2005, pp. 141-142) and other liquid crystal display devices such as the BOA method, or Japanese Patent Laid-Open No. 10-206888, Japanese Patent Laid-Open No. 2002-277899 In the COA type liquid crystal display device disclosed in Japanese Patent Publication and the like.

The following examples are used to explain the present invention in detail, but it is not meant to limit the present invention to the contents disclosed in these examples.

<Preparation of the first alkali-soluble resin (A-1)>

<Preparation Example A-1-1>

A four-necked conical flask was provided with a stirrer, a thermometer, a condenser tube, and a nitrogen inlet, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) was added to a four-necked conical flask, and the temperature was raised to 100 ° C. Next, 10 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate (hereinafter referred to as DMOA) and 25 parts by weight of methacrylic acid (hereinafter referred to as MAA) ), 40 parts by weight of styrene (hereinafter referred to as SM), 25 parts by weight of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), and 4.5 parts by weight of 2,2'-azobisazo-2- Methylbutyronitrile (hereinafter abbreviated as AMBN) was dissolved in 100 parts by weight of PGMEA, and the mixed solution was dropped into a four-necked conical flask dropwise within 2 hours. After reacting at 100 ° C for 6.5 hours, the alkali-soluble resin (A-1-1) of Synthesis Example A-1-1 was obtained.

<Preparation Examples A-1-2 to A-1-3>

Production Examples A-1-2 to A-1-3 are the same production methods as those of the first alkali-soluble resin in Production Example A-1-1, except that Production Examples A-1-2 to A The 1-3 series changes the type and amount of raw materials in the first alkali-soluble resin, and its formula is shown in Table 1, which is not repeated here.

<Preparation Example A-1-4>

A four-necked conical flask was provided with a stirrer, a thermometer, a condenser tube, and a nitrogen inlet, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol methyl ether acetate (hereinafter PGMEA for short) into a four-necked conical flask, and the temperature was raised to 100 ° C. Next, 10 parts by weight of diethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate (hereinafter referred to as DEOA) and 25 parts by weight of dicyclohexyl-2,2' -[Oxybis (methylene)] bis-2-acrylate (hereinafter referred to as DCOA), 40 parts by weight of acrylic acid (hereinafter referred to as AA), 25 parts by weight of benzyl methacrylate (hereinafter referred to as BzMA ) And 4.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) (hereinafter referred to as ADVN) are dissolved in 100 parts by weight of PGMEA, and this mixed solution is gradually removed within 2 hours. Drop into a four-necked conical flask. After reacting at 100 ° C for 6.5 hours, 1 part by weight of 3,4-epoxycyclohexyl methyl methacrylate (hereinafter referred to as ECMMA) was added to a four-necked conical flask filled with nitrogen, and the temperature was raised to 110 ° C. . After 6 hours of reaction, the alkali-soluble resin (A-1-4) of Synthesis Example A-1-4 was obtained.

<Preparation Examples A-1-5 to A-1-8>

Production Examples A-1-5 to A-1-8 are the same production methods as those of the first alkali-soluble resin in Production Example A-1-4, except that Production Examples A-1-5 to A The -1-8 series changes the type and amount of raw materials in the first alkali-soluble resin, and its formula is shown in Table 1, which is not repeated here.

<Preparation of the second alkali-soluble resin (A-2)>

<Preparation Example A-2-1>

100 parts by weight of a rhenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd. and model ESF-300; epoxy equivalent weight is 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 Parts by weight of 2,6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled to 25 parts by weight per minute, and the temperature was controlled. Maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixed solution having a solid content concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixed solution was dissolved in 25 parts by weight of ethylene glycol ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added at the same time. And heated to 110 ° C to 115 ° C. After the reaction for 2 hours, a second alkali-soluble resin (A-2-1) having an acid value of 98.0 mgKOH / g and a number average molecular weight of 1623 was obtained.

<Preparation example A-2-2>

100 parts by weight of a rhenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd. and model ESF-300; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, Parts by weight of 2,6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled to 25 parts by weight per minute, and the temperature was controlled. Maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixed solution having a solid content concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above-mentioned mixed solution was dissolved in 25 parts by weight of ethylene glycol ether acetate, and 13 parts by weight of benzophenonetetracarboxylic dianhydride was added at the same time. After reacting at 90 ° C to 95 ° C for 2 hours, adding 6 parts by weight of tetrahydrophthalic anhydride and reacting at 90 ° C to 95 ° C for 4 hours, an acid value of 99.0 mgKOH / g and an average number can be obtained. The second alkali-soluble resin (A-2-2) having a molecular weight of 2162.

<Preparation Example A-2-3>

400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd. and model number NC-3000; epoxy equivalent weight is 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, 5 Part by weight of triphenylphosphine and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mgKOH / g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a second alkali-soluble resin (A having an acid value of 102 mgKOH / g and a number average molecular weight of 2589. -2-3).

<Preparation of other alkali-soluble resins (A-3)>

<Preparation Example A-3-1>

1 part by weight of 2,2'-azobisisobutyronitrile, 240 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, 15 parts by weight of styrene, and 35 parts by weight of methyl Benzoyl acrylate, 10 parts by weight of glycerol monomethacrylate and 20 parts by weight of nitrogen-phenylmaleimide were placed in a round bottom flask equipped with a stirrer and a condenser, and the inside of the flask was placed After filling with nitrogen, the temperature was gradually stirred to 80 ° C., and the reactants were uniformly mixed and polymerized for 4 hours. Thereafter, the temperature was further increased to 100 ° C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added for polymerization for 1 hour to obtain another alkali-soluble resin (A-3-1).

<Preparation example A-3-2>

2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl ether, 15 parts by weight of methacrylic acid, 15 parts by weight of ethyl 2-hydroxyacrylate, and 70 parts by weight of The benzyl methacrylate was placed in a round-bottomed flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen. After that, it was slowly stirred and heated to 80 ° C, so that the reactants were uniformly mixed and polymerized. Reaction for 3 hours. Thereafter, the temperature was further increased to 100 ° C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added for polymerization for 1 hour to obtain another alkali-soluble resin (A-3-2).

<Preparation example A-3-3>

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 is precipitated with ultrapure water, filtered, and dried to obtain another alkali-soluble resin (A-3-3).

<Example>

<Preparation of black photosensitive resin composition>

<Example 1>

60 parts by weight of the aforementioned alkali-soluble resin A-1-1, 40 parts by weight of the aforementioned alkali-soluble resin A-3-1, and 60 parts by weight of EO modified trimethylolpropyl triacrylate (hereinafter referred to as B -1), 10 parts by weight of 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3-substituent] -ethanone-1- (O-ethyl Fluorenyl oxime) (hereinafter referred to as C-2-1), 70 parts by weight of the first black pigment (E-1-1), and 10 parts by weight of the second black pigment (trade name MA220; hereinafter referred to as E-2) -1) After adding to 1200 parts by weight of propylene glycol methyl ether acetate (hereinafter abbreviated as D-1), and stirring it with a shaking type stirrer, the black photosensitivity of Example 1 can be obtained Resin composition. The obtained black photosensitive resin composition was evaluated by the following evaluation method of development residue, and the obtained results are shown in Table 2.

<Examples 2 to 16 and Comparative Examples 1 to 5>

Examples 2 to 16 and Comparative Examples 1 to 5 use the same manufacturing method as that of the black photosensitive resin composition of Example 1, except that Example 2 is different 16 to 16 and Comparative Examples 1 to 5 change the types and amounts of raw materials in the black photosensitive resin composition, and their formulations and evaluation results are shown in Tables 2 and 3, respectively, and are not repeated here.

<Comparative Example 6>

8 parts by weight of the aforementioned alkali-soluble resin A-3-3 and 20 parts by weight of a black pigment (trade name MA100) were added to 72 parts by weight of propylene glycol monomethyl ether acetate and ground with zirconia beads. After being dispersed by a mill type disperser, a black pigment dispersion liquid can be obtained.

Next, 100 parts by weight of the aforementioned black pigment dispersion liquid, 5 parts by weight of a monomer of the following formula, 5 parts by weight of dipentaerythritol pentaacrylate, 1.6 parts by weight of a photoinitiator CGI242 (manufactured by Ciba Specialty Chemicals), and 3.2 parts by weight were taken. The black photosensitive resin composition of Comparative Example 6 was prepared by adding 5 parts by weight of a photoinitiator CGI113 (manufactured by Ciba Specialty Chemicals) to 55.2 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA). The obtained black photosensitive resin composition was evaluated by the following evaluation method of development residue, and the evaluation result was x.

<Evaluation method>

<Development residue>

The black photosensitive resin compositions of the above Examples and Comparative Examples were applied to two sets of 100 mm × 100 mm glass substrates by spin coating. Then, it is dried under reduced pressure for about 30 seconds under a pressure of about 100 millimeters of mercury (mmHg). Next, the two sets of glass substrates were pre-baked at 80 ° C. for 3 minutes to form a pre-baked coating film with a film thickness of 2.5 μm. The two sets of pre-baking coating films were placed under a mask with different line widths, and the pre-baking coating films were irradiated with an exposure amount capable of forming a line width of 20 μm , and then the two sets of pre-baking coating films were dipped separately In a developer (0.04% potassium hydroxide) at 23 ° C for 40 and 80 seconds to remove the part of the pre-baked coating film that is not irradiated with ultraviolet light, and then wash it with pure water, and then carry out in an oven at 230 ° C Post-bake for 60 minutes. Next, use a microscope (manufactured by Nikon, model Eclipse 50i) and a scanning electron microscope (manufactured by Hitachi, model S-3000N) to observe whether there are development residues on the edges of the two groups of patterns. The evaluation methods are shown in Table 4:

The above embodiments are only for explaining the principle of the present invention and its effects, but not for limiting the present invention. Modifications and changes made by those skilled in the art to the above embodiments still do not violate the spirit of the present invention. The scope of rights of the present invention should be listed in the scope of patent application described later.

Claims (10)

A black photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment (E), wherein : The alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1) and a second alkali-soluble resin (A-2), wherein the first first alkali-soluble resin (A-1) has the formula (I) Structure shown: In the formula (I), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent; and the first alkali-soluble resin (A-1) has at least An ethylenically unsaturated group, which is prepared by reacting a first mixture, the first mixture is composed of an ethylenically unsaturated monomer (a-1-1) having the following formula (I-1), A copolymer obtained by copolymerizing an ethylenically unsaturated monomer (a-1-2) having at least one carboxylic acid or carboxylic anhydride and other copolymerizable ethylenically unsaturated monomer (a-1-3) , And then react with the ethylenically unsaturated monomer (a-1-4) with epoxy group to obtain: In the formula (I-1), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent; the second alkali-soluble resin (A-2) It is obtained by polymerizing a second mixture, which contains an epoxy compound (a-2-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. (a-2-2), wherein the epoxy compound (a-2-1) having at least two epoxy groups has a compound represented by formula (III) or formula (IV) or a combination thereof: In formula (III), B ₁ , B ₂ , B _3, and B ₄ are the same or different, and B ₁ , B ₂ , B _3, and B ₄ each represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 5 An alkyl group, an alkoxy group having 1 to 5 carbon atoms, an aromatic group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms; In formula (IV), B ₅ to B ₁₈ are the same or different, B ₅ to B ₁₈ are 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 a represents an integer from 0 to 10. And the black pigment (E) includes a first black pigment (E-1), wherein the first black pigment (E-1) includes a compound having a formula (EI), a geometric isomer thereof, and a salt thereof; , Or its geometric isomer salt: In formula (EI), R ^1e and R ^6e are each independently a hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ^2e , R ^3e , R ^4e , R ^5e , R ^7e , R ^8e , R ^9e And R ^10e series and all others are hydrogen atom, halogen atom, R ^11e , COOH, COOR ^11e , COO-, CONH ₂ , CONHR ^11e , CONR ^11e R ^12e , CN, OH, OR ^11e , COCR ^11e , OOCNH ₂ , OOCNHR ^11e , OOCNR ^11e R ^12e , NO ₂ , NH ₂ , NHR ^11e , NR ^11e R ^12e , NHCOR ^12e , NR ^11e COR ^12e , N = CH ₂ , N = CHR ^11e , N = CR ^11e R ^12e , SH, SR ^11e , SOR ^11e , SO ₂ R ^11e , SO ₃ R ^11e , SO ₃ H, SO _3- , SO ₂ NH ₂ , SO ₂ NHR ^11e, or SO ₂ NR ^11e R ^12e ; and selected from R ^2e and R ^3e , At least one combination of the group consisting of R ^3e and R ^4e , R ^4e and R ^5e , R ^7e and R ^8e , R ^8e and R ^9e , and R ^9e and R ^10e , is directly bonded to each other, or ^Bonded to each other by bridging with oxygen atom, sulfur atom, NH or NR ^11e ; R ^11e and R ^12e are independently of each other alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and 2 to 12 carbon atoms Alkenyl, cycloalkenyl having 3 to 12 carbons or alkynyl having 2 to 12 carbons; The use amount of the alkali-soluble resin (A) is 100 parts by weight, the use amount of the first alkali-soluble resin (A-1) is 45 parts by weight to 95 parts by weight, and the second alkali-soluble resin (A-2) ) Is used in an amount of 5 to 55 parts by weight. The black photosensitive resin composition according to claim 1, wherein the photoinitiator (C) includes a first photoinitiator (C-1) having a structure represented by formula (CI): In Formula (CI), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen, Or COR ₁₆ ; and R ₃ and R ₄ or R ₅ and R ₆ together are ; R ₉ , R ₁₀ , R _11, and R ₁₂ are each independently hydrogen; X is CO or a direct bond; R ₁₃ is C ₁ -C ₂₀ alkyl, which is unsubstituted; or R ₁₃ is C ₂ -C ₁₂ alkenyl, which is interspersed with one or more O, wherein the interspersed C ₂ -C ₁₂ alkenyl is substituted with one or more halogens; R ₁₄ is C ₁ -C ₂₀ alkyl, which is unsubstituted ; R ₁₅ is a C ₆ -C ₂₀ aryl group, which is substituted with one or more of the following groups: OR ₁₇ ; or R ₁₅ is a C ₁ -C ₂₀ alkyl group, the C ₁ -C ₂₀ alkyl group is unsubstituted Substituted; or R ₁₅ is unsubstituted naphthylmethyl; R ₁₆ is C ₆ -C ₂₀ aryl, which is substituted with one or more C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl Unsubstituted; R ₁₇ is C ₁ -C ₂₀ alkyl, which is substituted with one or more of the following: halogen; provided that at least one group is present in the molecule . The black photosensitive resin composition according to claim 1, wherein the used amount of the alkali-soluble resin (A) is 100 parts by weight, and the used amount of the ethylenically unsaturated compound (B) is 40 to 200 parts by weight. Parts by weight; the use amount of the light initiator (C) is 5 parts by weight to 50 parts by weight; the use amount of the solvent (D) is 1,000 parts by weight to 3500 parts by weight; and the use amount of the black pigment (E) It is 50 to 180 parts by weight. The black photosensitive resin composition according to claim 2, wherein the use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the photoinitiator (C-1) is 2 to 20 parts by weight . The black photosensitive resin composition according to claim 1, wherein the used amount of the black soluble resin (A) is 100 parts by weight, and the used amount of the black pigment (E-1) is 40 to 180 parts by weight. A black gap body is formed by subjecting the black photosensitive resin composition according to any one of claims 1 to 5 to a pre-baking process, an exposure process, a developing process, and a post-baking process. A black matrix is formed by subjecting the black photosensitive resin composition according to any one of claims 1 to 5 to a pre-baking process, an exposure process, a developing process, and a post-baking process. A color filter comprising a black gap body according to claim 6. A color filter comprising a black matrix according to claim 7. A liquid crystal display including a color filter according to any one of claims 8 to 9.