TW201736968A - Negative photosensitive resin composition and application thereof - Google Patents

Abstract

The present invention relates to a negative photosensitive resin composition and an application thereof. The negative photosensitive resin composition includes a pigment (A), an alkali-soluble resin (B), a compound having an unsaturated ethylenically group (C), a photoinitiator (D), a compound (E) and a solvent (F). The photoinitiator(D) and the compound (E) have specific structures, respectively, thereby increasing sputtering resistence of a color filter made by such negative photosensitive resin composition.

Description

Negative photosensitive resin composition and application thereof

The present invention relates to a photosensitive resin composition, and more particularly to a negative photosensitive resin composition having good sputter resistance and an application thereof.

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

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

For example, those disclosed in Japanese Laid-Open Patent Publication No. Hei 6-95211, No. Hei 8-183819, for example, A copolymer obtained by polymerizing (meth)acrylic acid as a monomer component, which is an alkali-soluble resin of a photosensitive resin.

However, in the manufacturing process of the color filter, it is necessary to undergo multiple heat treatment steps, such as red (Red), green (green) and blue (Blue), and the like, after the formation of the pixel colored layer pattern is post-bake. a step of forming a transparent conductive film (ITO film), etc., which are generally required to be operated at a high temperature of 200 ° C or higher, but the above-mentioned photosensitive resin is easily heated at 180 ° C for about 1 hour. Pigment aggregated particles are generated in the pigmented layer (generally, the pigment agglomerated particles have a particle diameter of from 1 μm to 10 μm), and the heat resistance of the pixel colored layer is also poor.

In order to improve the above-mentioned problem, a photosensitive resin composition comprising a polymer obtained by polymerizing an unsaturated monomer of a carboxylic acid group and a monomer containing a glycidyl group is disclosed in JP-A-2001-075273. An alkali-soluble resin of a photosensitive resin. However, in the sputtering forming process of the subsequent transparent conductive film, the color filter obtained by using the photosensitive resin composition of the prior art described above has a problem of poor sputtering resistance, especially the pixel coloring layer is After being subjected to the sputtering process of a strong electron beam, problems such as chromaticity loss are liable to occur.

In view of the above, there is a need to develop a negative photosensitive resin composition to overcome problems such as poor sputtering resistance and chromaticity loss of a conventional photosensitive resin composition.

Therefore, an aspect of the present invention provides a negative photosensitive resin composition comprising a pigment (A) and an alkali soluble Resin (B), compound (C) having ethylenically unsaturated group, photoinitiator (D), compound (E) and solvent (F), and the negative photosensitive resin composition has better resistance to splashing Plating.

Another aspect of the present invention provides a method of producing a color filter comprising the step of forming a pixel colored layer using the negative photosensitive resin composition described above.

Still another aspect of the present invention is to provide a color filter which is produced by the aforementioned method.

Still another aspect of the present invention provides a liquid crystal display device comprising the above-described color filter.

According to the above aspect of the invention, a negative photosensitive resin composition is proposed. The photosensitive resin composition contains the pigment (A), the alkali-soluble resin (B), the compound (C) having an ethylenically unsaturated group, the photoinitiator (D), the compound (E), and the solvent (F), and the following Analysis of it.

It is to be noted that “and/or” or “or/and” as used in the context of the present invention means that not only one of the defined substituents but also a plurality of defined substitutions may be present. Base, a mixture of different substitutes (substituents).

As used herein, "at least" means one or more, such as one or both or three, preferably one or both.

Throughout this specification and the claims below, the words "comprise" or variant (eg, "comprises" or "comprising") are understood to include the integer or Step or integer group or group of steps, but does not exclude either His integer or step or integer group or step group. The term "(meth)acrylate" as used in the context of the present invention is intended to mean the acrylate and the corresponding methacrylate.

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

Pigment (A)

The pigment (A) of the present invention may be an inorganic pigment, an organic pigment or a combination thereof.

The inorganic pigment may be a metal compound such as a metal oxide or a metal salt, which may be selected from the group consisting of oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, and antimony, and the foregoing. A composite oxide of a metal and a metal salt.

The organic pigment may be selected from CI Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81 , 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139 , 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17 , 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 14, 19 , 23, 29, 32, 33, 36, 37, 38, 39, 40, 50; CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 21, 22, 60, 61, 64, 66; CI Pigment Green 7, 36, 37, 42, 58; CI Pigment Brown 23, 25, 28; and CI Pigment Black 1, 7. The above organic pigments may be used singly or in combination of plural kinds.

In one embodiment, the pigment (A) preferably has an average particle diameter of from 10 nm to 200 nm, more preferably from 20 nm to 150 nm, still more preferably from 30 nm to 130 nm.

The pigment (A) is used in an amount of 50 parts by weight to 500 parts by weight, preferably 60 parts by weight to 450 parts by weight, based on the amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight, and more preferably 70% by weight. Parts by weight to 400 parts by weight.

If necessary, the pigment (A) can also optionally use a dispersing agent such as a cationic, anionic, nonionic, amphoteric, polyoxyalkylene or fluorine surfactant.

The aforementioned surfactant may include, but is not limited to, polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether; Polyethylene oxide alkyl phenyl ether surfactants such as polyethylene oxide octyl phenyl ether and polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate and polyethylene glycol Polyethylene glycol diester surfactant such as fatty acid ester; sorbitan fatty acid ester surfactant; fatty acid modified polyester surfactant; tertiary amine modified polyurethane interface Active agent; manufactured by Shin-Etsu Chemical Co., Ltd. and model KP; manufactured by Toray Dow Corning Silicon and model SF-8427; manufactured by Kyoritsu Oil & Fat Chemical Industry, model of Polyflow; Dekm Corporation Produced by Tochem Products Co., Ltd., and model F-Top; manufactured by Dainippon Ink Chemical Industry, and model of Megafac; manufactured by Sumitomo 3M and modeled by Fluorad; manufactured by Asahi Glass, and model number It is a product of Asahi Guard and Surflon. The surfactants may be used singly or in combination of plural kinds.

Alkali soluble resin (B)

The alkali-soluble resin (B) of the present invention may comprise a first alkali-soluble resin (B-1) and a second alkali-soluble resin (B-2).

First alkali soluble resin (B-1)

The first alkali-soluble resin (B-1) can be obtained by a polymerization reaction of a mixture, and the mixture contains an epoxy compound (b-1-1) having at least two epoxy groups and having at least one carboxylic acid group. And at least one ethylenically unsaturated group compound (b-1-2). Secondly, the mixture can also be selectively The carboxylic anhydride compound (b-1-3) and/or the compound (b-1-4) having an epoxy group are contained.

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

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

In the formula (III-1-1), Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different, respectively, and Y ₁ , Y ₂ , Y ₃ and Y ₄ may represent a hydrogen atom, a halogen atom, or a carbon number. An alkyl group of 1 to 5, 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.

The epoxy compound (b-1-1) having at least two epoxy groups as shown in the above formula (III-1-1) may contain bisphenol fluorene and halogenated propylene oxide (epihalohydrin) The epoxy group-containing bisphenol quinone type compound obtained by the reaction, but is not limited thereto.

Specific examples of the above bisphenol quinone type compound may include, but are not limited to, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis (4) -9-9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)indole [9,9 -bis(4-hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene[9,9-bis(4-hydroxy-3-fluorophenyl)fluorene], 9,9-bis(4-hydroxy-3-methoxy 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9-bis (4-hydroxy-3,5-dimethylphenyl)fluorene],9,9-bis(4-hydroxy-3,5-dichlorophenyl)indole [9,9-bis(4-hydroxy-3,5-dichlorophenyl) a compound such as fluorene], 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene.

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

The epoxy group-containing bisphenol quinoid compound obtained by reacting the bisphenol quinoid compound with the halogenated propylene oxide may include, but is not limited to: (1) manufactured by Nippon Steel Chemical Co., Ltd. Products such as ESF-300, etc.; (2) Products manufactured by Osaka Gas Co., Ltd.: PG-100, EG-210, etc.; (3) SMS technology Commercial products manufactured by (S.M.S. Technology Co., Ltd.): for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

Next, the epoxy compound (b-1-1) having at least two epoxy groups may have a structure represented by the following formula (III-1-2):

In the formula (III-1-2), Y ₅ to Y ₁₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and g represents 0 to An integer of 10.

The epoxy compound (b-1-1) having at least two epoxy groups represented by the above formula (III-1-2) is, for example, by the following formula (III- in the presence of an alkali metal hydroxide) The compound shown in 1-2-1) is reacted with a halogenated propylene oxide to obtain:

In the formula (III-1-2-1), Y ₅ to Y ₁₈ g of well defined lines, respectively of formula (III-1-2) Y ₅ to Y ₁₈ g of the same as defined in the, and are not further Narration.

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

In the formula (III-1-2-2), Y ₁₉ and Y ₂₀ each may be the same or different hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms. Y ₂₁ and Y ₂₂ are the same or different halogen atoms, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, respectively. Preferably, the aforementioned halogen atom may be, for example, chlorine or bromine, and the aforementioned alkyl group may be, for example, a methyl group, an ethyl group or a third butyl group, and the aforementioned alkoxy group may be, for example, a methoxy group or an ethoxy group.

Specific examples of the above phenols may include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butanol. (t-butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol (vinylphenol), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The above phenols may be used singly or in combination of plural kinds.

The compound represented by the above formula (III-1-2-2) is used in an amount of 1 mol, and the phenol may be used in an amount of 0.5 mol to 20 mol, and preferably 2 mol to 15 mol. ear.

Specific examples of the above acid catalyst may include, but are not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminium chloride. Chloride), zinc chloride, etc., of which p-toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. The above acid catalysts may be used singly or in combination of plural kinds.

Further, the amount of the acid catalyst to be used is not particularly limited, but the amount of the compound represented by the above formula (III-1-2-2) is preferably 100% by weight, and the amount of the acid catalyst used is preferably 0.1% by weight to 30% by weight.

The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Next, specific examples of the above organic solvent may include, but are not limited to, toluene, xylene, or methyl isobutyl ketone. The above organic solvents may be used singly or in combination of plural kinds.

The organic solvent is used in an amount of from 50% by weight to 300% by weight based on the total amount of the compound and the phenol used as shown in the formula (III-1-2-2), and preferably 100 parts by weight. Percentage to 250 weight percent. Further, the above condensation reaction may be carried out at a temperature of from 40 ° C to 180 ° C, and the operation time of the condensation reaction may be from 1 hour to 8 hours.

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

Specific examples of the above 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 of the above. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The above dehydrohalogenation reaction may be carried out at a temperature of from 20 ° C to 120 ° C and may be operated for a period of from 1 hour to 10 hours.

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

Before the dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or the like may be added. The ammonium salt is used as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is carried out at a temperature of 20 ° C to 120 ° C for 1 hour. 10 hours for the dehydrohalogenation reaction.

The halogenated propylene oxide may be used in an amount of 1 equivalent to 20 equivalents, and preferably 2 equivalents, based on the total equivalent of the hydroxyl group in the compound represented by the above formula (III-1-2-1). 10 equivalents. The alkali metal hydroxide added in the above dehydrohalogenation reaction may be used in an amount of from 0.8 to 15 equivalents, based on the total equivalent of the hydroxyl group in the compound represented by the above formula (III-1-2-1) being 1 equivalent. And preferably it is from 0.9 equivalents to 11 equivalents.

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

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

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the solution after the dehydrohalogenation reaction may be added to a solvent such as toluene or methyl isobutyl ketone, and a base such as sodium hydroxide or potassium hydroxide may be added. The metal hydroxide aqueous solution is again subjected to a dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total hydroxyl group equivalent weight in the compound represented by the above formula (III-1-2-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol. And preferably it is from 0.05 moles to 0.2 moles. Further, the above dehydrohalogenation reaction may be carried out at a temperature ranging from 50 ° C to 120 ° C, and its operation time is from 0.5 hours to 2 hours.

After completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, a solvent such as toluene or methyl isobutyl ketone may be distilled off by heating and pressure reduction to obtain a ring having at least two epoxy groups as shown in the formula (III-1-2). Oxygen compound (b-1-1). The epoxy compound (b-1-1) having at least two epoxy groups represented by the above formula (III-1-2) may include, but is not limited to, a trade name of NC-3000, A product manufactured by Nippon Kayaku Co., Ltd., such as NC-3000H, NC-3000S, and NC-3000P.

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

The aforementioned compound (b-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group may, for example, be selected from the group consisting of (1) to (3): (1) acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate, 2 -Methacrylic acid oxiranium adipic acid, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl Maleic acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene oxime Propyl tetrahydrophthalic acid, 2-methylpropenyl propyl phthalate, 2-methylpropenyl butyl phthalate or 2-methyl propylene oxybutyl phthalate Formic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate 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 obtained by reacting a (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group-containing (meth) acrylate includes, but not limited to, 2-hydroxyethyl acrylate; 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate], 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate ], 4-hydroxybutyl acrylate [(4-hydroxybutyl)acrylate], 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate. Further, the carboxylic anhydride compound described herein may be the same as the carboxylic anhydride compound (b-1-3) contained in the mixture of the first alkali-soluble resin (B-1) described below, and thus will not be described herein.

Carboxylic anhydride compound (b-1-3)

The aforementioned mixture may also optionally contain a carboxylic anhydride compound (b-1-3).

The above carboxylic anhydride compound (b-1-3) may be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, and 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 a dicarboxylic anhydride compound such as 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl ether A tetracarboxylic anhydride compound such as tetracarboxylic acid dianhydride.

Compound having epoxy group (b-1-4)

The above epoxy group-containing compound (b-1-4) may, for example, be selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and a glycidyl ether compound having an unsaturated group. A group consisting of an epoxy group-containing unsaturated compound or any combination of the above. The glycidyl ether compound having an unsaturated group may include, but is not limited to, manufactured by Nagase Chemical Co., Ltd., and its model numbers are Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, and Denacol EX- 146, Denacol EX-171 or Denacol EX-192 and other products.

Preparation of first alkali soluble resin (B-1)

The first alkali-soluble resin (B-1) may have an epoxy compound (b-1-1) having at least two epoxy groups as shown in the formula (III-1-1) and having at least one carboxylic acid group and At least one ethylenically unsaturated group compound (b-1-2) is subjected to polymerization to form a reaction product having a hydroxyl group. Next, the carboxylic anhydride compound (b-1-3) is added and the reaction is carried out. The equivalent weight of the acid group based on the above-mentioned reaction product having a hydroxyl group is 1 equivalent, and the equivalent weight of the acid anhydride group contained in the carboxylic anhydride compound (b-1-3) may preferably be 0.4 equivalent to 1 equivalent, and more preferably 0.75 equivalent to 1 equivalent. When a plurality of carboxylic anhydride compounds (b-1-3) are used, such carboxylic anhydride compounds (b-1-3) may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (b-1-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is preferably from 1/99 to 90/ 10, and more preferably 5/95 to 80/20. Further, the above reaction may be operated at a temperature ranging from 50 ° C to 130 ° C.

The first alkali-soluble resin (B-1) may be an epoxy compound (b-1-1) having at least two epoxy groups as shown in the formula (III-1-2) and having at least one carboxylic acid group and At least one ethylenically unsaturated group compound (b-1-2) is reacted to form a reaction product having a hydroxyl group. Next, a carboxylic anhydride compound (b-1-3) and/or a compound (b-1-4) having an epoxy group are added, and a polymerization reaction is carried out. The epoxy group-containing epoxy compound (b-1-1) having at least two epoxy groups represented by the formula (III-1-2) has a total equivalent weight of 1 equivalent, and the above has at least one carboxylic acid group and The acid value equivalent of at least one ethylenically unsaturated group compound (b-1-2) may preferably be from 0.8 equivalents to 1.5 equivalents, and more preferably from 0.9 equivalents to 1.1 equivalents. The carboxylic anhydride compound (b-1-3) may be used in an amount of from 10 mole percent to 100 mole percent, preferably from 20 mole percent, based on the total amount of hydroxyl groups of the above reaction product having a hydroxyl group of 100 mole percent. A percentage of 100 moles, and more preferably from 30 mole percent to 100 mole percent.

In the preparation of the above first alkali-soluble resin (B-1), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The above reaction catalyst may be used singly or in combination, and the above reaction catalyst may include, but is not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine. (triethanolamine), tetramethyl ammonium chloride, benzyltriethyl ammonium chloride, and the like. The total amount of the epoxy compound (b-1-1) having at least two epoxy groups and the compound (b-1-2) having at least one carboxylic acid group and at least one ethylenic unsaturated group is 100. Weight, reverse The amount of the catalyst to be used is preferably from 0.01 part by weight to 10 parts by weight, and more preferably from 0.3 part by weight to 5 parts by weight.

Further, in order to control the degree of polymerization, a polymerization inhibitor (polymerizatioh inhibitor) is usually added to the reaction solution. The above polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di- T-butyl-p-cresol) or phenothiazine. In general, the above polymerization inhibitors may be used singly or in combination of plural kinds. The total amount of the epoxy compound (b-1-1) having at least two epoxy groups and the compound (b-1-2) having at least one carboxylic acid group and at least one ethylenic unsaturated group is 100. The polymerization inhibitor may preferably be used in an amount of from 0.01 part by weight to 10 parts by weight, and more preferably from 0.1 part by weight to 5 parts by weight, per part by weight.

In the preparation of the first alkali-soluble resin (B-1), a polymerization solvent can be used as necessary. Specific examples of the polymerization reaction solvent include alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; and ketones such as methyl ethyl ketone or cyclohexanone. a compound; an aromatic hydrocarbon compound such as toluene or xylene; a celecin compound such as cellosolve or butyl cellosolve; carbitol or butyl carbitol (butyl) Carbitol); propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as di(propylene glycol) methyl ether [poly(poly(propylene glycol) methyl ether] Propylene glycol) alkyl ether] compound; ethyl acetate, butyl acetate, B Acetate compound such as ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate; alkyl lactate such as ethyl lactate or butyl lactate (alkyl lactate) compounds; or dialkyl glycol ethers; or ethyl 3-ethoxypropionate. The above polymerization solvent can be generally used singly or in combination of plural kinds. Further, the acid value of the above first alkali-soluble resin (B-1) is preferably from 50 mgKOH/g to 200 mgKOH/g, and more preferably from 60 mgKOH/g to 150 mgKOH/g.

Further, the first alkali-soluble resin (B-1) is measured by a gel permeation chromatography (GPC), and the number average molecular weight in terms of polystyrene is generally from 500 to 10,000, preferably 800. To 8,000, and more preferably 1,000 to 6,000.

In a specific example of the present invention, the total amount of the alkali-soluble resin (B) used is 100 parts by weight, and the first alkali-soluble resin (B-1) is used in an amount of 5 parts by weight to 100 parts by weight, preferably 10 parts by weight to 90 parts by weight, and more preferably 20 parts by weight to 80 parts by weight.

When the alkali-soluble resin (B) of the present invention contains the first alkali-soluble resin (B-1), the color filter formed of the negative-type photosensitive resin composition obtained has the advantage of better sputter resistance. .

Second alkali soluble resin (B-2)

The alkali-soluble resin (B) of the present invention may comprise a second alkali-soluble resin (B-2), wherein the second alkali-soluble resin (B-2) has an ethylenically unsaturated group, and the second alkali-soluble resin ( B-2) may have a structure represented by the following formula (III-2):

In the formula (III-2), Q ₁ and Q ₂ each independently represent a hydrogen atom or a halogen atom, wherein Q ₁ and Q ₂ are the same or different; and Q ₃ , Q ₄ and Q ₅ each independently represent a hydrogen atom, a halogen atom or an alkyl group, wherein Q ₃ , Q ₄ and Q ₅ are the same or different; and Q ₆ and Q ₇ each independently represent a hydrogen atom or an alkyl group, wherein Q ₆ and Q ₇ are the same or different; and e represents 1 An integer of up to 2.

The second alkali-soluble resin (B-2) may be an ethylenically unsaturated monomer (b-2-1) represented by the following formula (III-2-1), having one or more carboxylic acids or carboxylic anhydrides. Copolymerization of ethylenically unsaturated monomer (b-2-2) and other copolymerizable ethylenically unsaturated monomer (b-2-3), followed by ethylenically unsaturated monomer having epoxy group ( B-2-4) obtained by reaction.

In one embodiment, the second alkali-soluble resin (B-2) is an ethylenically unsaturated monomer (b-2-1) represented by the following formula (III-2-1), having one or one The ethylenically unsaturated monomer (b-2-2) of the above carboxylic acid or carboxylic anhydride is subjected to double bond copolymerization with other copolymerizable ethylenically unsaturated monomer (b-2-3) to form a polymerization. And wherein the side chain of the polymer has a carboxylic acid group. Then, the carboxylic acid group in the side chain of the polymer and the ethylene having an epoxy group The unsaturation monomer (b-2-4) is subjected to an addition reaction to prepare the second alkali-soluble resin (B-2).

In another embodiment, the second alkali-soluble resin (B-2) is an ethylenically unsaturated monomer (b-2-1) represented by the following formula (III-2-1). The polymerized ethylenically unsaturated monomer (b-2-3) is subjected to double bond copolymerization with an ethylenically unsaturated monomer (b-2-4) having an epoxy group to form a polymer, wherein the polymerization is carried out. The side chain of the substance has an epoxy group. Then, the epoxy group in the side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (b-2-2) having one or more carboxylic acids or carboxylic anhydrides to prepare the second base. Soluble resin (B-2).

In still another embodiment, the second alkali-soluble resin (B-2) is an ethylenically unsaturated monomer (b-2-1) represented by the following formula (III-2-1). The polymerized ethylenically unsaturated monomer (b-2-3) is subjected to double bond copolymerization with an ethylenically unsaturated monomer (b-2-4) having an epoxy group to form a polymer, wherein the polymerization is carried out. The side chain of the substance has an epoxy group. Then, the epoxy group in the side chain of the polymer is subjected to an addition reaction with the ethylenically unsaturated monomer (b-2-2) having one or more carboxylic acids or carboxylic anhydrides, and further subjected to an acid anhydride compound. The second alkali-soluble resin (B-2) is obtained by a half esterification reaction.

Ethylene unsaturated monomer (b-2-1) as shown in formula (III-2-1)

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

In the formula (III-2-1), Q ₁ and Q ₂ each independently represent a hydrogen atom or a halogen atom, wherein Q ₁ and Q ₂ are the same or different; and Q ₃ , Q ₄ and Q ₅ each independently represent hydrogen. An atom, a halogen atom or an alkyl group, wherein Q ₃ , Q ₄ and Q ₅ are the same or different; and Q ₆ and Q ₇ each independently represent a hydrogen atom or an alkyl group, wherein Q ₆ and Q ₇ are the same or different; Represents an integer from 1 to 2.

The ethylenically unsaturated monomer (b-2-1) represented by the formula (III-2-1) may include, but is not limited to, N-benzyl maleimide, N-( 1-phenylethyl)N-(1-phenylethyl)maleimide, N-(2-phenylethyl)maleimide, 2 ,3-Dichloro-N-benzylmaleimide, 2,3-dichloro-N-(1-phenylethyl)maleimide, 2,3-dichloro-N-(2 -phenylethyl)maleimide, 2,3-dichloro-N-(2-chlorobenzyl)maleimide, 2,3-dichloro-N-(4-chlorobenzyl) Maleimide, 2,3-dichloro-N-(2-methylbenzyl)maleimide, 2,3-dichloro-N-(4-methylbenzyl)malaya Amine, 2,3-dichloro-N-(2,4-dimethylbenzyl)maleimide, 2,3-dichloro-N-(3,4-dimethylbenzyl)male Yttrium, 2,3-dichloro-N-(2,4-dichlorobenzyl)maleimide or 2,3-dichloro-N-(2,4,6-trimethylbenzyl ) Malay yttrium.

Preferably, the ethylenically unsaturated monomer (b-2-1) as shown in formula (III-2-1) may be selected from N-benzyl maleimide, N-(1-benzene). Base ethyl) maleimide, N-(2-phenylethyl)maleimide, 2,3-dichloro-N-(2-phenylethyl)maleimide, 2 ,3-dichloro-N-(2,4-dimethylbenzyl)maleimide, 2,3-dichloro-N-(2,4-dichlorobenzyl)maleimide or 2,3-Dichloro-N-(2,4,6-trimethylbenzyl)maleimide.

In a specific example of the present invention, the ethylenic unsaturated monomer (b-2-1) represented by the formula (III-2-1), and the ethylenicity having one or more carboxylic acids or carboxylic anhydrides are not The total amount of the saturated monomer (b-2-2) and other copolymerizable ethylenically unsaturated monomer (b-2-3) is 100 parts by weight, as shown in the formula (III-2-1). The ethylenically unsaturated monomer (b-2-1) may be used in an amount of 5 parts by weight to 50 parts by weight, preferably 10 parts by weight to 45 parts by weight, and more preferably 15 parts by weight to 40 parts by weight.

When the ethylenically unsaturated monomer (b-2-1) having the structure represented by the formula (III-2-1) is used, the negative photosensitive resin composition obtained is formed after the lithography process. The pixel colored layer has the advantage of better sputter resistance.

When the ethylenically unsaturated monomer (b-2-1) as shown in the formula (III-2-1) is used in an amount ranging from 5 parts by weight to 50 parts by weight, the negative form is obtained. The photosensitive resin composition has a advantage of better spatter resistance after the lithography process.

Ethylene unsaturated monomer having one or more carboxylic acids or carboxylic anhydrides (b-2-2)

In the ethylenically unsaturated monomer (b-2-2) having one or more carboxylic acids or carboxylic anhydrides, ethylene having one or more carboxylic acids The unsaturated monomer may include, but is not limited to, an unsaturated monocarboxylic acid compound, an unsaturated polycarboxylic acid compound, a polycyclic compound having an unsaturated group and a carboxylic acid group, or an unsaturated group and a plurality of carboxylic acid groups. Polycyclic compounds.

The aforementioned unsaturated monocarboxylic acid compound may include, but is not limited to, (meth)acrylic acid, crotonic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(methyl)acrylic acid ethoxylated succinate (2-methacryloyloxyethyl succinate monoester), 2-(methyl) propylene oxime ethoxy hexahydrophthalate, 2-(meth) propylene ethoxy ethoxylate or omega-carboxylic acid group Caprolactone polyol monoacrylate and the like. The omega-carboxylic acid polycaprolactone polyol monoacrylate can be manufactured synthetically in East Asia and is commercially available as 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 or citraconic acid, and the like.

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

The above polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups may be, for example, 5,6-dicarboxylic acidbicyclo[2.2.1]hept-2-ene or the like.

Preferably, the ethylenically unsaturated monomer having one or more carboxylic acids may be selected from the group consisting of acrylic acid, methacrylic acid, 2-methylpropenyl ethoxy succinate, 2-methyl propylene sulfhydryl. Ethoxy hexahydrophthalate, or any combination of the above.

In the ethylenically unsaturated monomer (b-2-2) having one or more carboxylic acids or carboxylic anhydrides, the ethylenically unsaturated monomer having one or more carboxylic anhydrides may include, but is not limited to, an unsaturated carboxylic acid. An acid 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 or citraconic anhydride, and the like. The above polycyclic compound having an unsaturated group and a carboxylic anhydride may include, but is not limited to, 5,6-dicarboxylic anhydride bicyclo[2.2.1]hept-2-ene and the like.

Preferably, the ethylenically unsaturated monomer having one or more carboxylic anhydrides is maleic anhydride.

The above ethylenically unsaturated monomer (b-2-2) having one or more carboxylic acids or carboxylic anhydrides may be used singly or in combination of plural kinds.

Based on the ethylenically unsaturated monomer (b-2-1) represented by the formula (III-2-1), an ethylenically unsaturated monomer having one or more carboxylic acids or carboxylic anhydrides (b-2- 2) and the other copolymerizable ethylenically unsaturated monomer (b-2-3) is used in an amount of 100 parts by weight, the ethylenically unsaturated monomer having one or more carboxylic acids or carboxylic anhydrides (b) -2-2) may be used in an amount of 5 parts by weight to 40 parts by weight, preferably 10 parts by weight to 35 parts by weight, and more preferably 15 parts by weight to 30 parts by weight.

Other copolymerizable ethylenically unsaturated monomers (b-2-3)

The other copolymerizable ethylenically unsaturated monomer (b-2-3) may include, but is not limited to, alkyl (meth)acrylate, alicyclic (meth)acrylate, aryl (meth)acrylate Ester, unsaturated dicarboxylate, (meth)acrylic acid a hydroxyalkyl ester, a polyether having a (meth) acrylate group, a styrene compound or an unsaturated compound other than the above compounds.

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 acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate or t-butyl (meth)acrylate.

The aforementioned alicyclic (meth) acrylate may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate {or Tricyclo [5.2.1.0 ^2,6 ]癸-8-yl (meth) acrylate}, dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate or (meth) acrylate Tetrahydrofuran ester and the like.

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

The aforementioned unsaturated dicarboxylic acid ester may include, but is not limited to, diethyl maleate, diethyl fumarate or diethyl itaconate.

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

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

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

The unsaturated compound other than the foregoing compounds may include, but is not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, Isoprene, 2,3-dimethyl1,3-butadiene, N-butylenediamine-3-maleimide benzoate, N-butanediimide- 4-maleimide butyrate, N-butanediamine-6-maleimide caproate, N-butylenediamine-3-maleimide propionate , N-(9-acridinyl)maleimide, N-octylmaleimide, N-cyclohexylmaleimide or N-phenyl N-phenylmaleimide and the like.

The other copolymerizable ethylenically unsaturated monomer (b-2-3) may be used singly or in combination of plural kinds.

Preferably, the other copolymerizable ethylenically unsaturated monomer (b-2-3) may be selected from methyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid 2- Hydroxyethyl ester, tert-butyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl methacrylate, dicyclopentyloxy (meth)acrylate Ethyl ester, styrene, p-methoxystyrene or any combination of the above.

Based on the ethylenically unsaturated monomer (b-2-1) represented by the formula (III-2-1), an ethylenically unsaturated monomer having one or more carboxylic acids or carboxylic anhydrides (b-2- 2) and the other copolymerizable ethylenically unsaturated monomer (b-2-3) is used in a total amount of 100 parts by weight, and the other copolymerizable ethylenically unsaturated monomer (b-2-3) The amount can be from 10 parts by weight to 90 parts by weight The portion is preferably from 20 parts by weight to 80 parts by weight, and more preferably from 30 parts by weight to 70 parts by weight.

Epoxy group-containing ethylenically unsaturated monomer (b-2-4)

The epoxy group-containing ethylenically unsaturated monomer (b-2-4) may include, but is not limited to, a (meth) acrylate compound having an epoxy group, an α -alkyl acrylate compound having an epoxy group or A glycidyl ether compound or the like.

The above epoxy group-containing (meth) acrylate compound may include, but is not limited to, glycidyl (meth) acrylate, 2-methyl propyl propyl (meth) acrylate, (meth) acrylate 3, 4 -butyl butyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexyl (meth) acrylate Wait.

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

The aforementioned glycidyl ether compound may include, but is not limited to, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether or p-vinylbenzene. P-vinylbenzylglycidylether or the like.

The above epoxy group-containing ethylenically unsaturated monomer (b-2-4) may be used singly or in combination of plural kinds.

Preferably, the epoxy group-containing ethylenically unsaturated monomer (b-2-4) may be selected from the group consisting of glycidyl methacrylate and 2-methyl methacrylate. Glycidyl propyl ester, 3,4-epoxycyclohexyl methyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl epoxidized propyl ether, m-vinyl benzyl Glycidyl ether, p-vinylbenzyl glycidyl ether or any combination of the above.

Based on the ethylenically unsaturated monomer (b-2-1) represented by the formula (III-2-1), an ethylenically unsaturated monomer having one or more carboxylic acids or carboxylic anhydrides (b-2- 2) and a total amount of the other copolymerizable ethylenically unsaturated monomer (b-2-3) used in an amount of 100 parts by weight, the epoxy group-containing ethylenically unsaturated monomer (b-2-4) The amount used may be 1 part by weight to 35 parts by weight, preferably 3 parts by weight to 30 parts by weight, and more preferably 5 parts by weight to 25 parts by weight.

Next, the second alkali-soluble resin (B-2) may have a polystyrene-equivalent number average molecular weight measured by a colloidal permeation chromatography of generally 1,000 to 35,000, preferably 3,000 to 30,000, and more preferably 5,000 to 5,000. 25,000.

The second alkali-soluble resin (B-2) may be used in an amount of from 0 part by weight to 95 parts by weight, based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight, preferably from 10 parts by weight to 90 parts by weight. Parts, and more preferably 20 parts by weight to 80 parts by weight.

When the alkali-soluble resin (B) of the present invention contains the second alkali-soluble resin (B-2), the pixel-colored layer formed of the negative-type photosensitive resin composition obtained has better sputter resistance.

Compound having ethylenically unsaturated group (C)

The compound (C) having an ethylenically unsaturated group according to the present invention may contain 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 above unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, propylene morpholine, methacryl morpholine, acetyl 7-amino-3,7-dimethyl Octyl ester, 7-amino-3,7-dimethyloctyl methacrylate, isobutoxymethyl acrylamide, isobutoxymethyl methacrylamide, isobornyl acrylate , isobornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyl diglycol acrylate , ethyl diglycol methacrylate, third octyl acrylamide, third octyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, dimethyl urethane, A Dimethylamino acrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentene oxyethyl acrylate, dicyclopentene oxyethyl methacrylate, dicyclopentenyl acrylate, Dicyclopentenyl methacrylate, N,N-dimethyl decylamine, N,N-dimethyl methacrylamide, C Tetrachlorophenyl ester, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, methacrylic acid Hydroquinone ester, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichloroacrylate Phenoxyethyl ester, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, methacrylic acid - 2-tribromophenoxyethyl ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propylene Acid 2-hydroxypropyl ester, 2-hydroxypropyl methacrylate, vinyl caprolactam, nitrogen-vinyl tyrosinone, phenoxyethyl acrylate, phenoxyethyl methacrylate, Pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate Ester, polypropylene glycol methacrylate, borneol acrylate or borneol methacrylate. The above unsaturated compound having at least one ethylenically unsaturated group may be used singly or in combination of plural kinds.

Specific examples of the above unsaturated compound having at least two ethylenically unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, and dimethacrylic acid. Dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris(2-hydroxyethyl)isocyanate diacrylate, tris(2-hydroxyethyl) Isocyanate dimethacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, tris(2-hydroxyethyl)isocyanate trimethacrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate Triacrylate (caprolactone modified) tris(2-hydroxyethyl)isocyanate trimethacrylate, trimethylolpropyl triacrylate, trimethylolpropyl trimethacrylate, ethylene oxide ( Hereinafter referred to as EO) modified trimethylol propyl triacrylate, 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 dimethyl Ethyl ester, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6- Hexanediol diacrylate, 1,6-hexane Alcohol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, polyester dimethacrylate, polyethylene glycol II Acrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol Acrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexamethacrylate, caprolactone modified dipentaerythritol pentaacrylate, Lactone modified dipentaerythritol pentamethyl acrylate, ditrimethylol propyl tetraacrylate, ditrimethylol propyl tetramethacrylate, EO modified bisphenol A diacrylate, EO modified Bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO modified hydrogen Bisphenol A diacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethacrylate, PO modified Triglyceride, EO modified bisphenol F diacrylate, EO modified bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polyglycidyl ether methacrylate, Japan A product manufactured by Toagosei Co., Ltd. and model number TO-1382, or manufactured by Nippon Kayaku Co., Ltd. and model number KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 Or a business such as KAYARAD DPEA-12 Product. The above unsaturated compound having at least two ethylenically unsaturated groups may be used singly or in combination of plural kinds.

Preferably, the compound (C) having an ethylenically unsaturated group is selected from trimethylolpropyl acrylate, EO-modified trimethylolpropyl acrylate, and PO-modified tris-trisyl triacrylate. Methyl propyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrihydroxy hydroxytetraacrylate Methyl propyl ester, PO modified triglyceride, KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 or any combination of the above.

The above compound (C) having an ethylenically unsaturated group may be used singly or in combination of plural kinds.

The compound (C) having an ethylenically unsaturated group may be used in an amount of from 20 parts by weight to 200 parts by weight, preferably from 30 parts by weight to 180%, based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight. Parts by weight, and more preferably 50 parts by weight to 150 parts by weight.

Photoinitiator (D)

The photoinitiator (D) of the present invention may comprise a photoinitiator (D-1) as shown in formula (I). Secondly, the photoinitiator (D) may optionally further comprise other radical photoinitiators (D-2).

Photoinitiator (D-1)

The photoinitiator (D) of the present invention may comprise a photoinitiator (D-1) as shown in formula (I):

In the formula (I), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ , OE ₁₇ , halogen atom, NO ₂ or ; Or E ₁ and E _2, E _2, and E _3, E ₃ and E _4, E ₅ and E _6, E ₆ or E ₇ and E ₇ and E ₈ each independently represent by Alternate carbon number is 2 to 10 alkenyl; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are respectively independent Commonly represented by -(CH ₂ ) _p -W-(CH ₂ ) _q -; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are independently represented Wherein at least one of E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or at least one group as shown below. Substituted, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, CN, OH, SH, an alkoxy group having a carbon number of 1 to 4, (CO)OH or (CO)O(R ₁ ), wherein R ₁ represents an alkyl group having 1 to 4 carbon atoms; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, The at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ are independently represented a halogen atom, CN, OE ₁₇ , SE ₁₈ , SOE ₁₈ , SO ₂ E ₁₈ or NE ₁₉ E ₂₀ , wherein the substituents OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ are not or via such groups E ₁₇ , E ₁₈ , E ₁₉ and/or E ₂₀ form a five-membered or six-membered ring with one carbon atom of the naphthalene ring; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ respectively represent independently , COE ₁₆ or NO ₂ ; W represents O, S, NE ₂₆ or a single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z ₁ represents CO or a single bond; and E ₁₃ represents a carbon number of 1. The alkyl group having a carbon number of from 1 to 20 is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from a halogen atom, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ , NE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ or Or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interspersed with one or more of O, S, SO, SO ₂ , NE ₂₆ or CO; or E ₁₃ represents carbon The number of alkenyl groups of 2 to 12, the alkenyl group having 2 to 12 carbon atoms which is undoped or inter-hetero-doped with one or more O, CO or NE ₂₆ , wherein the inter-alkyl group has a carbon number of 2 to 20 And the alkenyl group having 2 to 12 carbon atoms without inter- or inter-heteropoly is unsubstituted or substituted with at least one halogen atom; or E ₁₃ represents a cycloalkenyl group having 4 to 8 carbon atoms and having a carbon number of 2 to 12 An alkynyl group, or a cycloalkyl group having one or more O, S, CO or NE ₂₆ carbon atoms of 3 to 10; or E ₁₃ representing a phenyl or naphthyl group, and the phenyl group or the The naphthyl groups are each unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , , COE ₁₆ , CN, NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, intermixed with one or more O, S, CO or NE ₂₆ and having a carbon number of 2 An alkyl group of up to 20; or the phenyl group or the naphthyl group is each substituted with a cycloalkyl group having a carbon number of 3 to 10 or each interstitial having one or more O, S, CO or NE ₂₆ and having a carbon number of 3 to 10 Cycloalkyl substituted; k represents an integer from 1 to 10; E ₁₄ represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms which is substituted with or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, a phenyl group, and an alkyl group having 1 to 20 carbon atoms. Phenylphenyl or CN; or E ₁₄ represents phenyl or naphthyl, each unsubstituted or substituted by at least one group as shown below, and the at least one group is selected from the group consisting of a C 1 to 6 alkane a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, CN, OE ₁₇ , SE ₁₈ and/or NE ₁₉ E ₂₀ ; or E ₁₄ representing a heteroaryl group having 3 to 20 carbon atoms and having a carbon number of 1 to Alkoxy, benzyloxy or phenoxy group, the benzyloxy group and the phenoxy group are not taken Or the group substituted with at least one of the following, and the at least one group selected from an alkyl group having a carbon number of 1 to 6 carbon atoms, a haloalkyl group of 1 to 4 and / or a halogen atom; E ₁₅ represents a carbon An aryl group having 6 to 20 or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group and a halogen group. Atom, haloalkyl having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ , bonded to SO and having a carbon number of 1 to 10 An alkyl group, an alkyl group bonded to SO ₂ and having a carbon number of 1 to 10, an intervening one or more O, S or NE ₂₆ and an alkyl group having 2 to 20 carbon atoms; or each carbon number thereof is 1 An alkyl group substituted to 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms Oxycarbonyl, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents a hydrogen atom, carbon An alkenyl group having 2 to 12 alkenyl groups, having no or hetero or one or more O, CO or NE ₂₆ and having a carbon number of 3 to 8; or E ₁₅ representing an alkyl group having 1 to 20 carbon atoms; The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OE ₁₇ , SE ₁₈ , and a carbon number of 3 to 8. a cycloalkyl group, a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ , , a phenyl group, wherein the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, and the phenyl group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E _{20 is} substituted; or E ₁₅ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is one or more O, SO or SO ₂ . The alkyl group having a carbon number of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OE ₁₇ , COOE ₁₇ , and CONE ₁₉ E _{20 .} a phenyl group or a phenyl group substituted with OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents an alkanoyl group or a benzamidine group having a carbon number of 2 to 20, which is unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents an unsubstituted group Or a naphthylmethyl group substituted with at least one OE ₁₇ or a heteroarylcarbonyl group having a carbon number of 3 to 14; or E ₁₅ represents an alkoxycarbonyl group having a carbon number of 2 to 12, and the carbon number is 2 to 12 The alkoxycarbonyl group is unintercalated or at least one O Wherein the interrupted or not interrupted by a carbon atoms and an alkoxycarbonyl group having 2 to 12 lines of unsubstituted or substituted by at least one hydroxyl group; or E ₁₅ Representative phenoxycarbonyl, phenoxycarbonyl which is unsubstituted lines Or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents CN, CONE ₁₉ E ₂₀ , NO ₂ , haloalkyl having a carbon number of 1 to 4, S(O) _r -R ₂ , bonded to S(O) _r a phenyl group, wherein the phenyl group bonded to S(O) _r is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO ₂ -R ₂ , and R ₂ represents a carbon number of 1 to 6 alkyl; or E ₁₅ represents a phenyl group bonded to the SO ₂ O, diphenylphosphino acyl or di (R ₃₎ - phosphino acyl, SO ₂ O wherein the bond with the phenyl unsubstituted or lines Substituted by an alkyl group having 1 to 12 carbon atoms, and R ₃ represents an alkoxy group having 1 to 4 carbon atoms; r represents an integer of 1 to 2; and E' ₁₄ represents one of the definitions for E ₁₄ ; E _'15 represents a ₁₅ for one of those defined in E; Z ₂ representative of O, S, SO, or SO _2; Z ₃ Table O, CO, S or a single bond; E ₁₆ represents a carbon atoms or an aryl group of 6 to 20 carbon atoms of the 3 to 20 hetero aryl group, each of which is unsubstituted or is at least as shown by a substituted And the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , one or more O, S Or NE ₂₆ and an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or at least one group as shown below And wherein the at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, a heteroaryl group having a carbon number of 3 to 20, and a carbon number of An aryloxycarbonyl group of 6 to 20, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ representing a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a phenyl group, an OH group, a SH group, a CN group, and a carbon number. 3 to 6 alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO O(R ₁ ), O(CO)-(R ₁ ), O(CO)-phenyl or (CO)OH or (CO)O(R ₁ ); or E ₁₆ represents a carbon number of 2 to 12 An alkyl group having 2 to 12 alkyl interstitials having one or more O, S or NE ₂₆ ; or E ₁₆ representing (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO) -(R ₄ ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R ₄ represents an alkyl group having 1 to 8 carbon atoms; or E ₁₆ represents a substitution with SE ₁₈ a phenyl group, wherein E ₁₈ represents a single bond to the phenyl group or the naphthyl ring to which the carbazole moiety is attached to the COE ₁₆ ; n represents an integer from 1 to 20; and E ₁₇ represents a hydrogen atom, benzene group -R _5, an alkyl group having a carbon number of 1 to 20, which system the at least one substituent group is unsubstituted or illustrated by the following, and the at least one group selected from a halogen atom, OH, SH, CN, Alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ), O(CO)-(R ₆ ), a phenyl group bonded to O(CO), (CO)OH, (CO)O(R ₁ ), a cycloalkyl group having a carbon number of 3 to 20, SO ₂ -(R ₇ ), O(R ₇ ) or interrupted by O and at least one cycloalkyl group having a carbon number of 3 to 20, wherein R ₅ represents an alkyl group having a carbon number of 1-3, R ₆ represents a carbon number of 2 to 4 Group, and R ₇ represents a haloalkyl group having a carbon number of 1 to 4; or E ₁₇ represents a carbon atoms of an alkyl group of 2 to 20, carbon atoms and the alkyl group of 2 to 20 based interrupted by one or more O, S Or NE ₂₆ ; or E ₁₇ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), alkane fluorenyl group having 1 to 8 carbon atoms, carbon number Is an alkenyl group of 2 to 12, an olefin group having a carbon number of 3 to 6, or a cycloalkyl group having a carbon number of 3 to 20, which is one or more O, S, CO or NE ₂₆ without impurity or impurity; Or E ₁₇ represents a group formed by bonding an alkyl group having 1 to 8 carbon atoms to a cycloalkyl group having 3 to 10 carbon atoms, and the group is uninterfering or via at least one O; or E ₁₇ Represents a benzamidine group which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or An alkoxy group having a carbon number of 1 to 3; or E ₁₇ represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group as shown below, and The at least one group is selected from the group consisting of a halogen atom, OH, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN, NO ₂ , Phenyl-R ₈ , phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N(R ₉ ) ₂ , diphenyl-amino or Wherein R ₈ represents an alkoxy group having a carbon number of 1 to 3, and R ₉ represents an alkyl group having a carbon number of 1 to 12; or E ₁₇ and has or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R ₅ group, wherein The alkenyl group having 2 to 12 carbon atoms, the cycloalkyl group having 3 to 20 carbon atoms, and the phenyl-R ₅ group having no or hetero or one or more O, S, CO, NE ₂₆ or COOE ₁₇ Or E ₁₈ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group of the formula: wherein the at least one group is selected from OH , SH, CN, alkoxy groups having a carbon number of 3 to 6, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₆ ), O(CO)- (R ₁ ), O(CO)-phenyl or (CO)OE ₁₇ ; or E ₁₈ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms has one or more O , S, CO, NE ₂₆ or COOE ₁₇ ; or E ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), alkane having 2 to 8 carbon atoms a mercapto group or an olefin group having a carbon number of 3 to 6; or E ₁₈ represents a benzamidine group which is unsubstituted or substituted with at least one group as shown below, and the at least one group Is selected from a carbon number of 1 to 6 a group, a halogen atom, an OH group, an alkoxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms; or E ₁₈ represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20 Each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. Alkoxy group having a carbon number of 1 to 12, CN, NO ₂ , phenyl-R ₈ , phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N(R ₉ ) ₂ , diphenylamino, (CO)O(R ₄ ), (CO)-R ₄ , (CO)N(R ₄ ) ₂ or E ₁₉ and E ₂₀ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of 2 Alkenyl group to 5, cycloalkyl group having 3 to 20 carbon atoms, phenyl-R ₅ , alkanoyl group having 1 to 8 carbon atoms, alkyl alkoxy group having 1 to 8 carbon atoms, carbon number 3 to 12 olefinic groups, SO ₂ -R ₇ or benzamidine groups; or E ₁₉ and E ₂₀ represent a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 1 to 12 An alkyl group, a benzhydryl group or an alkoxy group having a carbon number of 1 to 12; or an E ₁₉ and E ₂₀ system together with an attached nitrogen atom to form a five-membered member having no inter or heterogeneous O, S or NE ₁₇ Or a six-membered saturated or unsaturated ring, and the five or six member saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of 1 carbon number to an alkyl group having a carbon number of 20 is alkyl group of 1 to _{20, = O, OE 17, SE} 18, NE 21 E 22 _{(CO) E 23, NO 2} , a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, phenyl, Or a cycloalkyl group having one or more O, S, CO or NE ₁₇ and having a carbon number of 3 to 20 without interstitial or heterogeneous; or E ₁₉ and E ₂₀ together with the attached nitrogen atom to form a heteroaromatic a ring system, the heteroaromatic ring system being unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and having a carbon number of 1 to 4 Haloalkyl, alkoxy with 1 to 20 carbon atoms, =0, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , (CO) E ₂₃ , a halogen atom, NO ₂ , CN, phenyl, or a cycloalkyl group having one or more O, S, CO or NE ₁₇ and having a carbon number of 3 to 20 without interstitial or heterogeneous; E ₂₁ and E ₂₂ are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; and a nitrogen atom to which E ₂₁ and E _{22 are} bonded thereto Forming a five- or six-membered saturated or unsaturated ring having no or interstitial or O, S or NE ₂₆ , wherein the five or six member saturated or unsaturated ring system is not fused or fused to the benzene ring; ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O, CO or NE ₂₆ and having a carbon number of 2 to 20, which is not a cycloalkyl group having an O, S, CO or NE ₂₆ and having a carbon number of 3 to 20; or E ₂₃ representing a phenyl group, a naphthyl group, a phenyl-R ₁ , OE ₁₇ , SE ₁₈ or NE ₂₁ E ₂₂ E ₂₄ stands for (CO) OE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E ₁₇ or has one of the definitions for E ₁₉ and E ₂₀ ; E ₂₅ stands for COOE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E _17; or wherein E ₂₅ has one of those defined for the E _17; E ₂₆ represents a hydrogen atom Is an alkyl group having a carbon number of 1 to 20 carbon atoms, a haloalkyl group of 1 to 4, interrupted by at least one O or CO and alkyl having 2 to 20; or E ₂₆ represents phenyl -R _1, without a heterocyclo group or a cycloalkyl group having at least one O or CO and having a carbon number of 3 to 8; or E ₂₆ representing (CO)E ₁₉ ; or E ₂₆ representing a phenyl group, E ₂₆ being unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or , but the condition is that the photoinitiator (D-1) as shown in formula (I) has at least one

The photoinitiator (D-1) as shown in formula (I) is characterized in that it contains at least one annelated unsaturated ring on its carbazole moiety. In other words, at least one pair of E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are .

The above-mentioned alkyl group having a carbon number of 1 to 20 is linear or branched and has, for example, a carbon number of 1 to 18, a carbon number of 1 to 4, a carbon number of 1 to 12, and a carbon number of 1 to 8. An alkyl group having 1 to 8 carbon atoms or 1 to 4 carbon atoms, or an alkyl group having 4 to 12 carbon atoms or 4 to 8 carbon atoms. Specific examples are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Pentyl, 2-ethylhexyl, octyl, decyl, decyl, dodecyl, tetradecyl, fifteen, hexadecyl, octadecyl and decyl. The alkyl group having 1 to 6 carbon atoms has the same definition as the above-mentioned alkyl group having 1 to 20 carbon atoms, and has the highest corresponding number of carbon atoms.

The unsubstituted or substituted alkyl group having 1 to 20 carbon atoms containing at least one carbon-carbon multiple bond is an alkenyl group described later.

The haloalkyl group having 1 to 4 carbon atoms is an alkyl group having a carbon number of 1 to 4 which is substituted by a halogen as defined below and which is as defined above. The alkyl group can be, for example, mono- or polyhalogenated until all hydrogen atoms are replaced by a halogen, and can be, for example, C _j H _w X _y , wherein w+y=2j+1 and X is a halogen, preferably a fluorine atom. . Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

The hydroxyalkyl group having 2 to 4 carbon atoms means an alkyl group having 2 to 4 carbon atoms which is substituted by one or two oxygen atoms. The alkyl group can be straight or branched. Specific 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.

The alkoxyalkyl group having 2 to 10 carbon atoms is an alkyl group having 2 to 10 carbon atoms. The alkyl group having a carbon number of 2 to 10 has the same definition as the aforementioned alkyl group having 1 to 20 carbon atoms, and has the highest corresponding number of carbon atoms. Specific examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl , propoxypropyl.

The alkyl group having one or more of O, S, NE ₂₆ or CO having a carbon number of 2 to 20 is, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times by O, S, NE ₂₆ or CO. , 1 or 2 times. If more than one meso group is present, it is the same species or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., exoethyl groups). These alkyl groups are linear or branched. For example, the following structural units will be present: -CH ₂ -CH ₂ -O-CH ₂ CH ₃ , -[CH ₂ CH ₂ O] _y -CH ₃ (where y = 1 to 9), -(CH ₂ - CH ₂ O) ₇ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ ,- CH ₂ -CH ₂ -S-CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-NE 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 .

In the present invention, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms are understood to be an alkyl group having at least one ring. Specific examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. In the present invention, a cycloalkyl group having a carbon number of 3 to 10 also encompasses an example of a bicyclic ring, that is, a bridged ring, and specific examples can be, for example, , , , and other corresponding rings. Other specific examples can be, for example, , , (E.g )or Equal structure, as well as bridging or fused ring systems, for example, the definition here also includes or And other structures wherein R ₁₀ represents an alkylene group and R ₁₁ represents an alkyl group.

The cycloalkyl group having a carbon number of 3 to 20 interposed between O, S, NE ₂₆ or CO has the same definition as defined above, wherein at least one -CH ₂ - group of the alkyl group is replaced by O, S, NE ₂₆ or CO. Specific examples are as , , (E.g ), , , , , or And other structures.

The group formed by the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 3 to 10 carbon atoms means a carbon as defined above substituted with at least one alkyl group having at most 8 carbon atoms. The number is from 3 to 10 cycloalkyl groups. The specific example is or Wait.

The group formed by the one or more alkyl groups having 1 to 8 carbon atoms bonded to a cycloalkyl group having 3 to 10 carbon atoms is substituted by at least one alkyl group having up to 8 carbon atoms. One or more of the cycloalkyl groups having a carbon number of from 3 to 10 are defined as defined above. Specific examples are as or Wait.

The alkoxy group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms which is substituted with one oxygen atom. An alkyl group having 1 to 12 carbon atoms has the same definition as the above-mentioned alkyl group having 1 to 20 carbon atoms, and has the highest corresponding carbon atom number. The alkoxy group having a carbon number of 1 to 4 is a straight chain or a branched chain, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, an isobutoxy group. Or a third butoxy group. The alkoxy group having 1 to 8 carbon atoms and the alkoxy group having 1 to 4 carbon atoms are the same as defined above, and have the highest corresponding number of carbon atoms.

The alkylthio group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms which is substituted by a sulfur atom. The alkyl group having 1 to 12 carbon atoms has the same definition as the above-mentioned alkyl group having 1 to 20 carbon atoms, and has the highest corresponding number of carbon atoms. An alkylthio group having a carbon number of 1 to 4 is a straight chain or a branched chain, such as a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, an n-butylthio group, a second butyl group. Sulfur, isobutylthio, tert-butylthio.

The phenyl-R ₅ may, for example, be benzyl, phenylethyl, α -methylbenzyl or α , α -dimethyl-benzyl, especially benzyl.

The phenyl-R ₈ may, for example, be a benzyloxy group, a phenylethoxy group, an α -methylbenzyloxy group or an α , α -dimethylbenzyloxy group, especially a benzyloxy group.

The alkenyl group having 2 to 12 carbon atoms is mono- or polyunsaturated and is, for example, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. . Specific examples are vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentyl Dienyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. The alkenyl group having 2 to 5 carbon atoms has the same definition of the alkenyl group having a carbon number of 2 to 12 as described above, and has the highest corresponding number of carbon atoms.

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

The cycloalkenyl group having 4 to 8 carbon atoms has at least one double bond, and may be, for example, a cycloalkenyl group having 4 to 6 carbon atoms or a cycloalkenyl group having 6 to 8 carbon atoms. Specific examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

The alkenyloxy group having a carbon number of 3 to 6 is mono- or polyunsaturated, and has one of the definitions of the alkenyl group as described above, and the attached oxy group has the highest corresponding number of carbon atoms. Specific examples are allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.

The alkynyl group having 2 to 12 carbon atoms is a mono- or polyunsaturated linear or branched chain, and may, for example, be an alkynyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 6 carbon atoms or a carbon number of 2 Alkynyl group to 4. Specific examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl , octynyl and the like.

The alkane group having a carbon number of 2 to 20 is linear or branched, and may have, for example, a carbon number of 2 to 18, a carbon number of 2 to 14, a carbon number of 2 to 12, and a carbon number of 2 to 8. An alkanoyl group having a carbon number of 2 to 6 or a carbon number of 2 to 4 or an alkanoyl group having a carbon number of 4 to 12 or a carbon number of 4 to 8. Specific examples are, for example, ethyl, propyl, butyl, isobutyl, pentylene, hexyl, decyl, octyl, fluorenyl, fluorenyl, fluorenyl, tetradecyl, fifteen Sulfhydryl, hexadecanyl, octadecyl, and decyl, preferably acetyl. Alkane with a carbon number of 1 to 8 The group has the same definition as the alkynylene group having a carbon number of 2 to 20 as described above, and has the highest corresponding number of carbon atoms.

The alkoxycarbonyl group having 2 to 12 carbon atoms is linear or branched, and is, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, and 1 , 1-dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially A The oxycarbonyl group, the ethoxycarbonyl group, the propoxycarbonyl group, the n-butoxycarbonyl group or the isobutoxycarbonyl group is preferably a methoxycarbonyl group.

The alkoxycarbonyl group having one or more carbon atoms of 2 to 12 may be linear or branched. The two oxygen atoms are separated by at least two methylene groups (ie, ethyl groups). The meta-alkyloxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups. The aryloxycarbonyl group having 6 to 20 carbon atoms may, for example, be a phenyloxycarbonyl group [=phenyl-O-(CO)O-], a naphthyloxycarbonyl group, a decyloxycarbonyl group or the like. The heteroarylcarbonyl group having a carbon number of 5 to 20 may be a heteroaryl group having a carbon number of 5 to 20 bonded to -O-CO-.

The cycloalkylcarbonyl group having a carbon number of 3 to 10 may be a cycloalkyl group having a carbon number of 3 to 10 bonded to the CO, wherein the cycloalkyl group has the same definition as described above and has the highest corresponding number of carbon atoms. A cycloalkylcarbonyl group having one or more carbon atoms of 3 to 10 in the group consisting of O, S, NE ₂₆ or CO means a heterocyclic CO-bonded cycloalkyl group, wherein the heterocyclic cycloalkyl group has the same The definition.

The cycloalkoxycarbonyl group having 3 to 10 carbon atoms may be a cycloalkyl group having a carbon number of 3 to 10 bonded to -O-(CO)-, wherein the cycloalkyl group has the same definition as described above and has The highest corresponding number of carbon atoms. A cycloalkoxycarbonyl group having one or more O, S, NE ₂₆ or CO having a carbon number of 3 to 10 is a hetero- and -O-(CO)-bonded cycloalkyl group, wherein The cycloalkyl group has the same definition as described above.

The alkylphenyl group having 1 to 20 carbon atoms means a phenyl group substituted with at least one alkyl group, wherein the total of the carbon atoms is at most 20.

The aryl group having 6 to 20 carbon atoms may, for example, be a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an anthracenyl group, a 1,2-benzophenanthrenyl group, a tetraphenylene group, a co-triphenyl group, etc., especially Phenyl or naphthyl, preferably phenyl. Naphthyl 1-naphthyl or 2-naphthyl.

In the photoinitiator (D-1) of the present invention, the heteroaryl group having a carbon number of 3 to 20 contains a monocyclic or polycyclic system such as a fused ring system. Specific examples are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thioxyl, furyl, dibenzofuranyl, fluorenyl, xanthenyl, thioxanthyl, Phenylthio, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, mesoindolyl, isodecyl, decyl, oxazolyl, fluorenyl, quinazolidyl , isoquinolyl, quinolyl, pyridazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, porphyrinyl, acridinyl, oxazolyl, beta-carboline, phenanthryl, Acridinyl, naphthyldiazophenyl, phenanthroline, phenazinyl, isothiazolyl, phenothiazine, isoxazolyl, furazanyl, phenanthrenyl, 7-phenanthryl, anthracene -2-yl (=9,10-di-oxy-9,10-dihydroindol-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2- Benzo[b]thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-indenyl, 8-methyl- 2-oxanyl, 3-xanthyl, 2-morphothinyl, 2,7-morphothinyl, 2-pyrrolyl, 3- Pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2- Ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl ,5,6-Dimethyl-2-pyrazinyl, 2-indolylindolyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl 2-mercapto, 1-methyl-3-indolyl, 1,5-dimethyl-2-indenyl, 1-methyl-3-oxazolyl, 2,7-dimethyl -8-fluorenyl, 2-methoxy-7-methyl-8-fluorenyl, 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 3 -Methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolinyl, 2-methoxy-6- Quinolinyl, 6-oxazinyl, 7-pyridazinyl, 1-methoxy-6-pyridazinyl, 1,4-dimethoxy-6-pyridazinyl, 1,8-naphthyridine- 2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2 -quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-carbolinyl, 6-carbolinyl, 7-carbolinyl, 3- Oxy-7-carbolinyl, 2-acridinyl, 6-acridinyl, 7-acridinyl, 6,7-dimethoxy-2-acridinyl, 2-oxazolyl, 3- Carbazolyl, 9-methyl-2-oxazolyl, 9-methyl-3-oxazolyl, β-carboline-3-yl, 1-methyl-β-carboline-3-yl, 1 -Methyl-β-carboline-6-yl, 3-phenanthryl, 2-acridinyl, 3-acridinyl, 2-naphthyldiazophenyl, 1-methyl-5-naphthalene Diazophenyl, 5-phenanol, 6-phenanthroline, 1-phenazinyl, 2-phenazine, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazine, 3-phenothiazine, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl A benzyl-3-furazyl group, a 2-oxo group, a 10-methyl-2-phenoxy group, and the like.

Preferably, the heteroaryl group having a carbon number of 3 to 20 may be a thienyl group, a benzo[b]thienyl group, a thioxanyl group, a thioxanthyl group, a 1-methyl-2-indenyl group or a 1-methyl group. Base-3-mercapto. More preferably, the heteroaryl group having a carbon number of 3 to 20 may be a thienyl group.

The heteroarylcarbonyl group having 4 to 20 carbon atoms is a heteroaryl group having a carbon number of 3 to 20 as defined above, which is bonded to the remainder of the molecule via a CO group.

The substituted aryl group (phenyl, naphthyl, aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms) is 1 to 7 times, 1 to 6 times or 1 to 4, respectively. Preferably, it is substituted by 1, 2 or 3 times. The aryl group defined cannot have more substituents than the free position on 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.

The at least one heterozygous group is intermixed, 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 Second or one or two times (the number of heteroatoms depends on the number of carbon atoms in the interphase). The group substituted at least once has, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.

A group substituted with the at least one substituent as defined above means having at least one substituent which is the same or different. Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine.

For example, if E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ or E ₅ and R ₆ , E ₆ and E ₇ , E ₇ and E ₈ are each independently Then, for example, a structure represented by the following formula (Ia) to formula (Ii) is formed, wherein the structure of the formula (Ia) is preferred: Formula (Ig) (Ih)

The compound of formula (I) is characterized in that at least one phenyl ring is partially fused to the carbazole to form a "naphthyl" ring. That is, one of the structures of the above formulas (Ia) to (Ii) is based on the formula (I).

If E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ or E ₅ and R ₆ , E ₆ and E ₇ , E ₇ and E ₈ are each independently -(CH ₂ ) _p -W-( CH ₂ ) _q -, for example, or And other structures.

If the substituent OE ₁₇ , SE ₁₈ , SOE ₁₈ , SO ₂ E ₁₈ or NE ₁₉ E ₂₀ on the phenyl or naphthyl ring is via the groups E ₁₇ , E ₁₈ , E ₁₉ and/or E ₂₀ and the naphthyl ring When a carbon atom forms a five- or six-membered ring, a structure comprising three or more rings (including a naphthyl ring) is obtained. Specific examples can be, for example,

If E ₁₇ has or One of the carbon atoms of the phenyl or naphthyl ring of the group forms a single bond, for example, or And other structures.

If E ₁₆ is a phenyl group substituted by SE ₁₈ , wherein E ₁₈ represents a single bond bonded to a phenyl or naphthyl ring having a carbazole moiety of COE ₁₆ , the structure formed may be, for example, , . That is, if E ₁₆ is a phenyl group substituted by SE ₁₈ , wherein the group E ₁₈ represents a single bond bonded to a phenyl or naphthyl ring having a carbazole moiety of COE ₁₆ , and is formed to have a thioxyl moiety at the same time. a phenyl or naphthyl ring with a carbazole moiety.

If the E ₁₉ and E ₂₀ systems together with the attached nitrogen atom form a five- or six-membered saturated or unsaturated ring without interstitial or interstitial with O, S or NE ₁₇ , the saturated or unsaturated ring formed may be For example, aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine. Preferably, if E ₁₉ and E ₂₀ are formed together with the attached nitrogen atom to form a five- or six-membered saturated or unsaturated ring which is unintermixed or intermixed with O, S or NE ₁₇ , There are five or six member saturated rings of O or NE ₁₇ , especially O.

If E ₂₁ and E ₂₂ are taken together with the attached nitrogen atom, a five- or six-membered saturated or unsaturated ring having no inter or hetero-organic O, S or NE ₂₆ is formed, and the benzene ring is selectively saturated with or When the unsaturated ring is fused, the saturated or unsaturated ring formed may be, for example, aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydro Pyridine or morpholine or corresponding ring formation (eg ).

If E ₁₉ and E ₂₀ are taken together with the attached nitrogen atom to form a heteroaromatic ring system, the heteroaromatic ring system means having more than one ring (eg 2 or 3 rings) and from the same species or different One or more heteroatoms of the species. Suitable heteroatoms can be, for example, N, S, O or P, especially N, S or O. Specific examples are carbazole, anthracene, isoindole, carbazole, anthracene, isoquinoline, quinoline, porphyrin, phenothiazine and the like.

The photoinitiator (D-1) (oxime ester) represented by the formula (I) is prepared by a conventional method, for example, by subjecting the corresponding hydrazine and hydrazine halide, particularly chloride, under the following conditions. Or anhydride reaction: in an inert solvent (eg, tert-butyl methyl ether, tetrahydrofuran (THF) or dimethylformamide), in the presence of a base (eg, triethylamine or pyridine), or in an alkaline solvent (eg, In pyridine). In one embodiment of the invention, the compound of formula (Ia) is prepared by the process shown in Scheme (i) below, wherein the E ₇ is an oxime ester group ( And Z ₁ is a single bond. However, the compounds of the formula (Ib) to the formula (Ih) are prepared in the same manner, but are carried out by using a suitable hydrazine.

In the scheme (i), E ₁ , E ₂ , E ₅ , E ₆ , E ₈ , E ₁₃ , E ₁₄ and E ₁₅ are as defined above, and X means a halogen atom, especially a chlorine atom. Preferably, E ₁₄ is a methyl group.

The above reaction represented by the formula (i) is well known to those skilled in the art and is usually carried out at a temperature of from -15 ° C to +50 ° C, preferably at a temperature of from 0 ° C to 25 ° C. .

When Z ₁ is CO, the corresponding lanthanide is obtained by using an alkyl nitrite (such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite). Methyl nitrosation to synthesize. Then, the esterification is carried out under the same conditions as described above, and the detailed preparation is as shown in the scheme (ii):

Therefore, the corresponding hydrazine compound can be obtained by, for example, in the presence of a mixture of a base or a base. Halogen or as The anhydride is reacted to produce a compound of formula (I) as defined above wherein X is a halogen atom, and especially a chlorine atom, and E ₁₄ is as defined above.

The desired starting material can be obtained by standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992) or monographs (eg SRSandler & W. Karo, Organic functional group preparations, A variety of methods are described in Volume 3, Academic Press).

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

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

Another convenient synthesis of hydrazine is the nitrosation of "active" methylene groups with nitrous acid or alkyl nitrite. Alkaline conditions (for example, as described in Organic Syntheses coll. (J. Wiley & Sons, New York, 1988), Vol. VI, pp. 199 and 840) and acidic conditions (eg, Organic Synthesis coll., Vol. V, p. 32). And page 373, Volume III, Section 191 Both pages and pages 513, Vol. II, pp. 202, 204 and 363 are suitable for the preparation of the crucibles used as starting materials in the present invention. Nitrous acid is generally produced from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.

In another embodiment, the photoinitiator (D-1) is a free hydrazine compound and has the structure shown by the following formula (IA):

In the formula (IA), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ , OE ₁₇ , halogen atom, NO ₂ or ; Or E ₁ and E _2, E _2, and E _3, E ₃ and E _4, E ₅ and E _6, E ₆ or E ₇ and E ₇ and E ₈ each independently represent by Alternate carbon number of 2 to 10, or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are respectively independent Commonly represented by -(CH ₂ ) _p -W-(CH ₂ ) _q -; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are independently represented Wherein at least one of E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which is unsubstituted or has at least one group as shown below. Substituted, and at least one group is selected from the group consisting of a phenyl group, a halogen atom, CN, OH, SH, an alkoxy group having a carbon number of 1 to 4, (CO)OH or (CO)O(R ₁ ), wherein R ₁ Or an alkyl group having a carbon number of 1 to 4; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, which is at least a group is selected from an alkyl group having a carbon number of 1 to 6, a halogen atom, CN, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a halogen atom , CN, OE ₁₇ , SE ₁₈ , SOE ₁₈ , SO ₂ E ₁₈ or NE ₁₉ E ₂₀ , wherein the substituent OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ is selectively via the groups E ₁₇ , E ₁₈ , E ₁₉ And/or E ₂₀ forms a five-membered or six-membered ring with one carbon atom of the naphthalene ring of formula (IA); or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ respectively represent independently , COE ₁₆ or NO ₂ ; W represents O, S, NE ₂₆ or a single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z ₁ represents CO or a single bond; and E ₁₃ represents a carbon number of 1. The alkyl group to 20, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, wherein at least one of the above groups is selected from a halogen atom, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ , NE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ or Or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, or one or more O, S, SO, SO ₂ , NE ₂₆ or CO; or E ₁₃ represents a carbon number An alkenyl group of 2 to 12, an alkenyl group having 2 to 12 carbon atoms, having no or hetero or one or more O, CO or NE ₂₆ , wherein the alkyl group having a carbon number of 2 to 20 is inter The hetero or interstacked alkenyl group having a carbon number of 2 to 12 is unsubstituted or substituted with at least one halogen atom; or E ₁₃ represents a cycloalkenyl group having 4 to 8 carbon atoms and an alkynyl group having 2 to 12 carbon atoms. Or a heterocyclic or heterozygous one or more of O, S, CO or NE _{26 having} a carbon number of 3 to 10; or E ₁₃ representing a phenyl or naphthyl group, each of which is unsubstituted or Substituting at least one group shown, wherein the at least one group is selected from the group consisting of OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , , COE ₁₆ , CN, NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, intermixed with one or more O, S, CO or NE ₂₆ and having a carbon number of 2 to 20 alkyl group; or each warp is not interrupted or is interrupted by one or more O, S, CO, or NE ₂₆ carbon atoms and substituted with a cycloalkyl group of 3 to 10; K represents an integer of from 1 to 10; E ₁₅ An aromatic group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ , bonded to SO and having a carbon number of 1 to An alkyl group of 10, an alkyl group bonded to SO ₂ and having a carbon number of 1 to 10, an intervening one or more O, S or NE ₂₆ and an alkyl group having 2 to 20 carbon atoms; or each carbon number thereof An alkyl group substituted with 1 to 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms An aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ representing a hydrogen atom and having a carbon number of 2 to 12 An alkenyl group, a heterocyclo group having one or more O, CO or NE ₂₆ and having a carbon number of 3 to 8; or E ₁₅ representing an alkyl group having 1 to 20 carbon atoms and having a carbon number of 1 to The alkyl group of 20 is unsubstituted or substituted by at least one group as shown below, and at least one group is selected from a halogen atom, OE ₁₇ , SE ₁₈ , a cycloalkyl group having a carbon number of 3 to 8, and a carbon number. a heteroaryl group of 3 to 20, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ , PO (OC _k H _2k+1 ) ₂ , , Or a phenyl group, wherein the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, and the phenyl group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ substituted; or E ₁₅ represents an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, one or more O, SO or SO ₂ , interstitial and carbon The alkyl group of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OE ₁₇ , COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl or via a phenyl group substituted with OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents an alkanoyl group or a benzamidine group having a carbon number of 2 to 20, which is unsubstituted or has at least one group as shown below Substituted, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents unsubstituted or via at least one OE ₁₇ a substituted naphthylmethyl group or a heteroarylcarbonyl group having a carbon number of 3 to 14; or E ₁₅ represents an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms is not Miscellaneous or intermixed with one or more O And intermingled with or without a carbon number of alkoxycarbonyl group of 2 to 12 based unsubstituted or substituted with at least one hydroxyl group; or E ₁₅ Representative phenoxycarbonyl, phenoxycarbonyl unsubstituted or system as shown by the following Substituting at least one group, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ Or E ₁₅ represents CN, CONE ₁₉ E ₂₀ , NO ₂ , a haloalkyl group having a carbon number of 1 to 4, S(O) _r -R ₂ , a phenyl group bonded to S(O) _r , wherein O) The phenyl group of the _r bond is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO ₂ -R ₂ , and R ₂ represents an alkyl group having 1 to 6 carbon atoms; or E ₁₅ represents SO ₂ O bonded phenyl, diphenylphosphonium or di(R ₃ )-phosphonium, wherein the phenyl group bonded to SO ₂ O is unsubstituted or substituted with a carbon number of 1 to 12 Substituted, and R ₃ represents an alkoxy group having a carbon number of 1 to 4; r represents an integer of 1 to 2; E' ₁₅ represents one of the definitions for E ₁₅ ; Z ₂ represents O, S, SO or SO _2; Z ₃ representative of O, CO, S or a single bond; E ₁₆ represents a carbon atoms or an aryl group of 6 to 20 carbon atoms of 3 to 20 heteroatoms of Group, each of which is unsubstituted or substituted with at least one of the groups shown below, and at least one group selected from a phenyl group, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, NO _2, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , an alkyl group having one or more O, S or NE ₂₆ and having a carbon number of 1 to 20, or an alkyl group having 1 to 20 carbon atoms, wherein the carbon number is 1 to 20 The alkyl group is unsubstituted or substituted with at least one group as shown below, wherein at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, and a cycloalkyl group having a carbon number of 3 to 8. a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen. Atom, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ) , O (CO) phenyl or (CO) OH or _{(CO) O (R 1)} ; or E ₁₆ represents a carbon atoms of an alkyl group having 2 to 12 An alkyl group having a carbon number of 2 to 12 based interrupted by one or more O, S or NE26; E _16, or on behalf of _{(CH 2 CH 2 O) n} + 1 H, (CH 2 CH 2 O) n (CO) - ( R ₄ ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R ₄ represents an alkyl group having 1 to 8 carbon atoms; or E ₁₆ represents a benzene substituted by SE ₁₈ a group, wherein E ₁₈ represents a single bond bonded to the phenyl or naphthyl ring of the carbazole moiety to which the COE _{16 is} attached; n represents an integer from 1 to 20; E ₁₇ represents a hydrogen atom, phenyl-R ₅ , An alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OH, SH, CN, and has a carbon number of 3 to 6 Alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ), O(CO)-(R ₆ ), and O(CO) bond a phenyl group, (CO)OH, (CO)O(R ₁ ), a cycloalkyl group having a carbon number of 3 to 20, SO ₂ -(R ₇ ), O(R ₇ ) or a heterogeneous one or more O And a cycloalkyl group having 3 to 20 carbon atoms, wherein R ₅ represents an alkyl group having 1 to 3 carbon atoms, R ₆ represents an alkenyl group having 2 to 4 carbon atoms, and R ₇ represents a carbon number of 1 to 4 Haloalkyl; or E ₁₇ represents an alkyl group having 2 to 20 carbon atoms and having a carbon number of 2 to The alkyl group of 20 has one or more O, S or NE ₂₆ ; or E ₁₇ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), An alkanoyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an olefinic group having 3 to 6 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, which is unintercalated or heterogeneous One or more of O, S, CO or NE ₂₆ ; or E ₁₇ represents a group formed by bonding an alkyl group having 1 to 8 carbon atoms to a cycloalkyl group having 3 to 10 carbon atoms, and the above group is One or more O; or E ₁₇ represents a benzhydryl group, the benzamidine group is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from carbon An alkyl group having 1 to 6 carbon atoms, a halogen atom, an OH group or an alkoxy group having 1 to 3 carbon atoms; or E ₁₇ representing a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is not Substituted or substituted with at least one group as shown below, and at least one group selected from the group consisting of a halogen atom, OH, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN, NO ₂ , phenyl-R ₈ , phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N(R ₉ ) ₂ , diphenyl-amino or Wherein R ₈ represents an alkoxy group having a carbon number of 1 to 3, and R ₉ represents an alkyl group having a carbon number of 1 to 12; or E ₁₇ and has or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R ₅ group, wherein An alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl-R ₅ group having no or hetero or one or more O, S, CO, NE ₂₆ or COOE ₁₇ ; or E ₁₈ represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group of the formula: wherein at least one group is selected from the group consisting of OH, SH, CN, Alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₆ ), O(CO)-(R ₁ ), O(CO)-phenyl or (CO)OE ₁₇ ; or E ₁₈ represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms, one or more O, S, CO, NE ₂₆ or COOE ₁₇ ; or E ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), an alkanoyl group having a carbon number of 2 to 8 or a carbon number of Or an alkylene group of 3 to 6; or E ₁₈ represents a benzamidine group, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a carbon number of 1 to 6 alkyl, halogen atom, OH Carbon atoms, alkoxy having 1 to 4 carbon atoms or an alkyl group of 1 to 4; or E ₁₈ represents phenyl, naphthyl or heteroaryl having a carbon number of 3 to 20 aryl group, each of which is unsubstituted or Substituting at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Base, CN, NO ₂ , phenyl-R ₈ , phenoxy, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N(R ₉ ) ₂ , diphenylamino group, (CO) O(R ₄ ), CO-R ₄ , (CO)N(R ₄ ) ₂ or E ₁₉ and E ₂₀ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of 2 to 5 alkenyl group, cycloalkyl group having 3 to 20 carbon atoms, phenyl-R ₅ , alkanoyl group having 1 to 8 carbon atoms, alkyl alkoxy group having 1 to 8 carbon atoms, carbon number Is an alkylene group of 3 to 12, SO ₂ -R ₇ or benzamidine; or E ₁₉ and E ₂₀ represent a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or Substituted by at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 1 to 12 An alkyl group, a benzyl group or an alkoxy group having a carbon number of 1 to 12; or an E ₁₉ and E ₂₀ group together with an attached nitrogen atom to form an unintermixed or intervening O, S or NE ₁₇ a member or a six member saturated or unsaturated ring, and the five or six member saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein at least one group is selected from a carbon number of 1 to 20 alkyl group, alkoxy group having 1 to 20 carbon atoms, =0, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , (C O) E ₂₃ , NO ₂ , a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, a phenyl group, Or interrupted or not by at least one O, S, CO, or NE ₁₇ carbon atoms and is interrupted by a cycloalkyl group having 3 to 20; or E ₁₉ and E ₂₀ together with the nitrogen atom based attached the heteroaromatic ring System, the heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a carbon number of 1 to 4. Haloalkyl, alkoxy with 1 to 20 carbon atoms, =0, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , (CO) E ₂₃ , a halogen atom, NO ₂ , CN, phenyl, or a cycloalkyl group having one or more O, S, CO or NE ₁₇ and having a carbon number of 3 to 20 without interstitial or heterogeneous; E ₂₁ and E ₂₂ are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; and a nitrogen atom to which E ₂₁ and E _{22 are} bonded thereto Forming a five- or six-membered saturated or unsaturated ring having no or interstitial or O, S or NE ₂₆ , wherein the five or six member saturated or unsaturated ring system is not fused or fused to the benzene ring; ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O, CO or NE ₂₆ and having a carbon number of 2 to 20, which is not a cycloalkyl group having an O, S, CO or NE ₂₆ and having a carbon number of 3 to 20; or E ₂₃ representing a phenyl group, a naphthyl group, a phenyl-R ₁ , OE ₁₇ , SE ₁₈ or NE ₂₁ E ₂₂ E ₂₄ stands for (CO) OE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E ₁₇ or has one of the definitions for E ₁₉ and E ₂₀ ; E ₂₅ stands for COOE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E _17; or for those having one of the definitions E _17; E ₂₆ represents a hydrogen atom, Alkyl having from 1 to 20, the haloalkyl group having a carbon number of 1 to 4, intermingled with at least one O or CO and alkyl having 2 to 20; or E ₂₆ represents phenyl -R _1, not intermingled Or a heterocyclic group having one or more O or CO and having a carbon number of 3 to 8; or E ₂₆ representing (CO)E ₁₉ ; or E ₂₆ representing a phenyl group, E ₂₆ being unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or , but the photoinitiator (D-1) having the structure of the formula (IA) has at least one

The group defined for the compound of the formula (IA) preferably corresponds to the one defined for the compound of the formula (I) below, except for the defined oxime ester group (for example). Are replaced by corresponding free sulfonium groups .

Each oxime ester group can exist in two configurations (Z) or (E). Isomers can be separated by conventional methods, but mixtures of isomers can also be used as (for example) a light starting material. Accordingly, the photoinitiator (D-1) of the present invention, such as the compound of the formula (I), comprises a mixture of configurational isomers.

In a preferred embodiment, the photoinitiator (D) comprises a photoinitiator (D-1) of the structure shown in formula (I), wherein E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ or NO ₂ ; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are respectively independently represented Wherein at least one of E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are Z ₁ represents CO or a single bond; E ₁₃ represents an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group The group is selected from a halogen atom, OE ₁₇ , SE ₁₈ , COOE ₁₇ , CONE ₁₉ E ₂₀ or PO(OC _k H _2k+1 ) ₂ ; or E13 represents an alkyl group having a carbon number of 2 to 20, and the interstitial a plurality of O, S, NE ₂₆ or CO; or E ₁₃ represents a phenyl or naphthyl group, both of which are unsubstituted or at least one Or COE ₁₆ substituted; E ₁₄ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms; and E ₁₅ represents a phenyl group, a naphthyl group, and a heterocyclic group having a carbon number of 3 to 20. a group, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, OE ₁₇ , SE ₁₈ , An alkyl group having at least one O or S and having a carbon number of 2 to 20, or each of which is substituted with one or more alkyl groups having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is not Substituted or substituted with at least one group as shown below, and at least one group selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of a heteroaryl group of 3 to 20, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or PO (OC _k H _{2k +1} ) ₂ ; or E ₁₅ represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE ₁₇ , SE ₁₈ , a cycloalkyl group having 3 to 8 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, and NE ₁₉ E _{2 0} , COOE ₁₇ , CONE ₁₉ E ₂₀ or PO(OC _k H _2k+1 ) ₂ ; E' ₁₄ represents one of the definitions for E ₁₄ ; E' ₁₅ represents one of the definitions for E ₁₅ E ₁₆ represents a phenyl group which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , at least one O, S or NE ₂₆ and an alkyl group having a carbon number of 2 to 20; or E ₁₆ represents a phenyl group which is substituted with at least one alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted Or substituted by at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of 3 to a heteroaryl group of 20, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ representing a carbon number of 1 To an alkyl group of 20, the E ₁₆ group is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, a phenyl group, an OH group, a SH group, a CN, and a carbon number of 3 to 6. Alkenyloxy, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ) or (CO)O(R ₁ ); E ₁₇ represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OCH ₂ CH ₂ (CO)O(R ₁ ), O(R ₁ ), (CO)O(R ₁ ), a cycloalkyl group having a carbon number of 3 to 20, wherein the carbon number is 3 to 20 The cycloalkyl group is undoped or heterozygous at least one O; or E ₁₇ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is at least one O; E ₁₈ represents trans (CO)OE ₁₇ Substituted methyl group; E ₁₉ and E ₂₀ each independently represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms or an alkyl fluorenyl group having 1 to 8 carbon atoms. An oxy group; or an E ₁₉ and E ₂₀ system together with an attached nitrogen atom to form a heteroaromatic ring system, the heteroaromatic ring system being unsubstituted or via Substituting, but the photoinitiator (D-1) having the structure of the formula (I) has at least one or .

Must pay attention to the compound as defined above of formula (I), wherein _{E 1, E 2, E 3} , E 4, E 5, E 6, E 7 and E ₈ each independently represent a hydrogen atom, , COE ₁₆ or NO ₂ ; E ₃ and E ₄ together ; E ₉ , E ₁₀ , E ₁₁ and E ₁₂ are a hydrogen atom; Z ₁ is a single bond; E ₁₃ is an alkyl group having 1 to 20 carbon atoms; and E ₁₄ is an alkyl group having 1 to 20 carbon atoms; E ₁₅ a phenyl group having 1 to 20 carbon atoms or substituted with at least one of the following groups, wherein at least one group may be OE ₁₇ or an alkyl group having 1 to 20 carbon atoms; E ₁₆ phenyl group, benzene The group is substituted by at least one group, wherein at least one group may be OE ₁₇ or an alkyl group having 1 to 20 carbon atoms; and the E ₁₇ group is unsubstituted or substituted with at least one halogen atom and has a carbon number of 1 or a 20-alkyl or inter-system heteroatom having at least one oxygen atom having 1 to 20 carbon atoms, provided that at least one of the compounds of the formula (I) is present

In a more preferred embodiment, the photoinitiator (D) comprises a photoinitiator (D-1) of the structure shown in formula (I), wherein E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom; or E ₁ and E ₂ , E ₃ and E ₄ or E ₅ and E ₆ are independently represented independently And at least one of E ₁ and E ₂ , E ₃ and E ₄ or E ₅ and E ₆ are E ₂ represents , COE ₁₆ , NO ₂ or ; or E ₇ represents Or COE ₁₆ ; E ₉ , E ₁₁ and E ₁₂ represent a hydrogen atom; E ₁₀ represents a hydrogen atom, OE ₁₇ or COE ₁₆ ; Z ₁ represents CO or a single bond; and E ₁₃ represents an alkyl group having 1 to 20 carbon atoms; Is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, E ₁₇ , OE ₁₇ , SE ₁₈ or PO(OC _k H _2k+1 ) ₂ ; or E ₁₃ Represents an alkyl group having a carbon number of 2 to 20, the interstitial is at least one O; or E ₁₃ represents a phenyl group; k represents an integer 2; E ₁₄ represents an alkyl group having 1 to 20 carbon atoms or a thienyl group; and E ₁₅ represents a benzene group. Or a naphthyl group, each of which is unsubstituted or substituted with at least one OE ₁₇ or an alkyl group having 1 to 20 carbon atoms; or E ₁₅ represents a thienyl group, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE ₁₇ , SE ₁₈ , a cycloalkyl group having 3 to 8 carbon atoms, NE ₁₉ E ₂₀ or COOE ₁₇ ; or E ₁₅ represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having a carbon number of 2 to 20 is interspersed with SO ₂ ; E ₁₆ represents a phenyl group or a naphthyl group, each of which is not Substituted or substituted with at least one group as shown below, and at least one Group selected from _{OE 17, SE 18, NE 19} E 20 carbon atoms or an alkyl group of 1 to 20; E _16, or on behalf of thienyl; E ₁₇ represents a hydrogen atom, an alkyl carbon atoms or acyl of 1 to 8 carbon An alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, O(CO) -(R ₁ ), O(CO)-(R ₆ ), or a cycloalkyl group having at least one O and having a carbon number of 3 to 20; or E ₁₇ representing an alkyl group having 2 to 20 carbon atoms, and having a carbon number Is an alkyl group of 2 to 20 at least one O; E ₁₈ represents a cycloalkyl group having 3 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms which are unsubstituted or have at least one OH, O (CO) - (R ₆ ) or (CO) OE ₁₇ substituted; or E ₁₈ represents a phenyl group which is unsubstituted or substituted with at least one halogen atom; the E ₁₉ and E ₂₀ systems independently represent a carbon number of 1 to 8 Alkanoyl or a carbon number of 1 to 8 alkyl fluorenyloxy; or E ₁₉ and E ₂₀ together with the attached nitrogen atom to form a five or six member saturated ring interspersed with O, provided that The photoinitiator (D-1) of the structure shown in (I) has at least one .

Specific examples of the photoinitiator (D-1) of the present invention are compounds of the formulae (Ia) to (Ig) as defined above, formula (Ia), formula (Ib), formula (Ic), especially formula ( Ia) or formula (Ic), or formula (Ia), formula (Ic) or formula (Id), especially a compound of formula (Ia) is of interest.

In one example, E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, Or COE ₁₆ , or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are respectively independently represented .

In an example, E ₁ and E ₂ or E ₃ and E ₄ are , or E ₃ and E ₄ , E ₅ and E ₆ are ; E ₃ and E _{4 are} especially common .

In one example, E ₁ , E ₅ , E ₆ and E ₈ represent a hydrogen atom. Preferably, E ₇ represents a hydrogen atom, Or COE ₁₆ or E ₇ represents Or COE ₁₆ , but with E ₇ For better. Preferably, E ₂ represents , COE ₁₆ or , or E ₂ and E ₁ are However, it is better to use E ₂ for COE ₁₆ . Z _{1 is} preferably a single bond.

In one example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or substituted with at least one group as shown below. a phenyl group, and at least one group is selected from the group consisting of a C 1 to 6 alkyl group, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a halogen atom, OE ₁₇ , SE ₁₈ , or NE ₁₉ E ₂₀ , wherein the substituent OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ is selectively via the groups E ₁₇ , E ₁₈ , E ₁₉ and/or E ₂₀ and formula (I) One carbon atom of the naphthalene ring forms a five-membered ring or a six-membered ring; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ are independently represented Or COE ₁₆ .

In a specific example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or at least one group as shown below a group substituted with a phenyl group, and at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently representing a halogen Atom, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ are independently represented Or COE ₁₆ .

In one example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or one or more carbon numbers of 1 to 6 alkyl substituted phenyl; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ are independently represented Or COE ₁₆ .

In another example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or substituted with at least one group as shown below. a phenyl group, and at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently representing a halogen atom, OE _17. SE ₁₈ or NE ₁₉ E ₂₀ wherein the substituent OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ is selectively via the groups E ₁₇ , E ₁₈ , E ₁₉ and/or E ₂₀ and in formula (I) One carbon atom of the naphthalene ring forms a five-membered ring or a six-membered ring.

Further, in one example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or at least one group as shown below a substituted phenyl group, at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently representing a halogen atom, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or COE ₁₆ .

Or, in one example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or at least one group as shown below a substituted phenyl group, at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently representing a halogen atom, OE ₁₇ , COE ₁₆ or NE ₁₉ E ₂₀ .

Preferably, E ₉ , E ₁₁ and E ₁₂ are hydrogen atoms, and E ₁₀ is a hydrogen atom, OE ₁₇ or COE ₁₆ .

The E _{13 group} , for example, represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as described below, wherein at least one of the above groups is selected from a halogen atom, COOE ₁₇ or CONE ₁₉ E ₂₀ ; or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms; one or more O, S, SO, SO ₂ , NE ₂₆ or CO; E ₁₃ represents carbon An alkenyl group having 2 to 12 alkenyl groups, an alkenyl group having 2 to 12 carbon atoms which is uninter or hetero-organic, having one or more O, CO or NE ₂₆ ; or E ₁₃ representing a cycloalkyl group having a carbon number of 3 to 10, The alkyl group is unintermixed or heterozygous with one or more O, S, CO or NE ₂₆ ; or E ₁₃ represents a phenyl or naphthyl group, and each of them is unsubstituted or substituted with at least one group as shown below, wherein At least one group is selected from the group consisting of OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , , COE ₁₆ , NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O and having a carbon number of 2 to 20; or a carbon number An alkyl group of 1 to 20 which is unsubstituted or substituted with at least one group as defined below, wherein at least one of the above groups is selected from the group consisting of a halogen atom, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ or PO(OC _k H _2k +1) ₂ ; or an alkyl group having a carbon number of 2 to 20, which has one or more O interphases.

Further, E ₁₃ represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, wherein at least one of the above groups is selected from a halogen atom, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ or PO(OC _k H _2k+1 ) ₂ ; or an alkyl group having a carbon number of 2 to 20, and an alkyl group having a carbon number of 2 to 20 having an O; Or an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms; or E ₁₃ representing a phenyl group or a naphthyl group, each of which is unsubstituted or at least one group as shown below Substituting at least one of the groups is selected from the group consisting of OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , And COE ₁₆ , NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having a carbon number of 2 to 20.

In another embodiment, E ₁₃ represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as defined below, wherein at least one of the above groups is selected from a halogen atom, E ₁₇ , OE ₁₇ , SE ₁₈ , or PO(OC _k H _2k+1 ) ₂ ; or an alkyl group having one or more O and having a carbon number of 2 to 20; or an alkene having 2 to 12 carbon atoms A cycloalkyl group having a carbon number of 3 to 10, a phenyl group or a naphthyl group.

Alternatively, E ₁₃ may, for example, represent an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as defined below, wherein at least one of the above groups is selected from a halogen atom, E ₁₇ , OE ₁₇ , SE ₁₈ or PO(OC _k H _2k+1 ) ₂ ; or an alkyl group having at least one O and having a carbon number of 2 to 20; or an alkenyl group or a carbon having a phenyl group and a carbon number of 2 to 12 The number is from 3 to 10 cycloalkyl groups.

Alternatively, E ₁₃ may represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Or E ₁₃ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Preferably, E ₁₃ may represent an alkyl group having a carbon number of 1 to 20, especially an alkyl group having a carbon number of 1 to 8, such as 2-ethylhexyl; and E ₁₄ may, for example, represent a hydrogen atom and have a carbon number of 3 to a cycloalkyl group of 8, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or has at least one halogen atom or benzene. Substituent; or E ₁₄ represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, carbon a halogenated alkyl group of 1 to 4, a halogen atom, OE ₁₇ , SE ₁₈ and/or NE ₁₉ E ₂₀ ; or E ₁₄ represents a heteroaryl group having a carbon number of 3 to 5, such as a thienyl group, or a carbon number of 1 To alkoxy, benzyloxy or phenoxy to 8.

Alternatively, E14 may, for example, represent an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms may be substituted with at least one halogen atom or a phenyl group; or E ₁₄ represents a heteroaryl group having a carbon number of 3 to 5. a group (for example, thienyl) or a phenyl group which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to 4 The haloalkyl group, the halogen atom, OE ₁₇ , SE ₁₈ and/or NE ₁₉ E ₂₀ ; or E ₁₄ represents an alkoxy group having a carbon number of 1 to 8, a benzyloxy group or a phenoxy group.

In another embodiment, E ₁₄ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with a phenyl group; or E ₁₄ is a phenyl group, and the phenyl group is not Substituted or substituted with at least one alkyl group having 1 to 6 carbon atoms.

Preferably, E ₁₄ is an alkyl group having 1 to 20 carbon atoms, a heteroaryl group having 3 to 5 carbon atoms (for example, thienyl group), or a phenyl group, especially an alkyl group having 1 to 20 carbon atoms or The thienyl group is more preferably an alkyl group having 1 to 8 carbon atoms.

E ₁₅ may, for example, be an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected From a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , an alkyl group having 1 to 20 carbon atoms; or an E ₁₅ hydrogen atom a cycloalkyl group having 3 to 8 carbon atoms, wherein the cycloalkyl group having 3 to 8 carbon atoms is undoped or inter-hetero-doped with one or more O, CO or NE ₂₆ ; or the E ₁₅ carbon number is 1 to 20 The alkyl group, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OE ₁₇ and a carbon number of 3 to 8. a cycloalkyl group, a heteroaryl group having 5 to 20 carbon atoms, a phenoxycarbonyl group having 8 to 20 carbon atoms, a heteroaryloxy-carbonyl group having 5 to 20 carbon atoms, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ , a phenyl group or a phenyl group substituted by a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ or NE ₁₉ E ₂₀ Or E ₁₅ is an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is at least one O, S or SO ₂ ; or an E ₁₅ alkyl group having 2 to 20 carbon atoms; And a benzepidine group, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group, CONE ₁₉ E ₂₀ , NO ₂ or a halogenated alkyl group having 1 to 4 carbon atoms.

Further, E ₁₅ may, for example, be a hydrogen atom, an aryl group having 6 to 20 carbon atoms, especially a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms. Or a heteroaryl group having a carbon number of 3 to 5, such as a thienyl group; or a cycloalkyl group having a carbon number of 3 to 8, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or as follows At least one group is substituted, and at least one group is selected from OE ₁₇ , SE ₁₇ , a cycloalkyl group having a carbon number of 3 to 8, NE ₁₉ E ₂₀ or COOE ₁₇ ; or an E ₁₅ carbon number of 2 An alkyl group of 20, and an alkyl group having 2 to 20 carbon atoms is interspersed with at least one O or SO ₂ .

In the compound of the formula (I), E ₁₅ may, for example, be a hydrogen atom, a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with an alkyl group having 1 to 8 carbon atoms; or an E ₁₅ -based thienyl group. An alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of OE ₁₇ and SE ₁₇ and having a carbon number of 3 to 8. An alkyl group, NE ₁₉ E ₂₀ or COOE ₁₇ ; or E ₁₅ is an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is interspersed with at least one O or SO ₂ .

E _{15 is} especially, for example, a cycloalkyl group having 3 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Alkyl group.

The preferred ones of E' ₁₄ and E' ₁₅ respectively have one of the definitions defined above for E ₁₄ and E ₁₅ .

Z ₂ is, for example, O, S or SO, such as O or S, especially O.

E ₁₆ may, for example, be an aryl group having 6 to 20 carbon atoms (especially a phenyl or naphthyl group, especially a phenyl group) or a heteroaryl group having a carbon number of 5 to 20 (especially a thienyl group), each of which is unsubstituted or Substituting at least one group as shown below, and at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ Or an alkyl group having at least one carbon number of 1 to 20; or each of which is substituted with at least one alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms unsubstituted or as shown below Substituting at least one group, and at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a heteroaryl group having a carbon number of 5 to 20. a aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 5 to 20 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or an E ₁₆ -based hydrogen atom having a carbon number of 1 to An alkyl group of 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, a phenyl group, an OH group, an SH group, and a carbon group. Number 3 to 6 alkenyloxy, OCH ₂ CH ₂ (CO)O(R ₁ ), O (CO)-(R ₁ ), O(CO)-phenyl, (CO)OH or (CO)O(R ₁ ); or an E ₁₆ alkyl group having 2 to 12 carbon atoms and having a carbon number of 2 Between the alkyl groups of 12, at least one O; or E ₁₆ (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), carbon number 2 to 12 The alkenyl group or a cycloalkyl group having a carbon number of 3 to 8 and n is 1 to 20, for example 1 to 12 or 1 to 8, especially 1 or 2.

Furthermore, E ₁₆ may, for example, be phenyl or naphthyl, especially phenyl, thienyl or oxazole, each unsubstituted or substituted by at least one group as shown below, and at least one group selected from a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or an alkyl group having 1 to 20 carbon atoms; or an E ₁₆ alkyl group having 1 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, a phenyl group, an OH group, and an SH group having a carbon number of 3 to 6 Alkenyloxy, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ), O(CO)-phenyl, (CO)OH or (CO)O(R ₁ ); Or an E ₁₆ alkyl group having 2 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms having at least one O; or an E ₁₆ system (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and n is 1 to 20, for example 1 to 12 or 1 to 8 Especially 1 or 2.

Furthermore, E ₁₆ may, for example, be phenyl or naphthyl, especially phenyl, each unsubstituted or substituted by at least one group as shown below, and at least one group selected from phenyl, halogen atom, a haloalkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or an alkyl group having 1 to 20 carbon atoms; or an E ₁₆ group heteroaryl group having 3 to 5 carbon atoms, especially a thienyl group .

E _{16 is} especially, for example, a phenyl group which is unsubstituted or substituted with at least one group as shown below, and at least one group selected from OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or a carbon number of An alkyl group of 1 to 20, or an E ₁₆ system thienyl group.

Preferably, E ₁₆ is, for example, phenyl or naphthyl, each unsubstituted or substituted with at least one alkyl group having from 1 to 20 carbon atoms.

E _{16 is} especially a phenyl group, and the phenyl group is substituted with at least one alkyl group having 1 to 20 carbon atoms.

E ₁₇ may, for example, be a hydrogen atom, a phenyl-R ₅ group, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from Halogen atom, OH, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ), O(CO)-(R ₆ ), O(CO)-phenyl, (CO)OH , (CO)O(R ₁ ), a cycloalkyl group having 3 to 20 carbon atoms or a cycloalkyl group having a carbon number of 3 to 20 intermixed with at least one O; or an E ₁₇ alkyl group having 2 to 20 carbon atoms And the alkyl group having a carbon number of 2 to 20 is interspersed with at least one O; or E ₁₇ (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ) An alkanoyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an olefinic group having 3 to 6 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, which is unintercalated or Between at least one O; or E ₁₇ benzyl fluorenyl, and the benzyl group is unsubstituted or substituted by at least one group as shown below, and at least one group is selected from a carbon number of 1 to An alkyl group, a halogen atom, an OH group or an alkoxy group having a carbon number of 1 to 3; or an E ₁₇ group phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 5 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and Less in a group selected from a halogen atom, OH, an alkyl group having a carbon number of 1-12, an alkoxy group having a carbon number of 1 to 12, CN, NO _2, phenyl -R _8, a phenoxy group, C a number of 1 to 12 alkylthio, phenylthio, N(R ₉ ) ₂ , diphenyl-amino or .

In another embodiment, E ₁₇ is, for example, a hydrogen atom, a phenyl-R ₅ , an alkyl group having from 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from a halogen atom, O(CO)-(R ₁ ), O(CO)-(R ₆ ) or an alkyl group having at least one O and having a carbon number of 2 to 20; or E ₁₇ And an alkylene group having 1 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an olefinic group having 3 to 6 carbon atoms, an alkyl group having 2 to 20 carbon atoms and at least one O, and not a heterocyclic or intervening heterocyclic alkyl group having at least one carbon number of 3 to 20; or an E ₁₇ benzhydryl group, which is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or an alkoxy group having 1 to 3 carbon atoms; or an E ₁₇ phenyl group or a naphthyl group, each of which is unsubstituted or Substituted by at least one group as shown below, and at least one group is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

E ₁₇ is also, for example, a hydrogen atom, a phenyl-R ₅ group, an alkanoyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or at least one as shown below. a group substituted, and at least one group is selected from a halogen atom, a cycloalkyl group having 3 to 20 carbon atoms, O(CO)-(R ₁ ), O(CO)-(R ₆ ) or at least O is an alkyl group of a carbon number of 2 to 20, E _17, or based carbon atoms of the alkyl group of 2 to 20, between at least one heteroatom O.

E _{17 is} especially a hydrogen atom, an alkanoyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group Is selected from O(CO)-(R ₁ ), O(CO)-(R ₆ ) or an alkyl group having at least one O carbon number of 2 to 20, or an E ₁₇ carbon number of 2 to 20 An alkyl group having at least one O intermixed therebetween.

E ₁₈ is, for example, a cycloalkyl group having 3 to 20 carbon atoms which is undoped or inter-heteromeric with at least one O; or an E ₁₈ alkyl group having 1 to 20 carbon atoms which is unsubstituted or as follows At least one group is substituted, and at least one group is selected from OH, O(CO)-(R ₆ ), O(CO)-(R ₁ ) or (CO)OE ₁₇ ; or E ₁₈ -based carbon a number of 2 to 20 alkyl groups interspersed with at least one O, S, CO, NE ₂₆ or COOE ₁₇ ; or an E ₁₈ alkylene group having 2 to 8 carbon atoms or an olefin having 3 to 6 carbon atoms a phenyl fluorenyl group; or an E ₁₈ phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group It is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or NO ₂ .

In another embodiment, E ₁₈ is, for example, a cycloalkyl group having from 3 to 20 carbon atoms, an alkyl group having from 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below And at least one group is selected from the group consisting of OH, O(CO)-(R ₆ ), O(CO)-(R ₁ ) or (CO)OE ₁₇ ; or E ₁₈ phenyl or naphthyl, each of which Unsubstituted or substituted with at least one halogen atom or an alkyl group having 1 to 12 carbon atoms, especially a halogen atom.

E ₁₈ is, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a phenyl group - R ₅ and a carbon number of 2 to 8 Alkyl, benzylidene, phenyl or naphthyl.

For example, E ₁₈ is an alkyl group having 1 to 20 carbon atoms which is substituted with at least one group as shown below, and at least one group is selected from OH, O(CO)-(R ₆ ), O(CO)-(R ₁ ) or (CO)OE ₁₇ , or an E ₁₈ -based phenyl group substituted with at least one halogen atom.

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

For example, E ₁₉ and E ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. a -R ₅ , phenyl or naphthyl group, an alkanoyl group having 1 to 8 carbon atoms, an alkyl fluorenyloxy group having 1 to 8 carbon atoms, an olefinic group having a carbon number of 3 to 12 or a benzamidine group; Or E ₁₉ and E ₂₀ together with the attached nitrogen atom to form a five or six member saturated or unsaturated ring without interstitial or interstitial O, S or NE ₁₇ ; or E ₁₉ and E ₂₀ with attached The nitrogen atoms together form a heteroaromatic ring system, the heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 20 carbon atoms. a halogenated alkyl group having 1 to 4 carbon atoms, or .

Further, for example, E ₁₉ and E ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, Phenyl-R ₅ , an alkanoyl group having a carbon number of 1 to 8, an alkanoyloxy group having 1 to 8 carbon atoms, an olefinic group having a carbon number of 3 to 12 or a benzhydryl group; or E ₁₉ and The E ₂₀ system together with the attached nitrogen atom forms a five- or six-membered saturated ring which is unintermixed or intermixed with O or NE ₁₇ ; or the E ₁₉ and E ₂₀ systems together with the attached nitrogen atom form an indazole ring .

For example, E ₁₉ and E ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. -R ₅ , an alkanoyl group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, an olefinic group having a carbon number of 3 to 12 or a benzamidine group; or E ₁₉ and E ₂₀ Together with the attached nitrogen atom, it forms a five- or six-membered saturated ring that is either inter- or hetero-organized with O or NE ₁₇ .

Preferably, E ₁₉ and E ₂₀ are each independently an alkanoyl group having a carbon number of 1 to 8, an alkanoyloxy group having a carbon number of 1 to 8, or an E ₁₉ and E ₂₀ system and an attached nitrogen; The atom forms a morpholine ring.

For example, E ₂₁ and E ₂₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; Or the E ₂₁ and E ₂₂ systems form a morpholine ring with the attached nitrogen atom. In particular, E ₂₁ and E ₂₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

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

The preferred of E ₂₄ is as defined for E ₁₉ and E ₂₀ . The preferred of E ₂₅ is one of those defined for E ₁₇ .

E ₂₆ is, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and at least one O or CO intermixed therebetween; or E ₂₆ series phenyl-R ₁ , cycloalkyl having 3 to 8 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms without inter- or hetero- or one or more O or CO; or E ₂₆ (CO) E ₁₉ or a phenyl group, and the phenyl group is unsubstituted or substituted by at least one of the following groups, and at least one group may be an alkyl group having 1 to 20 carbon atoms, a halogen atom, and an alkyl halide having 1 to 4 carbon atoms. a group, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ ; or E ₂₆ represents, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms; a phenyl group-R ₁ , The cycloalkyl group having a carbon number of 3 to 8, (CO) E ₁₉ or a phenyl group, and the phenyl group is unsubstituted or substituted with at least one alkyl group having 1 to 20 carbon atoms. Further, E ₂₆ is, for example, hydrogen or an alkyl group having 1 to 20 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms.

Specific examples of the photoinitiator (D-1) having the structure represented by the formula (I) may include a photoinitiator having a structure represented by the following formula (I-1) to (I-86) :

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

When the photoinitiator (D) of the present invention does not contain the photoinitiator (D-1), the pixel-colored layer formed by the negative photosensitive resin composition prepared has poor sputter resistance. Defects.

Other free radical photoinitiators (D-2)

The photoinitiator (D) of the present invention may optionally contain other radical type photoinitiators (D-2).

The other radical photoinitiator (D-2) may be selected from the group consisting of an acetophenone compound and a diimidazole compound. (biimidazole), acyl oxime or a combination of these.

The above acetophenone-based compound is selected from the group consisting of p-dimethylamino-acetophenone, α , α '-dimethoxy azo acetophenone (α, α'-dimethoxyazoxy-acetophenone). , 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone [2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone], 2- Benzyl-2-nitrogen, nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone [2-benzyl-2-N,N-di-methylamino-1-(4-morpholinophenyl) )-1-butanone].

The above diimidazole compound is selected from 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis (o-chlorophenyl) )-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyldiimidazole [2,2' -bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl 2,2'-bis(o-methyl phenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methoxyphenyl)-4, 4',5,5'-o-methoxyphenyl-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-double (o- Ethylphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(p-methoxyphenyl)-4,4',5, 5'-tetraphenyl-imimidazole [2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis (2,2',4, 4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4 ',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2 -chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl Imidazole [2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole].

The above lanthanide compound is selected from the group consisting of ethane ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3- substituent]-, 1- (Etho-acetonitrile) {Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), for example, manufactured by Ciba Specialty Chemicals The product name is CGI-242, and its structure is as shown in the following formula (VII-1)}, 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzene {1-[4-(benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), for example, a product of the trade name CGI-124 manufactured by Ciba Specialty Chemicals, the structure of which is as follows (VII-2)}, ethane ketone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzoyl)-9-hydrocarbazole-3 -Substituent]-,1-(oxy-acetamidine){Ethanone,1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]- , 1-(O-acetyl oxime), for example, manufactured by Asahi Kasei Co., Ltd., whose structure is as shown in the following formula (VII-3)}:

Preferably, the other radical photoinitiator (D-2) is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5, 5'-tetraphenyldiimidazole, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3-substituted group]-, 1-( Oxygen-acetamidine) or a combination of these.

The other radical type photoinitiator (D-2) of the present invention may further contain the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, Thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamino)benzophenone a benzophenone compound such as 4,4'-diethylaminobenzophenone; benzil or acetamidine (Acetyl), etc. α - dione (α-diketone) compound; benzoin-based compound (Benzoin) etc. ketol (acyloin); Benzoin methyl ether (benzoin methylether), benzoin ethyl ether (benzoin ethylether), benzoin isopropyl ether and other acyloin ether compounds; 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide (2,4 ,6-trimethyl-benzoyl-diphenyl-phosphineoxide), bis-(2,6-dimethoxybenzoquinone)-2,4,4-trimethylphenylphosphine oxide [bis-(2,6-dimethoxy) -benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide], etc. Ine oxide) compound; anthraquinone, quinone compound such as 1,4-naphthoquinone; phenacyl chloride, tribromomethylphenylhydrazine (tribromo methyl-phenylsulfone), tris(trichloromethyl)-s-triazine, etc.; and di-tertbutylperoxide, etc. Peroxide. Among them, a benzophenone-based compound is preferred, and 4,4'-bis(diethylamine)benzophenone is particularly preferred.

The above other radical type photoinitiators (D-2) may be used singly or in combination of plural kinds.

In a specific example of the present invention, the total amount of the alkali-soluble resin (B) used is 100 parts by weight, and the other radical type photoinitiator (D-2) is used in an amount of from 0 parts by weight to 95 parts by weight. It is preferably from 0 part by weight to 80 parts by weight, and more preferably from 0 part by weight to 65 parts by weight.

The photoinitiator (D) is used in an amount of 10 parts by weight to 100 parts by weight, preferably 15 parts by weight to 90 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B), and more preferably It is preferably from 20 parts by weight to 80 parts by weight.

Compound (E)

The compound (E) is an organophosphonium compound containing a polyfunctional epoxy group, and may contain a compound represented by the formula (II):

In the formula (II), D may represent a hydrogen atom, a glycidyl group, or a structure represented by the following formula (II-1), wherein at least one D represents a structure represented by the following formula (II-1), and at least two D represents a glycidyl group; a represents an integer from 1 to 100:

In the formula (II-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents an integer of 1 to 3; and d represents 1 An integer of up to 10.

The compound (E) may optionally comprise a compound as shown in formula (IV):

In the formula (IV), D' represents a hydrogen atom, a glycidyl group or a structure represented by the formula (II-1), wherein at least one D' represents a structure as shown in the formula (II-1), and at least two D' represents a glycidyl group; AO represents an alkylene oxide group having a carbon number of 2 to 6; f represents an integer of 4 to 10; g represents an integer of 0 to 10; and h represents an integer of 0 to 10. ; and i represents an integer from 0 to 10:

In the formula (II-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents an integer of 1 to 3; and d represents 1 An integer of up to 10.

In one embodiment, a, f, g, h, and i of the above formulas (II) and (IV) may independently represent different integers, respectively. Preferably, a represents an integer from 1 to 40, f represents an integer from 4 to 8, g represents an integer from 0 to 8, h represents an integer from 0 to 8, and i represents an integer from 0 to 8. More preferably, a represents an integer from 1 to 30, f represents an integer from 4 to 5, g represents an integer from 0 to 5, h represents an integer from 0 to 5, and i represents an integer from 0 to 5.

In the formula (II), a may represent an integer of 1 or more as described above. When a is 1, the compound represented by the formula (II) is a glycerol derivative. Based on From the viewpoint of adding a reactive group, the compound represented by the formula (II) may be a 2 bis glycerol derivative or a 3 1,3-triglycerol derivative or the like. Here, a may be an integer of 2 or more, preferably an integer of 3 or more, and more preferably an integer of 4 or more (that is, a polyglycerol derivative). Further, although g, h, and i each represent an integer of 0 or more, g, h, and i preferably each independently represent an integer of 1 or more. The sum of g, h and i may be an integer from 0 to 24, preferably an integer from 3 to 24, and more preferably an integer from 3 to 21.

The AO in the formula (IV) may represent an alkoxy group having a carbon number of 2 to 6. In one embodiment, AO may represent an Ethylene Oxide (EO) group, a Propylene Oxide (PO) group or a Butylene Oxide (BO) group. Further, when g, h and i each represent an integer of 2 or more, the alkoxy group may be a linking chain, wherein each of EO, PO and BO may be a structure of a single alkoxy group, or two or more The structure formed by the combination of alkoxy groups. Furthermore, when g, h and i respectively represent an integer of 3 or more, and the AO segment is composed of two or more alkyleneoxy groups, the AO segment may be a random polymer or a block polymerization. Things.

In the formula (II-1), a specific example of D ₁ may be a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group or a hexyl group. When D ₂ represents an alkyl group having 1 to 4 carbon atoms, D ₂ may be a methyl group, an ethyl group, a propyl group or a butyl group or the like.

In the formula (II), the content of the glycidyl group [hereinafter referred to as (i)] and the content of a functional group such as an alkoxyalkyl group or a stanol group (hereinafter abbreviated as (ii)] are molar ratios [(i). And / (ii)] may be from 0.02 to 100, preferably from 0.05 to 50, and more preferably from 0.1 to 10. If the aforementioned molar ratio is less than 0.02, the content of functional groups such as alkoxyalkyl or stanol groups is excessive, based on the designed knot. The structure is difficult to synthesize, and the obtained product has the defect of poor stability. When the aforementioned molar ratio is more than 100, the content of a functional group such as an alkoxyalkyl group or a stanol group is extremely small, and the effect of a functional group such as an alkoxyalkyl group or a stanol to be introduced is eliminated.

In the above formula (IV), the content of the glycidyl group [hereinafter referred to as (iii)] and the content of a functional group such as an alkoxyalkyl group or a stanol group (hereinafter abbreviated as (iv)] are molar ratios [hereinafter referred to as (iv)] [ (iii) / (iv)] may be from 0.1 to 9, and preferably from 0.2 to 5.

The organogermanium compound containing a polyfunctional epoxy group is formed by reacting a part of a hydroxyl group and a decane coupling agent to form a bond in the structure of the polyfunctional epoxy group-containing polyglycidyl ether compound. In a specific example, a decane coupling agent having an isocyanate group (hereinafter simply referred to as an isocyanate group) can be used as a decane coupling agent. Among them, a hydroxyl group may form a urethane bond with an isocyanate group.

In one embodiment, the polyfunctional epoxy group-containing organogermanium compound may be a polyfunctional epoxy group-containing compound having at least two epoxy groups and at least one alkoxyalkyl group and a stanol group. The polyfunctional epoxy group-containing compound having at least two epoxy groups and at least one alkoxyalkyl group and a stanol group may be a polyglycidyl ether compound having at least two epoxy groups and at least one hydroxyl group. The hydroxy group is prepared by reacting an isocyanate group of a decane coupling agent having an isocyanate group and at least one alkoxy or stanol group.

In this specific example, when (poly)glycerol polyglycidyl ether is used as the polyglycidyl ether compound having at least two epoxy groups and at least one hydroxyl group, a compound represented by the above formula (II) can be obtained. (E). When the mountain When the sorbitol polyglycidyl ether is used as the above polyglycidyl ether compound having at least two epoxy groups and at least one hydroxyl group, the compound (E) represented by the above formula (IV) can be obtained.

The aforementioned (poly)glycerol polyglycidyl ether may have a structure represented by the following formula (V):

In the formula (V), D ₃ represents a hydrogen atom or a glycidyl group, wherein at least one D ₃ represents a hydrogen atom, and at least two D ₃ represent a glycidyl group. The definition of a is as described above.

As shown in the formula (V), the molar ratio [(v)/(vi)] of the content of the glycidyl group [hereinafter abbreviated as (v)] and the content of the hydroxyl group [hereinafter referred to as (vi)] may be 0.01 to 100, preferably from 0.02 to 50, and more preferably from 0.1 to 40. Further, the epoxy equivalent thereof may be from 100 to 500, preferably from 100 to 400, and more preferably from 100 to 300. When the epoxy equivalent is less than 100, the (poly)glycerol polyglycidyl ether represented by the formula (V) is not easily synthesized, and if the epoxy equivalent is more than 500, the epoxy group content is too low, and the obtained content is contained. The compound of a polyfunctional epoxy group is added to the negative photosensitive resin composition, and after the lithography process, the formed pixel colored layer is less likely to achieve the effect of improving the splash resistance.

The aforementioned sorbitol polyglycidyl ether may have a structure represented by the following formula (VI):

In the formula (VI), D ₄ represents a hydrogen atom or a glycidyl group, wherein at least one D ₄ represents a hydrogen atom, and at least two D ₄ represent a glycidyl group. AO represents an alkoxy group having a carbon number of 2 to 6. f represents an integer of 4 to 10, g represents an integer of 0 to 10, h represents an integer of 0 to 10, and i represents an integer of 0 to 10.

As shown in the formula (VI), the molar ratio [(vii) / (viii)] of the content of the glycidyl group [hereinafter referred to as (vii)] and the content of the hydroxyl group [hereinafter referred to as (viii)] may be 0.1 to 9, and preferably from 0.2 to 5. Second, the epoxy equivalent may be from 100 to 500, preferably from 100 to 400, and more preferably from 100 to 300. When the epoxy equivalent is less than 100, the sorbitol polyglycidyl ether represented by the formula (VI) is not easily synthesized. When the epoxy equivalent is more than 500, the content of the epoxy group is too low, and the obtained compound containing a polyfunctional epoxy group is added to the negative photosensitive resin composition, which is formed after the lithography process. The pixel coloring layer is not easy to achieve the effect of improving the splash resistance.

The (poly)glycerol polyglycidyl ether and the sorbitol polyglycidyl ether of the polyglycidyl ether compound may be commercially available products, for example, manufactured by Sakamoto Pharmaceutical Co., Ltd., and model number SR-4GL. It is manufactured by Nagase Industrial Co., Ltd. and is modeled after Denacol Ex-1310, Denacol EX-1410, Denacol E-1610 or Denacol EX-610U.

Next, in the reaction with the polyglycidyl ether, a decane coupling agent having a hydrolyzable alkylene group is introduced, which does not react with an epoxy group, and has a functional group which selectively reacts with a hydroxyl group. Among them, the decane coupling agent is preferably an isocyanate decane.

Specific examples of the isocyanate decane may be 3-isocyanate propyl trimethoxy decane, 3-isocyanate propyl methyl dimethoxy decane, 3-isocyanate propyl dimethyl methoxy decane, 3-isocyanate propyl trisole Ethoxy decane, 3-isocyanate propyl methyl diethoxy decane, 3-isocyanate propyl dimethyl ethoxy decane, isocyanate methyl trimethoxy decane, isocyanate methyl methyl dimethoxy decane, Isocyanate methyl dimethyl methoxy decane, isocyanate methyl triethoxy decane, isocyanate methyl methyl diethoxy decane, isocyanate methyl dimethyl ethoxy decane, and the like. Among them, the isocyanate decane may preferably be 3-isocyanate propyl triethoxy decane or 3-isocyanate propyl trimethoxy decane.

In the reaction of the polyglycidyl ether compound and the isocyanate decane, the content of the hydroxyl group in the polyglycidyl ether compound is 1 mol, and the content of the isocyanate group in the isocyanate decane may be 0.01 mol to 1 mol. And preferably from 0.1 mole to 1 mole.

The organofluorene compound having a polyfunctional epoxy group of the present invention can be obtained by reacting a polyglycidyl ether compound with an isocyanate decane. The reaction temperature may be from 25 ° C to 90 ° C, and preferably from 40 ° C to 80 ° C. When the reaction temperature is not within the above range, the reaction rate becomes lower when the reaction temperature is lower than 25 ° C, and the hydroxyl group of the polyglycidyl ether compound and the alkoxyalkyl group of the isocyanate decane are esterified when the reaction temperature is higher than 90 ° C. When exchanging reactions, it may A side reaction occurred. Secondly, the reaction time of the aforementioned reaction is not particularly limited and may generally be from 10 minutes to 24 hours.

In the reaction of the polyglycidyl ether compound and the isocyanate-based decane, the solvent to be used is not particularly limited as long as the solvent does not react with the isocyanate-based decane. Specific examples of the solvent include a hydrocarbon solvent, an aromatic solvent, a ketone solvent, a guanamine solvent, an ester solvent, or an ether solvent. Specific examples of the solvent may be a hydrocarbon solvent such as pentane, hexane, heptane, octane, decane or cyclohexane; an aromatic solvent such as benzene, toluene or xylene; acetone or methyl ethyl ketone; a ketone solvent such as methyl isobutyl ketone or cyclohexanone; a guanamine solvent such as formamide, dimethylformamide, pyrrolidone or N-methylpyrrolidone; ethyl acetate, butyl acetate or An ester solvent such as a lactone; an ether solvent such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran or 1,4-dioxane.

In the reaction of the aforementioned polyglycidyl ether compound with isocyanate decane, a catalyst may be added to the reaction to increase the reaction rate. The catalyst can be the catalyst used in the general polyurethane reaction. Specific examples of the catalyst may be a tertiary amine compound, dibutyltin oxide, dioctyltin oxide or tin(II) bis(2-ethylhexanoate).

The total amount of the polyglycidyl ether compound and the isocyanate decane used is 100% by weight, and the catalyst may be included in an amount of 0.001% by weight to 1% by weight.

The organic ruthenium compound containing the polyfunctional epoxy group can be obtained by a colloidal permeation chromatography method, and the polyvalent epoxy group-containing organic ruthenium compound can have a weight average molecular weight of 200. Up to 10,000, and preferably from 300 to 8,000. When the weight average molecular weight of the organofluorene compound containing a polyfunctional epoxy group is less than 200, the organofluorene compound containing a polyfunctional epoxy group is not easily synthesized. If the organofluorene compound containing a polyfunctional epoxy group has a weight average molecular weight of more than 10,000, it has a defect of being inferior in handleability.

Specific examples of the compound of the present invention can be listed as follows: in the formula (II), b is 3, d is 3, the average value of a is 9, and the content of the glycidyl group and the content of the ethoxylated alkyl group are not The ear ratio is 3; in the formula (II), b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 6; In (II), b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 0.3; in the formula (II), b is 3, d is 3, the average value of a is 7, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 3; in the formula (IV), b is 3, and d is 3, f 4, g, h, and i are both 2, AO is an extended ethoxy group, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 3; in the formula (IV), b is 3 , d is 3, f is 4, g, h and i are both 2, AO is a propoxyl group, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 3; In the formula, b is 3, d is 3, f is 4, g, h and i are both 2, AO is a buttoxy group, and the content of glycidyl group and ethoxy decane are The molar ratio of content is 3; In the formula (IV), b is 3, d is 3, f is 4, g, h and i are both 2, AO is a mixture of an extended ethoxy group and a propenyloxy group, and the content of the glycidyl group is The molar ratio of the content of oxyalkylene group is 3; in the formula (IV), b is 3, d is 3, f is 4, g, h and i are 4, and AO is ethoxylated and extended. a mixture of oxy groups, each AO group is formed as a random polymer, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated decyl group is 3; and in the formula (IV), b is 3, d 3, f is 4, g, h and i are 4, AO is a mixture of ethoxylated and propoxylated, each AO group is formed as a block polymer, and the content of glycidyl group and B The molar ratio of the content of oxyalkylene group is 3.

The compound (E) may be used in an amount of 1 part by weight to 10 parts by weight, preferably 2 parts by weight to 9 parts by weight, based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight, and more preferably 3 parts by weight to 8 parts by weight.

When the negative photosensitive resin composition of the present invention does not contain the compound (E), the pixel-colored layer formed of the negative photosensitive resin composition obtained has a defect of poor sputtering resistance.

Solvent (F)

The solvent (F) is selected from a soluble pigment (A), an alkali-soluble resin (B), an ethylenically unsaturated group-containing compound (C), a photoinitiator (D), and a compound (E), and The components that react with each other and have appropriate volatility.

The solvent (F) may be the same as the solvent used to prepare the alkali-soluble resin (B), and will not be described herein. Preferably, the solvent (F) is selected from the group consisting of propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.

The solvent (F) is used in an amount of 500 parts by weight to 5000 parts by weight, preferably 800 parts by weight to 4,500 parts by weight, based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight, and more preferably 1000 parts by weight to 4000 parts by weight.

Dye (G)

The negative photosensitive resin composition of the present invention may optionally contain a dye (G). According to the use with the aforementioned pigment (A), the dye (G) can select a dye (G) of a specific spectrum. In a specific example of the present invention, the dye (G) may be an azo dye, an azo metal complex dye, an anthraquinone dye, an indigo dye, a sulfonium dye, a phthalocyanine dye, a diphenylmethane dye, or a triphenylmethane. Dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes or oxazine dyes, and the like.

In a preferred embodiment of the present invention, the dye (G) may be CI solvent red 2, CI solvent red 24, CI solvent red 27, CI solvent red 49, CI solvent red 52, CI solvent red 57, CI solvent red. 89, CI solvent red 111, CI solvent red 114, CI solvent red 119, CI solvent red 124, CI solvent red 135, CI solvent red 136, CI solvent red 137, CI solvent red 138, CI solvent red 139, CI solvent red 143, CI solvent red 144, CI solvent red 145, CI solvent red 146, CI solvent red 147, CI solvent red 148, CI solvent red 149, CI solvent red 150, CI solvent red 151, CI solvent red 152, CI solvent red 155, CI solvent red 156, CI solvent red 162, CI solvent red 168, CI solvent red 169, CI solvent red 170, CI solvent red 171, CI solvent red 172, CI solvent red 177, CI solvent red 178, CI solvent red 179, CI solvent red 181, CI solvent red 190, CI solvent red 191, CI solvent red 194, CI solvent red 199, CI solvent red 200, CI solvent red 201, CI solvent red 299, CI direct red 2, CI direct red 81, CI acid red 1. CI acid red 14, CI acid red 27, CI acid red 52, CI acid red 87, CI acid red 88, CI acid red 289, CI alkaline red 1, CI medium red 3, CI ice dyed red 21, CI Red reduction 1, CI reduction red 2, CI reduction red 15, CI reduction red 23, CI reduction red 41, CI reduction red 47, CI dispersion red 1, CI dispersion red 11, CI dispersion red 15, CI dispersion red 22, CI Disperse red 60, CI disperse red 92, CI disperse red 146, CI disperse red 191, CI disperse red 283, CI disperse red 288, CI active red 12. The aforementioned dyes (G) may be used singly or in combination of plural kinds.

The dye (G) is used in an amount of from 0 part by weight to 50 parts by weight, preferably from 0 part by weight to 40 parts by weight, based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight, and more preferably 0 parts by weight to 30 parts by weight.

Additive (H)

The negative photosensitive resin composition of the present invention may optionally include an additive (H) such as a filler, a polymer compound other than the alkali-soluble resin (B), an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomeration. Agents, etc.

The additive (H) may be used singly or in combination, and the additive (H) includes, but is not limited to, a filler such as glass or aluminum; an alkali-soluble resin such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate. Polymer compound other than (B); vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, nitrogen-(2-aminoethyl)-3- Aminopropyl Methyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidylpropyltrimethoxy Decane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, a adhesion promoter such as 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane; 2,2-thiobis (4) -Methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and other antioxidants; 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)- An ultraviolet absorber such as 5-chlorophenyl azide or alkoxyphenone; and an anti-agglomerating agent such as sodium polyacrylate.

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

Preparation of color filters

The present invention also provides a method of producing a color filter comprising the steps of forming a pixel colored layer on a substrate by using the negative photosensitive resin composition described above, thereby producing and providing a color filter.

In other words, the method for manufacturing the color filter of the present invention is mainly mixed into a solution by a coating method such as rotary coating, cast coating, ink-jet coating or roll coating. The aforementioned photosensitive composition in the state is coated on the substrate. After coating, most of the solvent is removed by drying under reduced pressure, and the solvent is removed by pre-bake to form a pre-baked coating film. Among them, the conditions of drying under reduced pressure and pre-baking, according to the type of each component, The ratio varies. The drying under reduced pressure is usually carried out at a pressure of from 0 to 200 mmHg for from 1 second to 60 seconds, and the prebaking is carried out at a temperature of from 70 ° C to 110 ° C for from 1 minute to 15 minutes. After prebaking, the prebaked film was exposed to a designated mask and immersed in a developing solution at a temperature of 23 ± 2 ° C for development. After 15 seconds to 5 minutes, the unexposed portions are removed to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet device may be a (super) high-pressure mercury lamp or a metal halide lamp.

The substrate may be, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, a soda glass, or a glass having a transparent conductive film attached thereto for a liquid crystal display device; or A photoelectric conversion device substrate (for example, a germanium substrate) such as a solid-state imaging device. These substrates generally form a black matrix that separates the colored layers of each pixel.

Further, specific examples of the developer may be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, and diethyl ether. Amine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine, 1,8-diazabicyclo-(5,4,0)-7-undecene An alkaline aqueous solution composed of a basic compound. The concentration of the developer may generally be from 0.001% by weight to 10% by weight, preferably from 0.005% by weight to 5% by weight, and more preferably from 0.01% by weight to 1% by weight.

When the developer composed of the alkaline aqueous solution is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen.

After drying, the substrate having the photo-curing coating layer is heated by a heating device such as a hot plate or an oven at a temperature of 100 ° C to 280 ° C for 1 to 15 minutes to remove volatile components in the coating film and to make the coating film The unreacted ethylenically unsaturated double bond undergoes a thermosetting reaction. A photosensitive resin composition of each color (mainly including red, green, and blue colors) is repeatedly operated in the same step three times on a predetermined pixel to obtain a pixel coloring layer of three colors of red, green, and blue.

Next, on the pixel colored layer, an ITO (indium tin oxide) deposited film is formed under vacuum at a temperature of 220 ° C to 250 ° C, and if necessary, after etching and wiring the ITO deposited film, the liquid crystal alignment film is coated. The quinone imine, which is then fired, can be used as a color filter for liquid crystal displays.

Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and any of an inorganic substance or an organic substance may be used. The technique for forming a liquid crystal alignment film is well known to those of ordinary skill in the art to which the present invention pertains, and is not the focus of the present invention, and therefore will not be further described.

Preparation of liquid crystal display device

The liquid crystal display device of the present invention mainly comprises a color filter (CF) substrate obtained by the above method for producing a color filter, and a drive substrate provided with a thin film transistor (TFT). First, a gap (cell gap) is interposed between the two substrates. After the peripheral portions of the two substrates are bonded together with a sealing agent, the liquid crystal is filled in the gap between the surface of the substrate and the sealing agent. Then, the injection hole is sealed to constitute a liquid crystal cell. Next, on the outer surface of the liquid crystal cell On the upper side (that is, on the other side surfaces of the respective substrates constituting the liquid crystal cell), a polarizing plate is bonded to obtain a liquid crystal display device.

The liquid crystal used in the above, that is, the liquid crystal compound or the liquid crystal composition is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

Preparation of first alkali soluble resin (B-1) Synthesis Example B-1-1

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent: 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight 2,6-di-t-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 at 25 parts by weight/min, and the temperature was maintained at 100. After reacting for 15 hours in the range of ° C to 110 ° C, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heating to 110 ° C to 115 ° C, after reacting for 2 hours, a first alkali-soluble resin (B-1) of Synthesis Example B-1-1 having an acid value of 98.0 mgKOH/g and a number average molecular weight of 1,623 was obtained. -1).

Synthesis Example B-1-2

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent: 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight 2,6-di-t-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 at 25 parts by weight/min, and the temperature was maintained at 100. After reacting for 15 hours in the range of ° C to 110 ° C, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 13 parts by weight of benzophenone tetracarboxylic dianhydride was added, and the reaction was carried out at 90 ° C to 95 ° C for 2 hours. Next, 6 parts by weight of tetrahydrophthalic anhydride was added and reacted at 90 ° C to 95 ° C for 4 hours to obtain Synthesis Example B-1 having an acid value of 99.0 mgKOH/g and a number average molecular weight of 2,162. -2 of a first alkali soluble resin (B-1-2).

Synthesis Example B-1-3

400 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent: 288), 102 parts by weight of acrylic acid, 0.3 Parts by weight of methoxyphenol, 5 parts 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, it was obtained. The acid value was an intermediate product of 2.2 mg KOH/g. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a synthetic example B-1- having an acid value of 102 mgKOH/g and a number average molecular weight of 2,589. The first alkali-soluble resin (B-1-3) of 3.

Synthesis Example B-1-4

200 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent: 288), 60 parts by weight of acrylic acid, 0.15 parts by weight of methoxyphenol, and 2.5 parts by weight The triphenylphosphine and 200 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 2.5 mg KOH / g was obtained. Next, 85 parts by weight of tetrahydrophthalic anhydride was added, and the reaction was carried out at 95 ° C for 4 hours to obtain a synthetic example B-1- having an acid value of 105 mgKOH/g and a number average molecular weight of 3,410. The first alkali-soluble resin (B-1-4) of 4.

Preparation of a second alkali soluble resin (B-2)

The second alkali-soluble resin of Synthesis Example B-2-1 to Synthesis Example B-2-7 was prepared according to Table 1 below.

Synthesis Example B-2-1

A stirrer, thermometer, condenser, and nitrogen inlet were placed on a four-necked flask and nitrogen was introduced. Then, adding 100 parts by weight of propylene glycol Methyl ether acetate (abbreviated as PGMEA) and the temperature was raised to 100 °C. Next, 3 parts by weight of N-(2-phenylethyl)maleimide (abbreviated as NPME), 82 parts by weight of benzyl methacrylate (abbreviated as BzMA), and 10 parts by weight of methyl group 3,4-epoxycyclohexylmethyl acrylate (abbreviated as ECMMA) and 4 parts by weight of 2,2'-azobis-2-methylbutyronitrile (abbreviated as AMBN) are dissolved in 100 parts by weight of propylene glycol methyl ether. In the acetate, the mixed solution was dropped into a four-necked flask in 2 hours. After reacting at 100 ° C for 6.5 hours, 15 parts by weight of acrylic acid (abbreviated as AA) was added to a four-necked flask filled with nitrogen, and the temperature was raised to 110 °C. After reacting for 6 hours, the second alkali-soluble resin (B-2) of Synthesis Example B-2-1 was obtained.

Synthesis Example B-2-2 to Synthesis Example B-2-7

Synthesis Example B-2-2 to Synthesis Example B-2-7 The same preparation method as that of the second alkali-soluble resin of Synthesis Example B-2-1 was used, except that Synthesis Example B-2-2 To Synthesis Example B-2-7, the type and amount of the raw materials in the second alkali-soluble resin were changed, and the formulations thereof are shown in Table 1, respectively, and are not described herein.

Preparation of other alkali soluble resins (B') Synthesis Example B'-1 to Synthesis Example B'-3

Synthesis Example B'-1 to Synthesis Example B'-3 The same preparation method as that of the second alkali-soluble resin of Synthesis Example B-2-1 was used, except that Synthesis Example B'-1 to Synthesis Example B'-3 is used to change the type and amount of raw materials in other alkali-soluble resins, and the formulations thereof are shown in Table 1, and are not described here.

Preparation of compound (E) Synthesis Example E-1

A stirrer, a condenser, a low-liquid funnel, and a thermometer were placed in a 1 liter reaction bottle. 100 g of polyglycerol polyglycidyl ether (epoxy equivalent: 168; manufactured by Sakamoto Pharmaceutical Co., Ltd. and model SR-4GL) was placed in a reaction flask. After heating to 80 ° C, 49.0 g of 3-isocyanate propyl triethoxy decane was added to the dropping funnel and added dropwise to the reaction flask. After stirring at 80 ° C for 4 hours, the absorption peak of the isocyanate group of the raw material was measured by infrared spectroscopy (IR spectroscopy), and it was confirmed that it disappeared, and it was confirmed by the absorption peak of the formed urethane bond, and it was confirmed. Completed for the reaction. The obtained product is the compound (E-1) of Synthesis Example E-1, which is a pale yellow liquid having a weight average molecular weight of 1800 and a viscosity of 1074 mPa. S, and the epoxy equivalent is 265. The obtained product has a structure represented by the formula (II), wherein b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated decyl group is 3. .

Synthesis Example E-2

A stirrer, a condenser, a low-liquid funnel, and a thermometer were placed in a 1 liter reaction bottle. 100 g of polyglycerol polyglycidyl ether (epoxy equivalent: 168; manufactured by Sakamoto Pharmaceutical Co., Ltd. and model SR-4GL) was placed in a reaction flask. After heating to 80 ° C, 24.5 g of 3-isocyanate propyl triethoxy decane was added to the dropping funnel and added dropwise to the reaction flask. After stirring at 80 ° C for 4 hours, infrared spectrum (Infrared Spectroscopy; IR Spectroscopy) The absorption peak of the isocyanate group of the starting material was measured, and it was confirmed that it had disappeared, and was replaced by the absorption peak of the generated urethane bond, and it was confirmed that the reaction was completed. The obtained product is the compound (E-1) of Synthesis Example E-1, which is a pale yellow liquid having a weight average molecular weight of 1,700 and a viscosity of 1,184 mPa. S, and the epoxy equivalent is 219. The obtained product has a structure represented by the formula (II), wherein b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated decyl group is 6. .

Synthesis Example E-3

A stirrer, a condenser, a low-liquid funnel, and a thermometer were placed in a 1 liter reaction bottle. 100 g of polyglycerol polyglycidyl ether (epoxy equivalent: 168; manufactured by Sakamoto Pharmaceutical Co., Ltd. and model SR-4GL) was placed in a reaction flask. After heating to 80 ° C, 441.0 g of 3-isocyanate propyl triethoxy decane was added to the dropping funnel and added dropwise to the reaction flask. After stirring at 80 ° C for 4 hours, the absorption peak of the isocyanate group of the raw material was measured by infrared spectroscopy (IR spectroscopy), and it was confirmed that it disappeared, and it was confirmed by the absorption peak of the formed urethane bond, and it was confirmed. Completed for the reaction. The obtained product is the compound (E-1) of Synthesis Example E-1, which is a pale yellow liquid having a weight average molecular weight of 2,500 and a viscosity of 1374 mPa. S, and the epoxy equivalent is 910. The obtained product has a structure represented by the formula (II), wherein b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated decyl group is 0.3. .

Preparation of negative photosensitive resin composition

The negative photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 9 were prepared according to Table 2 below.

Example 1

50 parts by weight of CI Pigment Red 254 (abbreviated as A-1), 100 parts by weight of the second alkali-soluble resin (abbreviated as B'-2-1) obtained in the above Synthesis Example B'-2-1, 20 Parts by weight of EO-modified trimethylolpropyl trimethacrylate (abbreviated as C-1), 5 parts by weight of a photoinitiator as shown in the above formula (I-1) (abbreviated as D-1- 1), 5 parts by weight of 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzofluorenyl) (abbreviated as D-2-1) And 1 part by weight of the compound obtained in the above Synthesis Example E-1 (abbreviated as E-1) is added to 500 parts by weight of ethyl 3-ethoxypropionate (abbreviated as F-1), and is shaken After the stirring type stirrer was uniformly stirred, the negative photosensitive resin composition of Example 1 was obtained. The negative photosensitive resin composition obtained was evaluated by the following evaluation method of sputtering resistance, and the obtained result is shown in the second table.

Example 2 to Example 17 and Comparative Example 1 to Comparative Example 9

Examples 2 to 17 and Comparative Examples 1 to 9 were prepared in the same manner as in the production method of the negative photosensitive resin composition of Example 1, except that Examples 2 to 17 and comparison were made. In the examples 1 to 9, the types and amounts of the raw materials in the photosensitive resin composition were changed, and the formulations and evaluation results are shown in Table 2, respectively, and are not described here.

Evaluation method Sputter resistance

The photosensitive resin compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 9 were changed in chromaticity before and after sputtering, whereby the sputtering resistance was evaluated. Briefly, the negative photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 9 were applied by spin coating to a glass substrate having a size of 100 mm × 100 mm. . Then, it was dried under reduced pressure at a pressure of 100 mmHg for 30 seconds. Next, a pre-bake process was carried out at a temperature of 80 ° C for 2 minutes to form a pre-baked film having a film thickness of 2.5 μm. After the pre-baking process, the pre-baked coating film was irradiated with ultraviolet light having an energy of 60 mJ/cm ² (exposure machine model: Canon PLA-501F), and the exposed pre-baked coating film was immersed in a developing solution at 23 ° C. . After 1 minute, the coating film was washed with pure water and baked at 230 ° C for 30 minutes to form a pixel colored layer on the glass substrate.

Next, the chromaticity (L*, a*, b*) was measured with a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model number MCPD), and then a film resistance was formed by sputtering on the pixel colored layer. An ITO film of 14.6 Ω/sq and a film thickness of 2040 Å was prepared to obtain the color filter in which the sputtering temperature was 220 °C.

Thereafter, the chromaticity of the color filter is measured again, and the chromaticity change (ΔEab*) is calculated by the following formula (VIII), and the smaller the chromaticity change (ΔEab*) is obtained, the better the sputter resistance is. And evaluated according to the following evaluation criteria:

☆: △ Eab * < 1; ◎: 1 ≦ △ Eab * < 2; ○: 2 ≦ △ Eab * < 3; ×: 3≦ΔEab*.

As is apparent from the results of the second table, when the photoinitiator (D) of the present invention does not contain the photoinitiator (D-1) as shown in the formula (I), the resulting negative photosensitive resin is composed. The pixel colored layer formed by the object has a defect of poor sputtering resistance.

When the negative photosensitive resin composition of the present invention does not contain the compound (E), the pixel-colored layer formed of the negative photosensitive resin composition obtained has a defect of poor sputtering resistance.

Further, when the alkali-soluble resin (B) of the present invention contains the first alkali-soluble resin (B-1), the pixel-colored layer formed of the negative-type photosensitive resin composition obtained can have better resistance to splashing. Plating. When the alkali-soluble resin (B) of the present invention contains the second alkali-soluble resin (B-2), the pixel-colored layer formed of the negative-type photosensitive resin composition obtained can have better sputter resistance.

It should be noted that, although the present invention is exemplified by specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments, the negative photosensitive resin composition of the present invention and its application are described, but in the technical field to which the present invention pertains It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds, compositions, reaction conditions, and other conditions may be used for the negative photosensitive resin composition of the present invention and its application without departing from the spirit and scope of the present invention. Process, analytical method or instrumentation.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any of the technical fields in the art to which the present invention pertains is generally known. The scope of protection of the present invention is defined by the scope of the appended claims, and the scope of the invention is defined by the scope of the appended claims.

A-1 C.I. Pigment Red 254

A-2 C.I. Pigment Green 36

A-3 C.I. Pigment Blue 15:6

A-4 C.I. Pigment Blue 66

A-5 C.I. Pigment Red 177

C-1 EO modified trimethylol propyl trimethacrylate

C-2 dipentaerythritol hexaacrylate

C-3 caprolactone modified dipentaerythritol hexaacrylate

D-1-1 photoinitiator represented by formula (I-1)

D-1-2 Light initiator as shown in formula (I-8)

D-1-3 Photoinitiator of formula (I-27)

D-2-1 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinium)

D-2-2 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyl-biimidazole]

D-2-3 4,4'-bis(diethylamino)benzophenone [4,4'-bis(diethylamino)benzophenone]

D-2-4 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1 -(4-morpholinophenyl)-1-butanone]

F-1 3-ethoxypropionate ethyl ester

F-2 propylene glycol methyl ether acetate

F-3 cyclohexanone

G-1 C.I. Solvent Red 24

G-2 C.I. Solvent Red 49

G-3 C.I. Acid Red 289

H-1 3-glycidylpropyltrimethoxydecane

H-2 vinyl triethoxy decane

Claims (11)

A negative photosensitive resin composition comprising: a pigment (A); an alkali-soluble resin (B); a compound (C) having an ethylenically unsaturated group; a photoinitiator (D); E); and a solvent (F), wherein the photoinitiator (D) comprises a photoinitiator (D-1) having the structure represented by the following formula (I): In the formula (I), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ , OE ₁₇ , halogen atom, NO ₂ or ; Or E ₁ and E _2, E _2, and E _3, E ₃ and E _4, E ₅ and E _6, E ₆ or E ₇ and E ₇ and E ₈ each independently represent by Alternate carbon number is 2 to 10 alkenyl; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are respectively independent Commonly represented by -(CH ₂ ) _p -W-(CH ₂ ) _q -; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are independently represented Wherein at least one of E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or at least one group as shown below. Substituted, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, CN, OH, SH, an alkoxy group having a carbon number of 1 to 4, (CO)OH or (CO)O(R ₁ ), wherein R ₁ represents an alkyl group having 1 to 4 carbon atoms; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, The at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ are independently represented a halogen atom, CN, OE ₁₇ , SE ₁₈ , SOE ₁₈ , SO ₂ E ₁₈ or NE ₁₉ E ₂₀ , wherein the substituents OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ are not or via such groups E ₁₇ , E ₁₈ , E ₁₉ and/or E ₂₀ form a five-membered or six-membered ring with one carbon atom of the naphthalene ring; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ respectively represent independently , COE ₁₆ or NO ₂ ; W represents O, S, NE ₂₆ or a single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z ₁ represents CO or a single bond; and E ₁₃ represents a carbon number of 1. The alkyl group having a carbon number of from 1 to 20 is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from a halogen atom, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ , NE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ or Or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interspersed with one or more of O, S, SO, SO ₂ , NE ₂₆ or CO; or E ₁₃ represents carbon The number of alkenyl groups of 2 to 12, the alkenyl group having 2 to 12 carbon atoms which is undoped or inter-hetero-doped with one or more O, CO or NE ₂₆ , wherein the inter- and hetero-carbon number is 2 to 20 And the alkenyl group having 2 to 12 carbon atoms without undoped or intervening is unsubstituted or substituted with at least one halogen atom; or E ₁₃ represents a cycloalkenyl group having 4 to 8 carbon atoms and having a carbon number of 2 An alkynyl group of 12, or a cycloalkyl group having 3 or 10 carbon atoms without an inter or hetero or hetero or O, S, CO or NE ₂₆ ; or E ₁₃ representing a phenyl or naphthyl group, and the phenyl group Or the naphthyl group is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , , COE ₁₆ , CN, NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, intermixed with one or more O, S, CO or NE ₂₆ and having a carbon number of 2 An alkyl group of up to 20; or the phenyl group or the naphthyl group is each substituted with a cycloalkyl group having a carbon number of 3 to 10 or each interstitial having one or more O, S, CO or NE ₂₆ and having a carbon number of 3 to 10 Cycloalkyl substituted; k represents an integer from 1 to 10; E ₁₄ represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms which is substituted with or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, a phenyl group, and an alkyl group having 1 to 20 carbon atoms. Phenylphenyl or CN; or E ₁₄ represents phenyl or naphthyl, each unsubstituted or substituted by at least one group as shown below, and the at least one group is selected from the group consisting of a C 1 to 6 alkane a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, CN, OE ₁₇ , SE ₁₈ and/or NE ₁₉ E ₂₀ ; or E ₁₄ representing a heteroaryl group having 3 to 20 carbon atoms and having a carbon number of 1 to Alkoxy, benzyloxy or phenoxy group, the benzyloxy group and the phenoxy group are not taken Or the group substituted with at least one of the following, and the at least one group selected from an alkyl group having a carbon number of 1 to 6 carbon atoms, a haloalkyl group of 1 to 4 and / or a halogen atom; E ₁₅ represents a carbon An aryl group having 6 to 20 or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group and a halogen group. Atom, haloalkyl having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ , bonded to SO and having a carbon number of 1 to 10 An alkyl group, an alkyl group bonded to SO ₂ and having a carbon number of 1 to 10, an intervening one or more O, S or NE ₂₆ and an alkyl group having 2 to 20 carbon atoms; or each carbon number thereof is 1 An alkyl group substituted to 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms butoxycarbonyl, OE _17, SE _18, or NE ₁₉ E _20; E ₁₅ represents a hydrogen atom or, Alkenyl group of 2 to 12, have interrupted or not interrupted by one or more O, CO, or NE ₂₆ carbon atoms and a cycloalkyl group of 3 to 8; or E ₁₅ represents a carbon atoms of an alkyl group having 1 to 20, The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OE ₁₇ , SE ₁₈ , and a carbon number of 3 to 8. a cycloalkyl group, a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ , PO(OC _k H _2k+1 ) ₂ , , a phenyl group, wherein the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, and the phenyl group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E _{20 is} substituted; or E ₁₅ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is one or more O, SO or SO ₂ . The alkyl group having a carbon number of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OE ₁₇ , COOE ₁₇ , and CONE ₁₉ E _{20 .} a phenyl group or a phenyl group substituted with OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents an alkanoyl group or a benzamidine group having a carbon number of 2 to 20, which is unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents an unsubstituted group Or a naphthylmethyl group substituted with at least one OE ₁₇ or a heteroarylcarbonyl group having a carbon number of 3 to 14; or E ₁₅ represents an alkoxycarbonyl group having a carbon number of 2 to 12, and the carbon number is 2 to 12 The alkoxycarbonyl group is unintercalated or at least one O Wherein the interrupted or not interrupted by a carbon atoms and an alkoxycarbonyl group having 2 to 12 lines of unsubstituted or substituted by at least one hydroxyl group; or E ₁₅ Representative phenoxycarbonyl, phenoxycarbonyl which is unsubstituted lines Or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents CN, CONE ₁₉ E ₂₀ , NO ₂ , haloalkyl having a carbon number of 1 to 4, S(O) _r -R ₂ , bonded to S(O) _r a phenyl group, wherein the phenyl group bonded to S(O) _r is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO ₂ -R ₂ , and R ₂ represents a carbon number of 1 to 6 alkyl; or E ₁₅ represents a phenyl group bonded to the SO ₂ O, diphenylphosphino acyl or di (R ₃₎ - phosphino acyl, SO ₂ O wherein the bond with the phenyl unsubstituted or lines Substituted by an alkyl group having 1 to 12 carbon atoms, and R ₃ represents an alkoxy group having 1 to 4 carbon atoms; r represents an integer of 1 to 2; and E' ₁₄ represents one of the definitions for E ₁₄ ; E _'15 represents a ₁₅ for one of those defined in E; Z ₂ representative of O, S, SO, or SO _2; Z ₃ Table O, CO, S or a single bond; E ₁₆ represents a carbon atoms or an aryl group of 6 to 20 carbon atoms of the 3 to 20 hetero aryl group, each of which is unsubstituted or is at least as shown by a substituted And the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , one or more O, S Or NE ₂₆ and an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or at least one group as shown below And wherein the at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, a heteroaryl group having a carbon number of 3 to 20, and a carbon number of An aryloxycarbonyl group of 6 to 20, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ representing a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a phenyl group, an OH group, a SH group, a CN group, and a carbon number. 3 to 6 alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO O(R ₁ ), O(CO)-(R ₁ ), O(CO)-phenyl or (CO)OH or (CO)O(R ₁ ); or E ₁₆ represents a carbon number of 2 to 12 An alkyl group having 2 to 12 alkyl interstitials having one or more O, S or NE ₂₆ ; or E ₁₆ representing (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO) -(R ₄ ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R ₄ represents an alkyl group having 1 to 8 carbon atoms; or E ₁₆ represents a substitution with SE ₁₈ a phenyl group, wherein E ₁₈ represents a single bond to the phenyl group or the naphthyl ring to which the carbazole moiety is attached to the COE ₁₆ ; n represents an integer from 1 to 20; and E ₁₇ represents a hydrogen atom, benzene group -R _5, an alkyl group having a carbon number of 1 to 20, which system the at least one substituent group is unsubstituted or illustrated by the following, and the at least one group selected from a halogen atom, OH, SH, CN, Alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ), O(CO)-(R ₆ ), a phenyl group bonded to O(CO), (CO)OH, (CO)O(R ₁ ), a cycloalkyl group having a carbon number of 3 to 20, SO ₂ -(R ₇ ), O(R ₇ ) or interrupted by O and at least one cycloalkyl group having a carbon number of 3 to 20, wherein R ₅ represents an alkyl group having a carbon number of 1-3, R ₆ represents a carbon number of 2 to 4 Group, and R ₇ represents a haloalkyl group having a carbon number of 1 to 4; or E ₁₇ represents a carbon atoms of an alkyl group of 2 to 20, carbon atoms and the alkyl group of 2 to 20 based interrupted by one or more O, S Or NE ₂₆ ; or E ₁₇ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), alkane fluorenyl group having 1 to 8 carbon atoms, carbon number Is an alkenyl group of 2 to 12, an olefin group having a carbon number of 3 to 6, or a cycloalkyl group having a carbon number of 3 to 20, which is one or more O, S, CO or NE ₂₆ without impurity or impurity; Or E ₁₇ represents a group formed by bonding an alkyl group having 1 to 8 carbon atoms to a cycloalkyl group having 3 to 10 carbon atoms, and the group is uninterfering or via at least one O; or E ₁₇ Represents a benzamidine group which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or An alkoxy group having a carbon number of 1 to 3; or E ₁₇ represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group as shown below, and The at least one group is selected from the group consisting of a halogen atom, OH, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN, NO ₂ , Phenyl-R ₈ , phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N(R ₉ ) ₂ , diphenyl-amino or Wherein R ₈ represents an alkoxy group having a carbon number of 1 to 3, and R ₉ represents an alkyl group having a carbon number of 1 to 12; or E ₁₇ and has or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R ₅ group, wherein The alkenyl group having 2 to 12 carbon atoms, the cycloalkyl group having 3 to 20 carbon atoms, and the phenyl-R ₅ group having no or hetero or one or more O, S, CO, NE ₂₆ or COOE ₁₇ Or E ₁₈ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group of the formula: wherein the at least one group is selected from OH , SH, CN, alkoxy groups having a carbon number of 3 to 6, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₆ ), O(CO)- (R ₁ ), O(CO)-phenyl or (CO)OE ₁₇ ; or E ₁₈ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms has one or more O , S, CO, NE ₂₆ or COOE ₁₇ ; or E ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), alkane having 2 to 8 carbon atoms a mercapto group or an olefin group having a carbon number of 3 to 6; or E ₁₈ represents a benzamidine group which is unsubstituted or substituted with at least one group as shown below, and the at least one group Is selected from a carbon number of 1 to 6 a group, a halogen atom, an OH group, an alkoxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms; or E ₁₈ represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20 Each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. Alkoxy group having a carbon number of 1 to 12, CN, NO ₂ , phenyl-R ₈ , phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N(R ₉ ) ₂ , diphenylamino, (CO)O(R ₄ ), (CO)-R ₄ , (CO)N(R ₄ ) ₂ or E ₁₉ and E ₂₀ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of 2 Alkenyl group to 5, cycloalkyl group having 3 to 20 carbon atoms, phenyl-R ₅ , alkanoyl group having 1 to 8 carbon atoms, alkyl alkoxy group having 1 to 8 carbon atoms, carbon number 3 to 12 olefinic groups, SO ₂ -R ₇ or benzamidine groups; or E ₁₉ and E ₂₀ represent a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 1 to 12 An alkyl group, a benzhydryl group or an alkoxy group having a carbon number of 1 to 12; or an E ₁₉ and E ₂₀ system together with an attached nitrogen atom to form a five-membered member having no inter or heterogeneous O, S or NE ₁₇ Or a six-membered saturated or unsaturated ring, and the five or six member saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of 1 carbon number to an alkyl group having a carbon number of 20 is alkyl group of 1 to _{20, = O, OE 17, SE} 18, NE 21 E 22 _{(CO) E 23, NO 2} , a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, phenyl, Or a cycloalkyl group having one or more O, S, CO or NE ₁₇ and having a carbon number of 3 to 20 without interstitial or heterogeneous; or E ₁₉ and E ₂₀ together with the attached nitrogen atom to form a heteroaromatic a ring system, the heteroaromatic ring system being unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and having a carbon number of 1 to 4 Haloalkyl, alkoxy with 1 to 20 carbon atoms, =0, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , (CO) E ₂₃ , a halogen atom, NO ₂ , CN, phenyl, or a cycloalkyl group having one or more O, S, CO or NE ₁₇ and having a carbon number of 3 to 20 without interstitial or heterogeneous; E ₂₁ and E ₂₂ are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; E ₂₁ and E ₂₂ and a nitrogen atom attached thereto Forming a five- or six-membered saturated or unsaturated ring having no or interstitial or O, S or NE ₂₆ , wherein the five or six member saturated or unsaturated ring system is not fused or fused to the benzene ring; ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O, CO or NE ₂₆ and having a carbon number of 2 to 20, which is not a cycloalkyl group having an O, S, CO or NE ₂₆ and having a carbon number of 3 to 20; or E ₂₃ representing a phenyl group, a naphthyl group, a phenyl-R ₁ , OE ₁₇ , SE ₁₈ or NE ₂₁ E ₂₂ E ₂₄ stands for (CO) OE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E ₁₇ or has one of the definitions for E ₁₉ and E ₂₀ ; E ₂₅ stands for COOE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E ₁₇ ; or E ₂₅ has one of the definitions for E ₁₇ ; E ₂₆ represents a hydrogen atom An alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O or CO and having a carbon number of 2 to 20; or E ₂₆ representing a phenyl-R ₁ group; a cycloalkyl group which is heterozygous or has at least one O or CO and a carbon number of 3 to 8; or E ₂₆ represents (CO)E ₁₉ ; or E ₂₆ represents a phenyl group, and the E ₂₆ system is unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or , but the photoinitiator (D-1) having the structure of the formula (I) has at least one The compound (E) comprises a compound represented by the formula (II) and/or a compound represented by the formula (IV): In the formula (II), D represents a hydrogen atom, a glycidyl group, or a structure represented by the following formula (II-1), wherein at least one D represents a structure represented by the following formula (II-1), and at least two D represents a glycidyl group; a represents an integer from 1 to 100: In the formula (II-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents an integer of 1 to 3, and d represents An integer from 1 to 10; In the formula (IV), D' represents a hydrogen atom, a glycidyl group or a structure represented by the following formula (II-1), wherein at least one D' represents a structure as shown in the formula (II-1), and at least two D' represents a glycidyl group; AO represents an alkylene group having a carbon number of 2 to 6; f represents an integer of 4 to 10; g represents an integer of 0 to 10; h represents an integer of 0 to 10; and i represents 0 An integer of up to 10: In the formula (II-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents an integer of 1 to 3; and d represents An integer from 1 to 10. The negative photosensitive resin composition according to claim 1, wherein in the photoinitiator (D-1) having the structure represented by the formula (1), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₂ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ or NO ₂ ; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are respectively independently represented Wherein at least one of E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are Z ₁ represents CO or a single bond; E ₁₃ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from a halogen atom, OE ₁₇ , SE ₁₈ , COOE ₁₇ , CONE ₁₉ E ₂₀ or PO(OC _k H _2k+1 ) ₂ ; or E ₁₃ represents an alkyl group having a carbon number of 2 to 20, An alkyl group having 2 to 20 carbon atoms having one or more O, S, NE ₂₆ or CO; or E ₁₃ representing a phenyl or naphthyl group, each of which is unsubstituted or at least one Or COE ₁₆ substituted; E ₁₄ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms; and E ₁₅ represents a phenyl group, a naphthyl group, and a heteroaryl group having a carbon number of 3 to 20. a group, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, OE ₁₇ , SE ₁₈ , An alkyl group having at least one O or S and having a carbon number of 2 to 20, or each of which is substituted with one or more alkyl groups having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is not Substituting or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of a heteroaryl group of 3 to 20, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or PO (OC _k H _{2k +1} ) ₂ ; or E ₁₅ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group The group is selected from OE ₁₇ , SE ₁₈ , a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of 3 to 20 heteroaryl, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ or PO(OC _k H _2k+1 ) ₂ ; E' ₁₄ represents one of the definitions for E ₁₄ ; E' ₁₅ represents One of the definitions of E ₁₅ ; E ₁₆ represents a phenyl group, E ₁₆ is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , an alkyl group having at least one O, S or NE ₂₆ and having a carbon number of 2 to 20; or E ₁₆ representing a phenyl group, and the phenyl group is substituted with at least one alkyl group having 1 to 20 carbon atoms, Wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl group, a cycloalkyl group having 3 to 8 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and The at least one group is selected from a halogen atom, a phenyl group, and an OH group. , SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ (CO)O(R ₁ ), O(CO)-(R ₁ ) or (CO)O(R ₁ ); E ₁₇ An alkyl group having a carbon number of 1 to 20, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OCH ₂ CH ₂ (CO)O(R ₁ ), O(R ₁ ), (CO)O(R ₁ ), a cycloalkyl group having 3 to 20 carbon atoms, wherein the carbon number is 3 to 20 cycloalkyl groups Is not hetero or heterozygous at least one O; or E ₁₇ represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having a carbon number of 2 to 20 is at least one O; and E _{18 is} substituted by (CO)OE ₁₇ Methyl; E ₁₉ and E ₂₀ each independently represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms or an alkanoyloxy group having 1 to 8 carbon atoms. Or E ₁₉ and E ₂₀ together with the attached nitrogen atom to form a heteroaromatic ring system which is unsubstituted or Substituting, but the photoinitiator (D-1) having the structure of the formula (I) has The negative photosensitive resin composition according to claim 1, wherein in the photoinitiator (D-1) having the structure represented by the formula (I), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom; or E ₁ and E ₂ , E ₃ and E ₄ or E ₅ and E ₆ are respectively independently represented And at least one of E ₁ and E ₂ , E ₃ and E ₄ or E ₅ and E ₆ are E ₂ represents , COE ₁₆ , NO ₂ or ; or E ₇ represents Or COE ₁₆ ; E ₉ , E ₁₁ and E ₁₂ represent a hydrogen atom; E ₁₀ represents a hydrogen atom, OE ₁₇ or COE ₁₆ ; Z ₁ represents CO or a single bond; and E ₁₃ represents an alkyl group having a carbon number of 1 to 20, The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, E ₁₇ , OE ₁₇ , SE ₁₈ or PO (OC _k H _2k+1 ) ₂ ; or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having a carbon number of 2 to 20 is at least one O; or E ₁₃ represents a phenyl group; k represents an integer 2; E ₁₄ An alkyl group or a thienyl group having a carbon number of 1 to 20; E ₁₅ represents a phenyl group or a naphthyl group, and each of them is unsubstituted or substituted with at least one OE ₁₇ or an alkyl group having 1 to 20 carbon atoms; or E ₁₅ And represents a thienyl group, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group Is selected from OE ₁₇ , SE ₁₈ , a cycloalkyl group having a carbon number of 3 to 8, NE ₁₉ E ₂₀ or COOE ₁₇ ; or E ₁₅ represents an alkyl group having a carbon number of 2 to 20, and the carbon number is 2 to 20 the alkyl group interrupted by SO _2; E ₁₆ represents a phenyl or naphthyl group, each of which is unsubstituted Substituted with at least one of the radicals shown below, and the at least one group selected from _{OE 17, SE 18, NE 19} E 20 carbon atoms or an alkyl group of 1 to 20; E _16, or on behalf of thienyl; E ₁₇ a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below And the at least one group is selected from a halogen atom, O(CO)-(R ₁ ), O(CO)-(R ₆ ), or a cycloalkyl group having at least one O and a carbon number of 3 to 20; Or E ₁₇ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is at least one O; E ₁₈ represents a cycloalkyl group having 3 to 20 carbon atoms and a carbon number of 1 to 20 An alkyl group, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one OH, O(CO)-(R ₆ ) or (CO)OE ₁₇ ; or E ₁₈ represents a phenyl group, The phenyl group is unsubstituted or substituted with at least one halogen atom; E ₁₉ and E ₂₀ each independently represent an alkanoyl group having a carbon number of 1 to 8 or a C 1 to 8 alkyl anthracene group; or E ₁₉ And the E ₂₀ system together with the attached nitrogen atom forms a five or six member saturated ring interspersed with O, provided that the formula (I) The photoinitiator (D-1) of the structure shown has at least one . The negative photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) comprises a first alkali-soluble resin (B-1), and the first alkali-soluble resin (B-1) Prepared by a polymerization reaction of a mixture, and the mixture comprises an epoxy compound (b-1-1) having at least two epoxy groups and one having at least one carboxylic acid group and at least one ethylenically unsaturated group Compound (b-1-2). The negative photosensitive resin composition according to claim 4, wherein the epoxy compound (b-1-1) having at least two epoxy groups has a formula (III-1-1) or a formula Structure shown in (III-1-2); In the formula (III-1-1), Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 An alkoxy group to 5, an aromatic group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms; In the formula (III-1-2), Y ₅ to Y ₁₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and g represents 0 to An integer of 10. The negative photosensitive resin composition according to Item 1, wherein the total amount of the alkali-soluble resin (B) used is 100 parts by weight, and the pigment (A) is used in an amount of 50 parts by weight to 500 parts by weight. The compound (C) having an ethylenically unsaturated group is used in an amount of 20 parts by weight to 200 parts by weight, and the photoinitiator (D) is used in an amount of 10 parts by weight to 100 parts by weight per part by weight of the compound ( E) is used in an amount of from 1 part by weight to 10 parts by weight, and the solvent (F) is used in an amount of from 500 parts by weight to 5000 parts by weight. The negative photosensitive resin composition according to claim 4, wherein the total amount of the alkali-soluble resin (B) is 100 parts by weight based on the total amount of the alkali-soluble resin (B), and the amount of the first alkali-soluble resin (B-1) is used. It is 5 parts by weight to 100 parts by weight. The negative photosensitive resin composition according to claim 1, wherein the total amount of the alkali-soluble resin (B) used is 100. The photoinitiator (D-1) having a structure represented by the formula (I) is used in an amount of from 5 parts by weight to 100 parts by weight per part by weight. A method of producing a color filter, comprising the step of forming a pixel colored layer by using the negative photosensitive resin composition according to any one of claims 1 to 8. A color filter produced by the method described in claim 9 of the patent application. A liquid crystal display device comprising the color filter of claim 10 of the patent application.