JP2013142087A - Highly sensitive oxime ester photopolymerization initiator and photopolymer composition containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerization initiator excellent in sensitivity and including an oxime ester structure.SOLUTION: There is provided an oxime ester compound having a carbazole group, useful as a photoinitiator in photo-crosslinking reaction, specifically, an oxime ester compound improved in solubility by substituting the ether or ester with the nitrogen group of a carbazole group. Such photoinitiator is useful for an LCD black resist, color resist, over coat, column spacer and organic insulation film and the like.

Description

  The present invention relates to an oxime ester compound useful as a photoinitiator (photopolymerization initiator) and a photopolymerization initiator composition using the oxime ester compound.

  The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and polymerizing by irradiating such photosensitive composition with mixed light of 365 nm, 405 nm, and 436 nm. Since it can be cured, it is used in photo-curable inks, photosensitive printing plates, various photoresists, and the like. Since a photosensitive composition having sensitivity to a light source having a short wavelength enables fine printing, a photopolymerization initiator having excellent sensitivity to a 365 nm light source is particularly required.

  Patent Document 1 discloses a photoinitiator having an oxime ester group as a photopolymerization initiator used in the photosensitive composition, and various oxime esters that can be used as a photoinitiator. The structure and synthesis of the compounds are described in detail.

International Patent Publication WO02 / 100903A1

  However, when such an oxime ester compound disclosed in the patent document is used as a photopolymerization initiator, a decomposition product due to light adheres to the mask at the time of exposure, resulting in a pattern defect in the printing process, The yield was reduced. Further, the decomposition temperature is 240 ° C. or lower, and the photopolymerization initiator is decomposed in the thermosetting step after the development process, thereby reducing the adhesion and alkali resistance of the photosensitive composition. Therefore, there is a demand for a photopolymerization initiator that has a high thermal decomposition temperature, causes the decomposition product of the initiator by light irradiation to volatilize, and does not contaminate the polymer or apparatus.

  The present invention, as a high-sensitivity photoinitiator, is not decomposed by light at the time of exposure to the mask, and at the same time is excellent in developability, adhesion, and alkali resistance, and by making the UV maximum absorbance close to 365 nm and 405 nm, It aims at providing the photoinitiator containing the oxime ester structure excellent in the sensitivity. Another object of the present invention is to provide a photoinitiator compound that can achieve appropriate solubility in a solvent used in the photopolymerization composition and a photosensitive compound containing the photoinitiator compound. According to another embodiment of the present invention, a photosensitive composition comprising such an oxime ester compound as a photoinitiator is provided. In particular, a resist for forming a black matrix, a color filter or a column spacer pattern with improved thin film characteristics, an organic insulating film, and a photosensitive composition for overcoat are provided.

  The present invention has been made to solve the above problems, and provides an oxime ester compound represented by the following chemical formulas 1 to 4.

In the above chemical formulas 1 to 4, R ₁ is —CH ₃ , —C ₂ H ₅ , —propyl, —butyl, —hexyl, —octyl, —benzoyl, —cyclohexyl,
R _{2 is, -CH 3, -C 2 H 5} , - propyl, - a benzoyl group,
R ₃ is —H, a is a methyl or ethyl group, and b is —H or a methyl group.

  In the chemical formulas 3 and 4, X is —O—, —S—, or —Se—.

  In addition, the present invention provides a photopolymerizable compound having at least one compound selected from the compounds represented by the above chemical formulas 1 to 4, a polymer compound soluble in a solvent or an alkaline aqueous solution, and / or an ethylenically unsaturated bond. The photosensitive resin composition containing is provided. The photosensitive resin composition may further include a colorant or a pigment.

  Moreover, this invention provides the column spacer formed from the said photosensitive resin composition.

  Moreover, this invention provides the black matrix formed from the said photosensitive resin composition.

  Moreover, this invention provides the color filter formed from the said photosensitive resin composition.

  Moreover, this invention provides the board | substrate which has an organic insulating film formed from the said photosensitive resin composition.

  Moreover, this invention provides the base material which has a film | membrane formed by coating the said photosensitive resin composition.

  The film is a word processor, computer, television or plasma display panel, polarizing plate surface used in liquid crystal display devices, sunglasses lens, power glasses lens, camera finder lens, instrument cover, automobile glass, train It can be used as glass, light brightness enhancement film, or optical waveguide.

  ADVANTAGE OF THE INVENTION According to this invention, the oxime ester compound excellent in the solubility with respect to PGMEA etc. useful as a solvent of a photosensitive composition can be provided, and, thereby, the oxime ester as a photoinitiator used at the time of a photocrosslinking reaction The amount of the compound can be minimized, and when the photosensitive composition containing this is coated with a thin film, when the solvent is volatilized, the phase separation between the binder and the photoinitiator is reduced and the thin film properties after crosslinking are improved. Can be made. Thereby, a good quality black matrix, a color filter, a column spacer, an insulating film, a photocrosslinkable film, etc. can be manufactured.

  The chitooxime ester compound and the alpha chitooxime ester compound of the present invention are useful as a photoinitiator for a polymerizable compound having an ethylenically unsaturated bond that can simultaneously achieve appropriate solubility and sensitivity in a solvent. And a photosensitive compound containing the same.

  The present invention provides a photosensitive resin composition containing a compound represented by any one of the following chemical formulas 1 to 4 and one or more of the following chemical formulas 1 to 4. Of the following chemical formulas 1 to 4, chemical formulas 1 and 3 include a chitooxime ester structure, and chemical formulas 2 and 4 include an alpha chitooxime ester structure. Moreover, the carbon atom double-bonded with the nitrogen atom of the oxime ester structure of the following chemical formulas 1-4 is combined with the nitrobenzyl group.

In the above chemical formulas 1 to 4, R ₁ is —CH ₃ , —C ₂ H ₅ , —propyl, —butyl, —hexyl, —octyl, —benzoyl, —cyclohexyl,
R _{2 is, -CH 3, -C 2 H 5} , - benzoyl - propyl or
R ₃ is —H, a is a methyl or ethyl group, and b is —H or a methyl group.

  In the chemical formulas 3 and 4, X is —O—, —S—, or —Se—.

  Preferred specific examples of the compounds represented by the above chemical formulas 1 to 4 can be represented by the following chemical formulas.

[Synthesis of Chitooxime Ester Compound of Chemical Formula 1 Containing Carbazole Structure]
The method for producing the compound of Formula 1 of the present invention can be synthesized, for example, by a synthesis process described in Reaction Formula 1 below. However, it is not limited to this.

  A carbazole compound, a carboxylic acid chloride, and a nitrocarboxylic acid chloride are sequentially reacted in the presence of aluminum chloride to obtain an acyl compound. An oxime compound is obtained by reacting the acyl compound with hydroxylamine hydrochloride. Next, when an oxime compound and a carboxylic acid chloride are reacted in the presence of a triethylamine catalyst, a photoinitiator having an oxime ester group represented by the above chemical formula 1 can be obtained.

[Synthesis of an oxime ester of Formula 3 having a diphenyl structure]
The method for producing the compound represented by Chemical Formula 3 of the present invention can be synthesized by, for example, a synthesis process described in Reaction Formula 2 below. However, it is not limited to this.

  A diphenyl compound, a carboxylic acid chloride, and a nitrocarboxylic acid chloride are sequentially reacted in the presence of aluminum chloride to obtain an acyl compound. An oxime compound is obtained by reacting the acyl compound with hydroxylamine hydrochloride. Next, the oxime compound and carboxylic acid chloride are reacted in the presence of a triethylamine catalyst to obtain a chitooxime ester compound represented by Formula 3 above.

[Synthesis of Alpha Chitooxime Ester of Formula 3 Having Carbazole Structure]
The method for producing the compound of Chemical Formula 2 of the present invention can be synthesized by, for example, a synthesis process described in Reaction Formula 3 below. However, it is not limited to this.

  A carbazole compound, a carboxylic acid chloride, and a nitrocarboxylic acid chloride are sequentially reacted in the presence of aluminum chloride to obtain an acyl compound. The acyl compound is reacted with isoamylnitrite in the presence of a hydrochloric acid catalyst to obtain an alpha chitooxime compound. Next, the alpha chitooxime compound and carboxylic acid chloride are reacted in the presence of a triethylamine catalyst to obtain the alpha chitooxime ester compound represented by the above chemical formula 3.

[Synthesis of Alpha Chitooxime Ester of Formula 4 Having Diphenyl Structure]
The method for producing the compound represented by Chemical Formula 4 of the present invention can be synthesized by, for example, a synthesis process described in Reaction Formula 4 below. However, it is not limited to this.

  A diphenyl compound, a carboxylic acid chloride, and a nitrocarboxylic acid chloride are sequentially reacted in the presence of aluminum chloride to obtain an acyl compound. The acyl compound is reacted with isoamylnitrite in the presence of a hydrochloric acid catalyst to obtain an alpha chitooxime compound. Next, the alpha chitooxime compound and carboxylic acid chloride are reacted in the presence of a triethylamine catalyst to obtain the alpha chitooxime ester compound represented by the above Chemical Formula 4.

  The photosensitive resin composition according to the present invention includes at least one oxime ester compound represented by any one of Chemical Formulas 1 to 4 as a photoinitiator.

  In the photosensitive resin composition of the present invention, the oxime ester compound represented by any one of Chemical Formulas 1 to 4 can be used alone as a photoinitiator, and any one of Chemical Formulas 1 to 4 can be used. It can also be used by mixing with other known photoinitiators other than the oxime ester compound represented by one.

  When the oxime ester compound represented by any one of the chemical formulas 1 to 4 is mixed with other known photoinitiators, the oxime ester compound is represented by any one of the chemical formulas 1 to 4. It is preferable that 50% by weight or more of the total oxime ester compound is included in the total amount of the photoinitiator. That is, the solubility of the photoinitiator and the sensitivity maintaining effect can be achieved by the oxime ester compound represented by any one of Chemical Formulas 1 to 4 including 50% by weight or more of the total amount of the total photoinitiator. it can.

  Here, examples of other known photoinitiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone. Acetophenones such as benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, Benzyldimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxa Organic compounds such as sulfa compounds such as tenth, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide Thiol compounds such as peroxides, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -Imidazolyl compounds such as imidazolyl dimer, triazine compounds such as p-methoxytriazine, 2,4,6-tris (卜 lichloromethyl) -s-triazine, 2-methyl-4,6-bis (卜 lichloromethyl) -S Azine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4, 6-bis (卜 lichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 , 6-bis (卜 trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4, 6-bis (卜 trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenol) ethenyl] -4,6-bis (卜 trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (卜 trichloromethyl) -s-triazine, 2- (4-Ethoxystyryl) -4,6-bis (卜 trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (卜 -trichloromethyl) -s-triazine, etc. And an aminoketone compound such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

  In addition, the photosensitive resin composition of the present invention includes, as an increase / decrease agent, cationic dyes such as cynin, xanthene, oxazine, thiazine, diarylmethane, triarylmethane and pyrylium, merocyanine, coumarin, indigo, aromatic amines, phthalocyanine. Neutral dyes such as azo, quinone and thioxanthene photosensitive dyes, and benzophenones, acetophenones, benzoins, thioxanthones, anthraquinones, imidazoles, biimidazoles, coumarins, ketocoumarins, triphenylpyryliums, Compounds such as triazines and benzoic acid can be further included.

  The photosensitive resin composition of the present invention can contain a polymer compound that is soluble in a solvent or an alkaline aqueous solution alone or a mixture of these polymer compounds and a photopolymerizable compound having an ethylenically unsaturated bond. Here, as an example of a polymer compound soluble in a solvent or an alkaline aqueous solution or a photopolymerizable compound having an ethylenic unsaturated bond, specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, fumaric acid, Monomethyl acid, monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate , Acrylic amide, methacrylic amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl Acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethyl Roll propane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, di Monomers, oligomers such as pentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate; polyhydric alcohols and monobasic acid or polybasic acid Obtained by reacting the resulting polyester prepolymer with (meth) acrylic acid Polyester (meth) acrylate, polyurethane (meth) acrylate obtained by reacting a compound having a polyol group and two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type Epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or finger ring epoxy resin, amine Examples thereof include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as an epoxy resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid. Furthermore, a resin obtained by reacting a polybasic acid anhydride with the epoxy (meth) acrylate resin can be used. These photopolymerizable compounds may be cardo resins.

  In particular, a polymer that is soluble in a solvent or an aqueous alkali solution is a polymer having high transparency and is soluble in a developer (solvent or aqueous alkali solution). Examples of such a high molecular polymer include a thermosetting resin, a thermoplastic resin, a photosensitive resin, and the like, and they are used alone or as a mixture of two or more. In particular, those excellent in heat resistance, solvent resistance and chemical resistance are preferred.

  As the compound having an ethylenically unsaturated bond, it may be advantageous to use a multi-functional (meth) acrylic monomer in terms of exposure sensitivity and various resistances after the effect.

  On the other hand, the photosensitive resin composition can contain a pigment or a colorant for application to a color filter or a resist for forming a black matrix, for example.

  Examples of the colorant include red, green, blue and amber mixed cyan, magenta, yellow and black pigments. Examples of the pigment include C.I. I. Pigment yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168, C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment brown 23, 25, 26, C.I. I. And CI pigment black 7 and titanium black.

  According to the present invention, a column spacer, a black matrix, a color filter, a substrate having an organic insulating film from such a photosensitive resin composition, and a substrate having a film formed by coating the substrate are provided, Films are plasma display panels, polarizing plate surfaces used in liquid crystal display devices, sunglasses lenses, power glasses lenses, camera finder lenses, instrument covers, automobile glass, train glass, light brightness enhancement films Or used as an optical waveguide film.

  As a method of forming a pattern using such a photosensitive composition, a photosensitive resin composition is applied on a substrate or a substrate, volatile components such as a solvent are removed from the applied photosensitive composition layer, An example is a method in which a layer from which a volatile component has been removed is exposed through a photomask and then developed. Thus, the present invention provides a cured film obtained through such a curing process.

  Examples of the substrate include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a substrate having a flat surface such as a GaAs substrate, and the like.

  The method for applying the photosensitive resin composition on the substrate is not limited. For example, a coater such as a spin coating method, a casting method, a roll coating method, a slit & spin coating method, or a spinless coater is used. It can apply | coat on a board | substrate etc. by the well-known application | coating methods etc. which apply | coat.

  Next, volatile components such as a solvent can be volatilized by heating. Thus, the layer which consists of solid content of a photosensitive composition is formed on a board | substrate etc. Next, the layer which consists of solid content of a photosensitive composition can be exposed, and an active energy ray can be selectively irradiated through a photomask, for example. As the exposure light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halogen lamp, or the like is usually suitable. A laser beam or the like can also be used as the exposure active energy ray. In addition, electron beams, α rays, β rays, γ rays, X rays, neutron rays and the like can also be used. The active energy ray is irradiated through a photomask. Here, the photomask has, for example, a light shielding layer that shields the active energy ray on the surface of a glass plate. The portion of the glass plate where the light-shielding layer is not provided is a translucent part through which the active energy ray is transmitted, and the photosensitive composition is exposed with a pattern based on the pattern of the translucent part, and the active energy ray is irradiated. There are no unirradiated regions and irradiated regions irradiated with active energy rays.

  The substrate thus exposed is developed with a thin alkaline aqueous solution as an example. When developing, for example, the photosensitive composition layer after exposure can be brought into contact with a thin alkaline aqueous solution. Specifically, a substrate having a photosensitive composition layer formed on the surface thereof is thinly alkaline. It can be immersed in an aqueous solution or a thin alkaline aqueous solution can be ejected in the form of a shower. Examples of the thin alkaline aqueous solution include aqueous solutions of alkaline compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and organic amines. The unirradiated area that is not irradiated with the active energy rays in the photosensitive composition layer is removed by development. On the other hand, the irradiation region of the active energy ray remains as it is to form a pattern.

  The substrate thus developed is usually washed with water and dried to obtain the desired pattern.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only and the scope of the present invention is not limited by these examples.

[Example 1]

1 step: 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) (4-nitrophenyl) methaneone [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ) (4-Nitrophenyl) methanone)] In a nitrogen atmosphere, 30.0 g of N-ethylcarbazole and 180 mL of dried CH ₂ Cl ₂ were added and dissolved. After the reaction was cooled to 0 ° C., 21.1 g of AlCl ₃ was slowly added. To this, 24.46 g of 2-methylbenzoyl chloride was slowly added dropwise at an internal temperature of 5 ° C. or lower. Further, after stirring at room temperature for 5 hours, the temperature of the reactor was brought to 0 ° C., 21.1 g of AlCl ₃ was added, and 29.37 g of 4-nitrobenzoyl chloride was gradually added dropwise so that the temperature did not exceed 5 ° C. did. After stirring for 3 hours, the internal temperature was lowered to 0 ° C. or lower, the solution of the reactor was slowly added to 200 mL of ice water, the mixture was stirred for 1 hour, the layers were separated, and further 1% NaOH
After neutralizing and washing with 200 mL, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator and purified to ethyl acetate and methylene chloride to obtain 55 g of a yellow solid with a yield of 77%.

¹ H-NMR (δ, ppm) DMSOd ₆ : 1.37 (t, 3H), 2.23 (s, 3H), 4.58 (q, 2H), 7.32 (m, 2H), 7. 38 (d, 1H), 7.45 (t, 1H), 7.83 (s, 2H), 7.87 (d, 1H), 7.99 to 8.01 (m, 3H), 8.39 (D, 2H), 8.73 (d, 2H)

Two steps: (E)-(9-ethyl-6-((hydroxyimino) (4-nitrophenyl) methyl) -9H-carbazol-3-yl) (o-tolyl) methane [(E)-(9-ethyl- Synthesis of 6-((hydroxyimino) (4-nitrophenyl) methyl) -9H-carbazol-3-yl) (o-toluyl) methanone] Compound 20 obtained in the above-mentioned step 1 was obtained by adding 68 mL of ethanol and 11 mL of distilled water. Added to. To this reaction was added hydroxylamine hydrochloride (3.3 g) and sodium acetate (6.4 g). The reaction solution was circulated and refluxed for 7 hours, and then cold distilled water was added to form a precipitate. The formed precipitate was filtered and washed with distilled water. The obtained white solid was washed with cold ethanol and then dried to obtain 18.0 g of a light yellow solid with a yield of 87%.

¹ H-NMR (δ, ppm) DMSOd ₆ : 1.37 (t, 3H), 2.23 (s, 3H), 4.58 (q, 2H), 7.32 (m, 2H), 7. 38 (d, 1H), 7.45 (t, 1H), 7.83 (s, 2H), 7.87 (d, 1H), 7.99 to 8.01 (m, 3H), 8.39 (D, 2H), 8.73 (d, 2H), 10.9 (s, 1H, -OH)

Three steps: (E) -1-((((9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) (4-nitrophenyl) methylene) amino) oxy) ethane [(E)- Synthesis of 1-((((9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) (4-nitrophenyl) methylene) amino) oxy) ethanone] The internal temperature was increased under a nitrogen atmosphere. The compound (15.0 g) obtained in the above two steps, methylene chloride (90 mL) and triethyleneamine (3.27 g) were added, and acetyl chloride (2.54 g) was added to methylene chloride (5 mL). The solution dissolved in was slowly added. The internal temperature is raised to 10 ° C. and then stirred for 3 hours. Water was added several times to the reaction solution, the organic layer was washed, and the solid compound obtained by distillation under reduced pressure was added with acetonitrile (100 mL) and methylene chloride (100 mL), and the mixture was circulated and refluxed for 1 hour, and the internal temperature was 0 ° C. The mixture was allowed to stand for 3 hours and then filtered to obtain 10.2 g of a light yellow solid with a yield of 61%. The thin yellow crystals were confirmed to be the target compound of Formula 5. The analysis results are shown below.

Analysis result (1) Melting point: 167.3 ° C
(2) ¹ H-NMR (δ, ppm) CDCl ₃ : 1.37 (t, 3H), 2.23 (s, 3H), 2.35 (s, 3H), 4.58 (q, 2H) 7.32 (m, 2H), 7.38 (d, 1H), 7.45 (t, 1H), 7.83 (s, 2H), 7.87 (d, 1H), 7.99- 8.01 (m, 3H), 8.39 (d, 2H), 8.73 (d, 2H)
(3) UV spectrum measurement (methylene chloride): λmax: 263, 299, 342
(4) Decomposition temperature (in nitrogen stream, rate of temperature increase 10 ° C / min, 5% weight loss temperature): 278.6 ° C

[Example 2]

Step 1: Synthesis of 2- (4-nitrophenyl) acetyl chloride [2- (4-nitrophenyl) acetyl chloride] 2- (4-nitrophenyl) acetic under a nitrogen atmosphere
Acid [2- (4-nitrophenyl) acetic acid] (60 g) and thionyl chloride (140 g) were added, the temperature was gradually raised, and the mixture was refluxed at 95 ° C. for 4 hours. After 4 hours, a distillation apparatus was installed at the same temperature, and thionyl chloride was distilled at normal pressure. After cooling the reactor temperature to room temperature, residual thionyl chloride was removed using a vacuum distillation apparatus. The residual viscous liquid was precipitated in petroleum ether and filtered to obtain yellow crystals. Yellow crystals are 61 g and the yield is 90%.
¹ H-NMR (δ, ppm) CDCl ₃ : 4.1 (s, 2H), 7.67 (d, 2H), 8.21 (d, 2H)

Two steps: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (4-nitrophenyl) ethanolone [1- (9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl) -2- (4-nitrophenyl) ethanone] Under a nitrogen atmosphere, 50.0 g of N-ethylcarbazole and 300 mL of dried CH ₂ Cl ₂ were added. Melted. After the reaction was cooled to 0 ° C., 35.2 g of AlCl ₃ was slowly added in three portions. To this, 40.7 g of 2-methylbenzoyl chloride was slowly added dropwise at an internal temperature of 3 ° C. or lower. Further, after stirring for about 8 hours at 15 ° C., the temperature of the reactor was brought to 0 ° C., 35.2 g of AlCl ₃ was added, and 2- (4-nitrophenyl) acetyl chloride [2- (4-nitrophenyl) acetyl was added. Chloride] 52.7 g was gradually added dropwise so that 5 ° C. was not exceeded. After stirring for 3 hours, the internal temperature was lowered to 0 ° C. or lower, the reactor solution was slowly added to 500 mL of ice water, stirred for 1 hour, separated into layers, further neutralized and washed with 200 mL of 1% NaOH, and then the organic layer was washed. After drying with MgSO ₄ , the solvent was removed by a rotary evaporator and recrystallized from methanol and methylene chloride to obtain 85 g of a yellow solid having a yield of 75%.

¹ H-NMR (δ, ppm) DMSOd ₆ : 1.29 (t, 3H), 2.48 (s, 3H), 4.13 (s, 2H), 4.53 (q, 2H), 7. 16 (d, 1H), 7.36 (t, 1H), 7.52 (t, 1H), 7.66 (m, 4H), 7.83 (d, 1H), 7.98 (d, 1H) ), 8.14 (d, 2H), 8.65 (s, 1H), 8.74 (s, 1H)

Three steps: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (4-nitrophenyl) ethanolone [1- (9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl) -2- (4-nitrophenyl) ethanone] Into a reactor, 300 mL of tetrahydrofuran was added, and 50 g of the compound obtained in Step 2 was added and dissolved. After cooling the temperature of the reaction product to 3 ° C. or less, 52 mL of 35% hydrochloric acid was slowly added dropwise. To this reaction product, 12.6 g of isopentylnitrite was slowly added dropwise while maintaining the internal temperature at 3 ° C. or lower. After the dropwise addition, the temperature was raised to 10 ° C. and stirred for 8 hours. After removing the solvent tetrahydrofuran by distillation under reduced pressure, 400 mL of methylene chloride and 400 mL of water were added and washed with water. After neutralizing and washing with saturated calcium carbonate, the organic layer was dried over MgSO ₄ and distilled under reduced pressure to obtain a liquid compound. Ethanol and methylene chloride were added to this liquid compound for recrystallization. 35 g of yellow crystals were obtained. The yield was 66%.

¹ H-NMR (δ, ppm) DMSOd ₆ : 1.29 (t, 3H), 2.48 (s, 3H), 4.53 (q, 2H), 7.16 (d, 1H), 7. 36 (t, 1H), 7.55 (m, 2H), 7.66 (d, 1H), 7.74 (d, 1H), 7.83 (d, 1H), 7.98 (d, 1H) ), 8.09 (d, 2H), 8.33 (d, 2H), 8.60 (s, 1H), 8.74 (s, 1H), 10.1 (s, 1H, -OH)

Four steps: ((E) -2- (acetoxyimino) -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (4-nitrophenyl) ethanol [((E ) -2- (Acetoxyimino) -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -2- (4-nitrophenyl) ethanone] under nitrogen atmosphere The internal temperature was lowered to 0 ° C. or lower, the compound obtained in the above three steps (30.0 g), methylene chloride (180 mL) and triethyleneamine (6.18 g) were added, and acetyl chloride (4.80 g) was added to methylene chloride. The solution dissolved in (10 mL) was slowly added, and the internal temperature was raised to 10 ° C., followed by stirring for 3 hours. Water was added to the solution several times, the organic layer was washed, and the solid compound obtained by distillation under reduced pressure was added to ethyl acetate and methylene chloride, and circulated and refluxed for 1 hour. The internal temperature was lowered to 0 ° C. and left for 3 hours. Then, filtration was performed to obtain 25 g of a pale yellow solid with a yield of 77%, and it was confirmed that the pale yellow crystal was a compound represented by the chemical formula 9, which was the target product. .

Analysis result (1) Melting point: 158.6 ° C
(2) ¹ H-NMR (δ, ppm) CDCl ₃ : 1.28 (t, 3H), 2.48 (s, 3H), 2.28 (s, 3H), 4.48 (q, 2H) 7.16 (d, 1H), 7.36 (t, 1H), 7.45 (d, 1H), 7.52 (t, 1H), 7.66 (m, 2H), 7.92 ( d, 1H), 8.09 (d, 3H), 8.33 (d, 2H), 8.51 (s, 1H), 8.87 (s, 1H)
(3) UV spectrum measurement (methylene chloride): λmax: 263, 298, 344
(4) Decomposition temperature (in nitrogen stream, temperature increase rate 10 ° C / min, 5% weight loss temperature): 256.4 ° C

[Example 3]

Step 1: Synthesis of (4-nitrophenyl) (4- (phenylthio) phenyl) methaneone [(4-nitrophenyl) (4- (phenylthio) phenyl) methanone] CH 2 dried with 50.0 g of diphenylsulfide under nitrogen atmosphere ₂ Cl ₂
300 mL was added and dissolved. After the reaction was cooled to 0 ° C., 36.87 g of AlCl ₃ was slowly added. 4-Nitrobenzoyl chloride [4-nitrobenzoyl chloride]
51.3 g was gradually added dropwise so that 5 ° C was not exceeded. After stirring for 3 hours, the internal temperature was lowered to 0 ° C. or lower, the reactor solution was slowly added to 500 mL of ice water and stirred for 1 hour, then the layers were separated, and further 1% NaOH
After neutralizing and washing with 200 mL, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator and purified to methanol and methylene chloride to obtain 72 g of a yellow solid with a yield of 80%.

¹ H-NMR (δ, ppm) CDCl ₃ : 7.19-7.25 (m, 3H), 7.41 (d, 2H), 7.51 (d, 2H), 7.58 (d, 2H) ), 8.04 (d, 2H), 8.39 (d, 2H)

Two steps: Synthesis of (Z)-(4-nitrophenyl) (4- (phenylthio) phenyl) methaneoneoxime [(Z)-(4-nitrophenyl) (4- (phenylthio) phenyl) methanone oxide] The obtained compound 50 was added to 350 mL of ethanol and 100 mL of distilled water. Hydroxylamine hydrochloride (10.67 g) and sodium acetate (20.9 g) were added to the mixture and reacted. The reaction solution was circulated and refluxed for 8 hours, and cold distilled water was added to form a precipitate. The formed precipitate was filtered and washed with distilled water. The obtained yellow solid was washed with cold ethanol and then dried to obtain 46 g of a yellow solid having a yield of 88%.
Got.

¹ H-NMR (δ, ppm) DMSOd ₆ : 7.19-7.25 (m, 3H), 7.43 (m, 4H), 7.63 (d, 2H), 8.24 (d, 2H) ), 8.50 (d, 2H), 10.2 (s, 1H-OH)

Three steps: Synthesis of (Z)-(4-nitrophenyl) (4- (phenylthio) phenyl) methanolone oxime [(Z)-(4-nitrophenyl) (4- (phenylthio) phenyl) methanone oxide] under nitrogen atmosphere Then, 240 mL of methylene chloride was added, and the internal temperature was lowered to 0 ° C. or lower. To this solution, 40.0 g of the compound obtained in the above two steps and triethyleneamine (11.9 g) were added, and a solution of acetyl chloride (9.23 g) dissolved in methylene chloride (20 mL) was slowly added. After raising the internal temperature to 10 ° C., the mixture was stirred for 3 hours. Water is added to the reaction solution several times to wash the organic layer and distilled under reduced pressure. The resulting solid compound is added with normal hexane and methylene chloride and circulated and refluxed for 1 hour to lower the internal temperature to 0 ° C., 3 After standing for a period of time, filtration was performed to obtain 38 g of a pale yellow solid with a yield of 85%. The thin yellow crystals were confirmed to be the compound of formula 13 which is the target product. The analysis results are summarized below.

Analysis result (1) Melting point: 124.3 ° C
(2) ¹ H-NMR (δ, ppm) CDCl ₃ : 2.09 (s, 3H), 7.23 (m, 3H), 7.42 (m, 4H), 7.65 (d, 2H) 8.21 (d, 2H), 8.49 (d, 2H)
(3) UV spectrum measurement (methylene chloride): λmax: 241, 328
(4) Decomposition temperature (in nitrogen stream, rate of temperature increase 10 ° C / min, 5% weight loss temperature): 258.6 ° C

[Example 4]

Step 1: Synthesis of 2- (4-nitrophenyl) acetyl chloride [2- (4-nitrophenyl) acetyl chloride] 2- (4-Nitrophenyl) acetic acid [2- (4-nitrophenyl) acetic acid] under nitrogen atmosphere (60 g) and thionyl chloride (140 g) were added, the temperature was gradually raised, and the mixture was refluxed at 95 ° C. for 4 hours. After 4 hours, a distillation apparatus was installed at the same temperature, and thionyl chloride was distilled at normal pressure. After cooling the reactor at room temperature, the remaining thionyl chloride was removed using a vacuum distillation apparatus. The residual viscous liquid was precipitated into petroleum ether and filtered to obtain yellow crystals. The yellow crystals are 61 g and the yield is 90%.

¹ H-NMR (δ, ppm) CDCl ₃ : 4.1 (s, 2H), 7.67 (d, 2H), 8.21 (d, 2H)

Two steps: 2- (4-nitrophenyl) -1- (4- (phenylthio) phenyl) ethanone [2- (4-nitrophenyl) -1- (4- (phenylthio) phenyl) ethanone]
50.0 g of biphenyl sulfide and dried CH ₂ Cl ₂ under nitrogen atmosphere
300 mL was added and dissolved. After the reaction was cooled to 0 ° C., 36.87 g of AlCl ₃ was slowly added. To this, 2- (4-nitrophenyl) acetyl chloride [2- (4-nitrophenyl) acetyl chloride]
55.18 g was slowly added dropwise at an internal temperature of 5 ° C. or lower. After stirring the reaction temperature at room temperature for about 5 hours, the internal temperature is lowered to 0 ° C. or lower, the solution of the reactor is slowly added to 300 mL of ice water, the mixture is stirred for 1 hour, the layers are separated, and further 1% NaOH
After neutralizing and washing with 200 mL, the organic layer was dried with MgSO ₄ , and then the solvent was removed by a rotary evaporator and purified to methanol and methylene chloride to obtain 75 g of a yellow solid with a yield of 80%.

¹ H-NMR (δ, ppm) CDCl ₃ : 4.14 (s, 2H), 7.19-7.25 (m, 3H), 7.41 (d, 2H), 7.52 (d, 2H) ), 7.68 (d, 2H), 7.74 (d, 2H), 8.14 (d, 2H)

Three steps: (E) -2- (hydroxyimino) -2- (4-nitrophenyl) -1- (4- (phenylthio) phenyl) ethanolone [(E) -2- (hydroxyimino) -2- (4-nitro Phenyl) -1- (4- (phenylthio) phenyl) ethanone]
420 mL of tetrahydrofuran was placed in the reactor, and 70 g of the compound obtained in the above two steps was added and dissolved. After cooling the temperature of the reaction product to 3 ° C. or lower, 22.9 mL of 35% hydrochloric acid was slowly added dropwise. To this reaction product, 35.2 g of isopentylnitrite was slowly added dropwise while maintaining the internal temperature at 3 ° C. or lower. Then, after heating up to 10 degreeC, it stirred for 8 hours. After removing the solvent tetrahydrofuran by distillation under reduced pressure, 400 mL of methylene chloride and 400 mL of water were added and washed with water. After neutralizing and washing with saturated calcium carbonate, the organic layer was dried over MgSO ₄ and distilled under reduced pressure to obtain a liquid compound. Petroleum ether and methylene chloride were added to this liquid compound and recrystallized. The yellow crystals were 50 g, and the yield was 66%.

¹ H-NMR (δ, ppm) DMSOd ₆ : 7.19-7.25 (m, 3H), 7.41 (d, 2H), 7.52 (d, 2H), 7.68 (d, 2H) ), 7.74 (d, 2H), 8.14 (d, 2H), 12.5 (s, 1H, -OH)

4 steps: (E) -2- (acetoxyimino) -2- (4-nitrophenyl) -1- (4- (phenylthio) phenyl) ethanolone [(E) -2- (acetoxyimino) -2- (4-nitro Phenyl) -1- (4- (phenylthio) phenyl) ethanone]
Reduce the internal temperature to 0 ° C. or lower under a nitrogen atmosphere, add 50 g of the compound obtained in the above three steps, 300 mL of methylene chloride and 13.77 g of triethyleneamine, and add a solution of 10.68 g of acetyl chloride in 15 mL of methylene chloride. Slowly added. After raising the internal temperature to 10 ° C., the mixture was stirred for 3 hours. Water was added to the reaction solution several times to wash the organic layer, and the solid compound obtained by distillation under reduced pressure was recrystallized by adding petroleum ether and methylene chloride. Filtration gave 45 g of a pale yellow solid with a yield of 81%. The thin yellow crystal was confirmed to be the compound of Formula 15 as the target product. The analysis results are shown below.

Analysis result (1) Melting point: 116.2 ° C
(2) ¹ H-NMR (δ, ppm) CDCl ₃ : 2.28 (s, 3H) 7.19-7.25 (m, 3H), 7.41 (d, 2H), 7.52 (d 2H), 7.68 (d, 2H), 8.09 (d, 2H), 8.33 (d, 2H)
(3) UV spectrum measurement (methylene chloride): λmax: 242, 332
(4) Decomposition temperature (in nitrogen stream, temperature increase rate 10 ° C / min, 5% weight loss temperature): 251.3 ° C

[Examples 5 to 10]
The following compounds were synthesized as shown in Table 1 according to the production methods of Examples 1 to 4 above.

[Example 11]
Manufacture of transparent resist composition 13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the compound obtained in Example 1 and 67 g of propylene glycol monoethyl ether are added to 17 g of acrylic copolymer, and the mixture is stirred and transparent. A photosensitive resist composition was obtained.

[Example 12]
Black resist composition 10 g of acrylic copolymer was charged with 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the compound obtained in Example 1, 48 g of pigment black 7, and 25 g of propylene glycol monoethyl ether, and stirred well. As a result, a black photosensitive resist composition was obtained.

[Example 13]
Red resist composition 13.6 g of dipentaerythritol hexaacrylate with respect to 10 g of acrylic copolymer, 1.5 g of the compound obtained in Example 1, Pigment Red 192
25 g and 49 g of propylene glycol monoethyl ether were added and stirred well to obtain a red photosensitive resist composition.

[Example 14]
Production of transparent resist composition 13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the compound obtained in Example 4 and 67 g of propylene glycol monoethyl ether were added to 17 g of the acrylic copolymer, and the mixture was well stirred and transparent. A photosensitive resist composition was obtained.

[Example 15]
Black resist composition 10 g of acrylic copolymer was charged with 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the compound obtained in Example 4, 48 g of pigment black 7, and 25 g of propylene glycol monoethyl ether and stirred well. As a result, a black photosensitive resist composition was obtained.

[Example 16]
Red resist composition 13.6 g of dipentaerythritol hexaacrylate with respect to 10 g of the acrylic copolymer, 1.5 g of the compound obtained in Example 4, Pigment Red 192
25 g and 49 g of propylene glycol monoethyl ether were added and stirred well to obtain a red photosensitive resist composition.

[Comparative example]
A photosensitive resist composition containing a compound represented by the following chemical formula 25 and chemical formula 26 was prepared. In addition, the manufacturing method shall be based on Examples 1-4.

[Comparative Example 1]
Production of transparent resist composition 13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the above chemical formula 25 and 67 g of propylene glycol monoethyl ether are added to 17 g of the acrylic copolymer, and the mixture is well stirred, and the transparent photosensitive resist composition Got.

[Comparative Example 2]
Black resist composition 10 g of acrylic copolymer was charged with 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the above chemical formula 25, 48 g of pigment black 7, and 25 g of propylene glycol monoethyl ether. A resist composition was obtained.

[Comparative Example 3]
Red resist composition 13.6 g of dipentaerythritol hexaacrylate with respect to 10 g of acrylic copolymer, 1.5 g of the above chemical formula 25, Pigment Red 192
25 g and 49 g of propylene glycol monoethyl ether were added and stirred well to obtain a red photosensitive resist composition.

[Comparative Example 4]
Production of transparent resist composition 13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the above chemical formula 26 and 67 g of propylene glycol monoethyl ether are added to 17 g of the acrylic copolymer, and the mixture is stirred well, and the transparent photosensitive resist composition Got.

[Comparative Example 5]
Black resist composition 10 g of acrylic copolymer was charged with 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the above chemical formula 26, 48 g of pigment black 7, and 25 g of propylene glycol monoethyl ether. A resist composition was obtained.

[Comparative Example 6]
Red resist composition 10 g of acrylic copolymer is charged with 13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the above chemical formula 26, 25 g of pigment red 192, and 49 g of propylene glycol monoethyl ether, and stirred well to obtain red photosensitivity. A resist composition was obtained.

Evaluation of the obtained photosensitive composition was performed as follows.
The photosensitive composition was applied to a spin coater at 800 to 900 rpm for 15 seconds, and then dried on a hot plate at 90 ° C. for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source using a predetermined mask, spin development was performed in a 0.04% potassium hydroxide solution at 25 ° C. for 60 seconds, followed by washing with water. After washing with water and drying, baking was performed at 230 ° C. for 40 minutes to obtain a pattern. The following evaluation proceeded on the obtained pattern. Table 1 shows the photopolymerization initiator used as each photosensitive composition and various evaluation results.

(1) Adhesiveness According to the test method of JIS D 0202, after exposure and development, the coating film heated at 200 ° C. for 30 minutes is cross-cut with a lattice shape, and then a peeling test is performed with a cellophane tape to separate the lattice shape. The state was observed and evaluated. When there was no peeling at all, ◯ and those where peeling was recognized were indicated by ×.

(2) Alkali resistance After development, after baking at 230 ° C. for 30 minutes, the coating film was subjected to 5% NaOH for 24 hours and 4% KOH.
After immersing at 50 ° C. for 10 minutes and 1% NaOH at 80 ° C. for 5 minutes, the state was observed. When there was no change in appearance and there was no peeling, ○ was indicated when the resist lift was observed, and × when the resist peeling was recognized.

(3) Sensitivity evaluation Each photosensitive resin composition having the above composition was applied to a glass substrate (Eagle 2000, manufactured by Samsung Corning Co., Ltd.) with a spin coater, and dried on a hot plate at 90 degrees for 1 minute. After drying, a stylus type film thickness measuring device (manufactured by KLA-Tencor, α-step)
The film thicknesses of the black resist and the transparent negative resist obtained by measuring 500) were 1 micron and 5 microns, respectively. Next, this sample was exposed to high pressure mercury or the like through a mask. Thereafter, spray development was performed with a 0.04% aqueous potassium hydroxide solution to obtain a resist pattern. An appropriate exposure amount (mJ / sqcm) capable of forming a dimension like a mask pattern of 40 microns was displayed. That is, a resist with a small exposure amount can form an image with a small amount of light energy, and thus shows high sensitivity.

(4) Whitening phenomenon Each photosensitive resin composition containing the synthesized photoinitiator was applied to an organic substrate with a spin coater. At this time, crystals are generated at the time of spin coating due to the solubility of the photoinitiator, and the case where the coated surface is very poor is indicated by x, and after the film is formed, crystals are generated during drying and the surface is cloudy. A symbol △ indicates that the surface is clean without forming crystals during film formation in a state well dissolved in the resist composition.

  Such results are shown in Table 2 below.

From the above results, it can be seen that the photosensitive composition containing the oxime ester-based compound and the alpha chitooxime ester-based compound according to the present invention is excellent in adhesion and alkali resistance, and has no whitening phenomenon of the thin film. Moreover, it turns out that the oxime ester type compound and alpha chito oxime ester type compound by this invention are excellent in the sensitivity.

Claims (12)

Oxime ester compound represented by the following chemical formula 1:

Wherein, _{R 1 is, -CH 3, -C 2 H 5} , - propyl, - butyl, - hexyl, - octyl, - benzoyl, - cyclohexyl,
R _{2 is, -CH 3, -C 2 H 5} , - propyl, - a benzoyl group,
R ₃ is —H, a is a methyl or ethyl group, and b is —H or a methyl group.

Alpha chitooxime ester compound represented by the following chemical formula 2:

Wherein, _{R 1 is, -CH 3, -C 2 H 5} , - propyl, - butyl, - hexyl, - octyl, - benzoyl, - cyclohexyl,
R ₂ is —CH ₃ , —C ₂ H ₅ , —propyl, —benzoyl,
R ₃ is —H, a is a methyl or ethyl group, and b is —H or a methyl group.

Oxime ester compound represented by the following chemical formula 3:

Wherein, _{R 1 is, -CH 3, -C 2 H 5} , - propyl, - butyl, - hexyl, - octyl, - benzoyl, - cyclohexyl,
R ₃ is —H, a is a methyl or ethyl group, and b is —H or a methyl group.

Alpha chitooxime ester compound represented by the following chemical formula 4:

Wherein, _{R 1 is, -CH 3, -C 2 H 5} , - propyl, - butyl, - hexyl, - octyl, - benzoyl, - cyclohexyl,
R ₃ is —H, a is a methyl or ethyl group, and b is —H or a methyl group.

One or more selected from the compound of formula 1 according to claim 1, the compound of formula 2 according to claim 2, the compound of formula 3 according to claim 3, and the compound of formula 4 according to claim 4. And a compound of
A polymer compound soluble in a solvent or an aqueous alkali solution and / or a photopolymerizable compound having an ethylenically unsaturated bond;
The photosensitive resin composition characterized by including.   The photosensitive resin composition according to claim 5, wherein the composition further contains a colorant or a pigment.   A column spacer formed from the photosensitive resin composition according to claim 5.   A black matrix formed from the photosensitive resin composition according to claim 5.   A color filter formed from the photosensitive resin composition according to claim 5.   A substrate having an organic insulating film formed from the photosensitive resin composition according to claim 5.   A substrate having a film formed by coating the photosensitive resin composition according to claim 5.   The film is a word processor, computer, television or plasma display panel, polarizing plate surface used in liquid crystal display devices, sunglasses lens, power glasses lens, camera finder lens, instrument cover, automobile glass, train The base material according to claim 11, wherein the base material is used for glass, a light brightness enhancement film, or an optical waveguide film.