TW200903160A - Photosensitive resin composition - Google Patents

Abstract

This invention provides a novel photosensitive composition capable of forming, with a high resolution, a cured resin pattern which exhibits excellent resistance to solvent and heat. The photosensitive resin composition contains a binder component (A) and photo-polymerizing initiator (B), wherein the binder component (A) contains a photo polymerizing compound (A1) having one or more than one of a carboxyl group and two or more than two of an unsaturated bond that can be photo polymerized, and a photo polymerizing compound (A2) free from a carboxyl group. The binder component (A) has a weight average molecular weight of 1,500 or less.

Description

200903160 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin composition. [Prior Art] The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition and a liquid crystal display device comprising the above-described cured resin pattern, which is suitable for forming a cured resin pattern constituting a part of a liquid crystal display device. A material of the type, for example, a photo spacer (10). An aer), an insulating film, and a liquid crystal alignment control. A large-up, overcoat layer, and a hardened resin pattern for aligning a colored pattern.叩 予 予 7 7 2 constituting the color filter side substrate of the liquid crystal display device and the alignment side substrate = keeping the interval between the two substrates constant, and providing a spacer ((4). This spacer is conventionally used; 疋 using glass beads Spherical particles such as plastic granules. When the mantle = glass = spherical particles, the spherical particles will be disordered or transparent: 2: components or electrodes cause damage, sub-scattering, contrast of liquid crystal display devices, shape The particle acts as a spacer, and _, does not use a ball spacer. According to this method, the wind object can solve the above problems. =1 The space formed by the space affects the display of the color filter. The thickness, heat resistance, and high hardness are required to be clamped, so the so-called height n is required. (IV) (Specially dedicated. It can be used for such spacers, / photosensitive resin composition, has been 320097 5 200903160 A composition containing a polymer component as a binder (Patent Document 2). With the refinement of the display performance of the liquid crystal display device, the fineness of the spacer is also progressed (Patent Document 3). (Patent Document U Japan Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. To the 13th aspect of the invention, the problem of the coating film obtained by using the photosensitive resin composition containing a polymer component having a weight average molecular weight of more than 1,500 as a binder is good, but the analysis is good. In view of the above, it is an object of the present invention to provide a novel photosensitive resin composition which can form a high-resolution, U-resistant agent and heat-resistant hardened resin pattern. Means for Solving the Problem The inventors of the present invention have found that the photosensitive resin composition of the present invention can solve the above-mentioned problems by focusing on a new means for solving the above problems. The present invention provides the following r丨" to "10". [1] A photosensitive resin composition containing a binder component (Α) and a photopolymerization_starting agent (Β) is characterized in that it is bonded Ingredients (Α) contains: 6 320097 200903160 A photopolymerizable compound (A1) having one or more carboxyl groups and two or more photopolymerizable unsaturated bonds, and a photopolymerizable compound (A2) having no carboxyl group The weight average molecular weight of the binder component (A) is ι, 5 〇〇 or less. [2] The photosensitive resin composition of [1], wherein one or more bases and two or more photopolymerizable groups The photopolymerizable compound (A1) of the unsaturated bond is a reaction product of an acid anhydride and a compound having one hydroxyl group and two or more unsaturated double bonds. [3] A photosensitive resin such as [1] or [2] a composition in which a photopolymerizable compound (A2) which does not have a rebel type is a compound (A2_1) represented by the formula (1); R2〇- «一r2 (丨) . Jm [in the formula (I) 'R1 represents an alkylene having 1 to 6 carbon atoms, R2 represents a group having a polymerizable unsaturated bond, and m represents an integer of 1 to 6]. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the photopolymerizable compound (A1) having more than one carboxyl group and two or more photopolymerizable unsaturated bonds The content of the photopolymerizable compound (A2) having no carboxyl group is from 1 to 90% by mass based on the component (A) of the binder, and the mass fraction is from 1 Torr to 99. [5] The photosensitive resin composition of [3] or [4], which is a compound represented by the formula (1) (A2-D contains 4, and is equivalent to a non-reactive group, a photopolymerizable compound ( A2), in terms of the mass fraction, is 〇1 to 7〇% by mass. [6] A type of hardened resin pattern formed by using a photosensitive resin composition as (1) to (10). 320097 7 200903160 m as [ The hardened resin pattern of the item 6), wherein the hardened resin pattern is a photo spacer. [8] The method for producing a hardened resin pattern is coated on a substrate as in (1) to [5] In one photosensitive resin composition, after removing the solvent, a light ray is irradiated through a mask, and then the image is formed by developing with an aqueous alkali solution, and then heating is performed. [9] Manufacture of a cured resin pattern The method of applying a photosensitive resin composition according to any one of (1) to [5] on a substrate, removing the solvent, irradiating the radiation with a mask, and then developing the image with an aqueous alkali solution. After the type, ultraviolet irradiation is carried out. ' [10] A liquid crystal display device having a hardened type as in [6] or [7]. [Effects of the Invention] When the photosensitive resin composition of the present invention is used, a cured resin pattern having high resolution and excellent solvent resistance and heat resistance can be formed. [Embodiment] [Best Mode for Carrying Out the Invention] The present invention is described in detail below. The photosensitive resin composition of the present invention is mainly used as a material for forming a cured resin pattern, and the binder component (A) contains one or more carboxyl groups and two or more. The photopolymerizable unsaturated photopolymerizable compound (A1), the photopolymerizable compound (A2) having no carboxyl group, and the photopolymerization initiator (B), which are soluble or dispersible in a solvent. The binder component is a component which is obtained by removing photopolymerization from the composition such as 320097 8 200903160 (B) and solvent (D) and, if necessary, the additive (E). The photosensitive resin composition of the present invention is used. The photopolymerizable compound (A1) having one or more carboxyl groups and two or more photopolymerizable unsaturated bonds is not particularly limited, but it is preferably an acid anhydride, and one or more hydroxyl groups and two or more. A reaction product of a compound of a polymerizable unsaturated bond, etc. An acid anhydride used in a reaction product having an acid anhydride and a compound having one hydroxyl group and two or more photopolymerizable unsaturated bonds may, for example, be a dicarboxylic anhydride. For example, succinic anhydride, 1-dodecenylsuccinic acid, maleic anhydride, glutaric anhydride, itaconic acid, & sour, hexachloroantimonate , methyl hexahydrofuric acid needle, tetradecyl maremic acid field, bismuth chloroformate, earth tetrahydrophthalic anhydride, terminal sulfhydryl tetrahydrophthalic anhydride, methyl terminal methylene = hydrogen anhydride, four Chlorhexidine liver, four desert sputum (10), Crondi (C bribery, 酉夂xuan, trimellitic anhydride, etc.). For example, butyl tetracarboxylic acid dianhydride, 1,2,3,4·cyclobutane 1 2 夂-anhydride, 1,3-dimethyl-, 1, 2, 3,4·cyclobutane tetracarboxylic dianhydride, anhydride^cyclohexyl (tetra) acid dianhydride, such as · tricarboxycyclopentyl acetic acid di-tetra- _ ^, silk ice m2 · succinic dianhydride, 2, 3, 4,5-tetrahydrogen bite South • l2_—,, _ _(2,5_-oxytetramine_3'•furanyl)-3-methyl-3-cyclohexene double (2 6 slow t one Ί4-bis(2,5-dioxotetrachloro_3. dimethyl) benzene, K j 3 ^ - hexamidine _4_pyranyl) stupid, bicyclo[2,2,2]-oct-7 -ene anhydride tetracarboxylic guanidine-anhydride, 3,4-dicarboxyl], 2,3, tetrahydronaphthalene, adipic acid group, 1,2,3,4-tetraammine methyl xiaocai Dreams, sour liver and other fats 320097 9 200903160 all tetrazoic acid dianhydride, 3,3',4,4'-dibenzimidone with tetrazoic acid dianhydride, 3,3,4,4_linked base Hard tetraacid acid, liver, 1,4,5,8-Caitetraic acid di野, 2,3,6,7-natetradecanoic acid dianhydride, 3,3,4,4'-biphenyl test Tetra-acid di-hepatic, 3,3,4,4-indenyl diphenyl monoxide, tetradecanoic acid dixanthine, 3,3,,4 4,-tetraphenyl decane tetracarboxylic dianhydride, 1,2 , 3,4-furan tetracarboxylic dianhydride, 4,4, _ double 3,4_Dimethylphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dibenzylphenoxy)diphenylphosphonium dianhydride, 4,4,-bis ( 3,4-Dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropanyl dicarboxylic acid dianhydride, 3,3,,4,4,_ Phenyltetracarboxylic dianhydride, bis(decanoic acid)phenylphosphine dianhydride, p-phenylene-bis(triphenylphosphonic acid) dianhydride, m-phenylexene-bis(triphenylphosphonic acid) An aromatic four of dianhydride, bis(triphenylphosphonium)-4,4'-diphenyl ether dianhydride, bis(triphenylphosphonic acid)_4,4,_diphenyl sulfonium dianhydride It is a compound of the following compounds. 〇 〇 〇

(Π) [In the formula, R3 represents a C. an alkyl group] Among the above-mentioned respective compounds, 轫-1,2,3,4-tetrahydro+naphthyl-5 leucovorin can be, for example, 3,4_2 Retinoic anhydride, 5-(2,5-dioxotetrahydro_3_furan 320097 10 200903160 4,4'-bis(3,4-dimercapto)-3-methyl-3-cyclohexene 2 di(tetra)bis(phenoxy)diphenylsulfone dianhydride. Photopolymerizable non-residual bond having one filament and two or more photopolymerizable unsaturated bonds, for example, derived from (mercapto) propylene, (meth) propylene based The description indicates at least one selected from the group consisting of a propyl group and a fluorenyl group. &(A) is a type selected from the group consisting of acrylic acid and methacrylic acid vinegar. It has one county and two or more photopolymerizable unsaturated bonds. The compound may, for example, be glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylic acid vinegar, or bis-trimethylmethylpropane tris(meth)acrylic acid^, Preferred examples of pentaerythritol di(meth)acrylic acid vinegar, dipentaerythritol penta (methyl) propyl vinegar vinegar, etc. may be glycerol di(methyl) acrylate, penta pentane 15 15 di(methyl) propyl group. Dilute vinegar. 'Reactant having an acid anhydride, a compound with two groups and two or more photopolymerizable compounds and a double bond, for example, stirring and mixing as needed. The temperature is generally from 2 to 〇〇. Preferably, it is from 3 to 18 Torr, more preferably from 40 to 16 Torr. If the temperature at the time of the reaction lies in the above range, the reaction can be appropriately adjusted. At the same time, '(A1) can be suppressed by reacting the unreacted raw materials on the way of the reaction with the obtained reaction product In the reaction of Lishao, in order to suppress the side reaction, polymerization inhibition 320097 11 200903160 may be used. The polymerization inhibitor may be used for polymerization inhibition, anti-shore test, etc. In the following, it is preferable that the amount of __^ is generally used in the measurement, and the touch can be performed in the non-catalyst, but the catalyst can be used as needed. For example, three Ethylamine is more known than biting, N_f-based 'salt, azo-bicyclo- 11-stone Rousseau _: material, minus tri-methyl silk yarn 1 (4). Also, other acids or bases may be used. Catalyst. The reaction system can be carried out even without solvent, but the solvent is used in the village, L is propylene glycol monomethyl sulphate acetate, etc. a bond such as a dimethyl group, a hydrazine such as a acetophenone, an aromatic hydrocarbon such as toluene or the like, and an aromatic hydrocarbon such as toluene, etc., having one or more secrets and two or more photopolymerizable The photopolymerizable compound (A1) having a saturated bond may, for example, be succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, or six. Hydrophthalic anhydride, trimellitic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4-dicarboxy- 1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride i mole and pentaerythritol triacrylate 2 molar reactant, trimellitic dianhydride, 4,4,_diphenyl steel Carboxylic dianhydride, 3,3,4,4,-biphenylsulfone tetracarboxylic dianhydride, etc., preferably 3,4·dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic dianhydride 1 molar with pentaerythritol diacrylate 2 molar reactant, 4,4,-biphenylsulfone tetradecanoic dianhydride oxime and pentaerythritol triacrylate 2 molar reactant, 5_(2, 5-Dioxotetrachloro_3_furanyl-3-indolyl-3-cyclohexene-1,2-dicarboxylic dianhydride 1 molar and quaternary tetraol triacrylate 2 molar reactant. 320097 12 200903160 The content of the photopolymerizable compound (A 1) having one or more carboxyl groups and two or more "polymerized non-remaining human bonds", the phase material # 'you are relative to the binder in terms of mass fraction' It is preferably 1 〇 199 mass%, more preferably 3 〇 to 99 mass%. have! When the content of the photopolymerizable compound (A1) of the photopolymerizable unsaturated bond of the above-mentioned age and the second is in the range of the above-mentioned range, it is difficult to reduce the film of the exposed portion at the time of development. Peak, soil nS, telling the unexposed part of the raw part is good, and there is a tendency to not easily develop the residue of the image, so it is good. The photopolymerizable compound (A2) which does not have a carboxyl group contained in the photosensitive resin composition of the present invention may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer having three or more functional groups. The monofunctional monomer may, for example, be benzyl (meth) acrylate, 2-phenylethyl (decyl) acrylate, cyclohexyl (decyl) acrylate, tricyclodecyl (methyl) Acrylate, mercaptophenyl carbitol (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (mercapto) acrylate, 2-ethylhexyl carbitol (meth) acrylate S is intended to be N-vinyl η than 0. Further, the bifunctional monomer may, for example, be ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, oxime butanediol di(meth)acrylate, tetramethylene Glycol bis(methyl;) acrylate, propylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, hexane diol di(meth) acrylate, 1,4-cyclohexane Glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, 1>6-hexanediol di(meth)acrylic acid vinegar, bisphenolphthalein Bis(propylene oxiranyl)ether, 3-methylpentanediol bis(f) acrylate, heptanediol di(meth) acrylate, octanediol di(meth) acrylate, decanediol Di(meth)acrylate, tricyclodecanediol 13 320097 200903160 mono(methyl)propanoic acid® 曰methylenebis-(indenyl)propanamide, hexamethylene bis-( Methyl) acrylamide, xylene-extension bis(meth) acrylamide, and the like. Other trifunctional or higher polyfunctional monomers include, for example, trimethylsulfate tri(meth)acrylate, trimethylolpropane tri(T-)acrylate, pentaerythritol tris(decyl)acrylate, Trimethylolpropane tris((meth)acryloxypropyl)ether, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbose Alcohol tri(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol penta (meth) acrylate, sorbitol hexa(meth) acrylate, tris((meth) propylene oxime Oxyethyl)trimeric isocyanate, diethylenetriamine tris(indenyl)propenylamine, a compound represented by formula (III), formula (IV), and the like. CH20 - R6 CH20-R7 r5_OCH2—c—ch2—〇—CH 2 —c—CH 2 〇—RS (III) CH 2 . R4 t-RS ' [R to r in the formula (III) independently represents a hydrogen atom or a group of any one of the formulas 1) to (ΠΙ-3).

II -C-ch=ch2 (HI-1) _II 〇c-ch2ch2ch2ch2ch20-c-ch=ch2 (ΙΠ-2) /0 —^c~ch2ch2ch2ch2ch2o^-ch=ch2' (^-3) But 'RS R9 At least four of the base equations are the basis of one of 320097 14 200903160, and the base of the at least one of R to Rf (111_2) or the formula (m_3). The preferred ones are, for example, a compound having 6 groups represented by the formula (〇_2) and a compound having 6 groups represented by the formula (m-3). Further, for example, benzoyl diisoxamate, hexamethylene monoisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polydiisocyanate, etc. may be mentioned. A polyaminoisocyanate compound having two or more isocyanate groups in the molecule, and a vinyl urethane compound obtained by adding a vinyl monomer represented by the formula (Iv). R11 R10 (IV) CH2-C-C-O-ch2-ch~oh

II 〇 [In the formula (IV)] and 1〇 and R11 are each independently represented by a chlorine atom or a methyl group as a vinyl urethane compound, for example, can be used for an anthracene molecule - two or more? K-bonded ethylene-based compound (Japanese Patent Publication No. -41708). Further, as the compound containing a polymerizable vinyl group, a urethane acrylate which is widely described in the above-mentioned JP-A-51-37193 can be used, and it can be used in Japan, followed by the association V〇1.20, No. 7. , 300 to 308 (1984) introduced as a photocurable monomer. As the photopolymerizable compound (A2) having no carboxyl group, a preferred one of the bifunctional monomers is, for example, the compound "24" represented by the formula (1). Π) R2〇- r1'〇- A r2 m [In the formula (1), R1 represents an alkylene group having 1 to 6 carbon atoms. It means a group having a polymerizable bond and a bond. 320097 15 200903160 m represents an integer of 1 to 6.] Carbon number 1 to 6 The alkyl group may, for example, be an anthracenylene group, an exoethyl group, a propyl group, an exo isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isoamyl group, a pentaerythritol group, and a stretching group. The hexyl group, the isohexyl group and the like are preferably, for example, an ethyl group and a propyl group. The group having a polymerizable unsaturated bond may, for example, be a (fluorenyl) propylene group. The compound shown may, for example, be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hydrazine, 3-butanediol bis(indometh) acrylate 'tetramethylene Glycol di(meth)acrylate, propylene glycol di(mercapto) acrylate, neopentyl glycol di(meth) acrylate, hexanediol di(meth) acrylate, 1,4-ring Hexanediol bis(indenyl) acrylate, tetraethylene glycol bis(meth) acrylate vinegar, etc., preferably, for example, ethylene glycol di(meth)acrylic acid

Ester, triethylene glycol bis(indenyl) acrylate, butyl butyl diol di(methyl) propionate, and the like. A such a photopolymerizable compound (A2) may be used alone or in combination of two or more. Among them, a compound represented by the formula (1) and a polyfunctional monomer having a trifunctional or higher functional group are preferably used in combination. When the content of the photopolymerizable compound (A2) having no carboxyl group is 1% by mass based on the total amount of the binder component (A), it is preferably 1 to 90% by mass in terms of mass fraction. More preferably, it is ^7〇% by mass. When the content of the photopolymerizable compound (A2) having no basis is within the above range, the strength, smoothness, and reliability of the exposed portion tend to be good. In the photosensitive resin composition of the present invention, the weight average molecular weight of the weight component (4) is 1500 or less. The above weight average molecular weight is determined according to the formula (1). Mw=(MlxWl)/(Wl+W2)+(M2xW2)/(Wl+W2) (1)

Mw : (A) Weight average molecular weight M1 : (A1) molecular weight or weight average molecular weight M2: (A2) molecular weight or weight average molecular weight W1 : (A1) (A) use ratio W2 : (A2) In the case of (A), the respective molecular weights (A1) and (A2) are different in molecular weight (when the mixture is a weight average molecular weight), and may exceed 1,500 ', but when one component exceeds Mwl, 500, the component is The use ratio in the binder component (A) is lowered, and the other component is selected such that the Mw is less than 1,500 and the use ratio in the binder component (A) of the component is increased, and the binder component obtained according to the formula (1) (A) The weight average molecular weight may be 1,500 or less. The weight average molecular weight of the binder component (A) in the present invention is 1,500 or less, preferably 300 or more and 1,500 or less, preferably 300 or more and 1,200 or less, more preferably 500 or more and 1,000 or less, and particularly preferably 700 or more and 900 or less. When the weight average molecular weight of the binder component (A) is within the above range, the resolution tends to be good, which is preferable. The photosensitive resin composition of the present invention may contain a curing agent (A3) as a binder component (A). The hardener (A3) is hardened by heat treatment after development, and is used to improve the mechanical strength such as recovery rate. Such a curing agent (A3) may, for example, be reacted with a rebel group by heating to crosslink a carboxyl group having one or more 17 320097 200903160 and two or more substances (A1), or to form an insufficient amount of S: The photopolymerizable compound of the bonded bond - X' can also be a compound which is polymerized early. • _ is a compound that is polymerized by a single force, and it is polymerized alone. It is difficult to polymerize and polymerize to form a hard acid. For example, an epoxidized person. Compounds of this type, such as base compounds. Examples of the gas-heterocyclic butyl gamma (tetra) compound and the methyl oxime compound include: A-based epoxy resin, double bis (four) lipid, hydrogenated bisphenol ruthenium, novolak-type epoxy resin, age F-based eucalyptus Ring-type epoxy _, (4) H-fragrance epoxy resin, wax glycidylamine arboreal month tr, % glycerol-based lanthanide tree, the desertification derivative of epoxy tree wax = month曰, -, such trimeric isocyanic acid or sulphur compound epoxy compound, triglycidyl dicentric =: for example, a carbonated bishydroxy heterocycle, f exemplified dioxyheterocycle Butane, acid ester dioxetane, 浐p ρ 文 日 日 日 虱 虱 、 、 、 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 乙基 乙基 乙基 乙基Methyl}H^(H3-yl)methoxy fluorene,]4-雔η, bis{(3-ethyloxetane 1 , _ double { _(3~ethyloxy) Heterocyclobutane)methoxy A丨Ψ, 4. bis(tetra)-ethyloxebutanyl)methoxy()-yl-(yloxyxanthene)methoxyl-based ring For calcination, etc., the methylol compound may, for example, be: gambling, alkoxymethylated urea The melamine tree such as fat can be exemplified by an oxymethylated melamine resin, for example, oxy yin 320097 18 200903160 melamine melamine resin, ethoxylated melamine melamine resin, propoxy guanidinated melamine resin, butoxy The methylated melamine resin or the like, and the alkoxylated urea resin may, for example, be a methoxylated urea resin, an ethoxylated urea resin, a propoxymethylated urea resin, or a butoxy group. In the photosensitive resin composition of the present invention, when the above-mentioned curing agent (A3) is used, these may be used alone or in combination of two or more. When the above-mentioned curing agent (A3) is contained The content of the photosensitive resin composition is preferably from 1 to 30%, and the amount of the curing agent (A3) is in the above range, because the photosensitive resin composition can be suppressed. The solubility and sensitivity in the developing solution are preferably lowered. When (A3) is contained, the weight average molecular weight of (A) is determined according to the formula (2).

Mw=(MlxWl)/(Wl+W2+W3)+(M2xW2)/(Wl+W2+W3)+ (M3xW3)/(Wl+W2+W3) (2)

Mw : (A) Weight average molecular weight M1: (A1) molecular weight or weight average molecular weight M2: (A2) molecular weight or weight average molecular weight M3: (A3) molecular weight or weight average molecular weight W1 : (A1) (A Use ratio W2 in the formula (A2): (A) The use ratio of (A) (A), the respective molecular weights (A2) and (A3) (in the case of a mixture, Although the weight average molecular weight) may exceed 1,500, when a component exceeds Mwl, 500 19 320097 200903160, the use ratio of the component (A) of the component is lowered, and the other component is selected to have a Mw of less than 1500. By increasing the use ratio in the binder component (a) of the component, the weight average molecular weight of the binder component (A) can be 1,500 or less. The weight average molecular weight of the binder component (A) is preferably 5% or more, preferably 300 or more and 1,200 or less, more preferably 5 Å or more and 1,000 or less, and particularly preferably 7 Å or more and 9 Å or less. When the weight average molecular weight of the binder component (A) is within the above range, the resolution tends to be good, which is preferable. The photosensitive resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator (B) may, for example, be an acetophenone compound, a bisimidazole compound, an anthraquinone compound, a triterpenoid compound, a fluorenyl phosphorus oxide compound, a benzoin compound, or a diphenyl group. The ketone compound, the thioxanthone compound, and the oxime compound are preferably, for example, an acetophenone-based compound, a biguanide-based compound m compound, a triterpenoid compound, or a fluorenyl oxide-based compound. Examples of the acetophenone compound described herein include 2,2•dimethoxy-2-diphenylethane-1-one, diethoxyethyl benzene, and 2-hydroxyphenyl propyl-1-one. , benzoquinone dimethyl _, 2, a small base [4_(2_ mercaptoethoxy) phenyl] m propyl! , Cyclohexylphenyl, ^methyl small (4-methylthiophenyl) 2 - phenanthroline propyl acetonide, 2 - benzyl dimethyl fluorenyl -1- (4- morphine Phenyl)butyrate small _, 2 fluorenyl phenyl hydrazino)_2_, methylaminol_1·(4-indolylphenyl)_τ _, 2_(3•methylbenzylamine peak: fluorenyl Amino group ·1·(4·?|ylphenyl)-butanthene, 2_(4_mercaptobenzylidene dimethylamino group·1.(4·吗琳基phenyl)_丁_, 2_ (2-ethylbenzyl)_2_ 320097 20 200903160 Dimercaptoamino-1-(4-morpholinylphenylbutanone, 2-(2-propylbenzyl)_2-didecylamino-1- (4·morpholinylphenylbutanone, 2_(2-butylbenzyl)_2_-decylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,3- Dimercaptobenzoyl)-2-didecylaminol_1_(4-morpholinylphenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamine (M-morpholinylphenyl)-butanone, 2-(2-chlorophenylhydrazino)-2-dimethylamino "-(decamorpholinylphenyl-butanone, 2-(2-bromophenyl)) -2-dimethylamino-helium 'morpholinophenyl)-butanone, 2_(3_ phenanthrenyl) 2 曱 曱 女 女 女 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Ding _, 2_ (4_ Benzoyl)-2-dimethylamino 4-(4-morpholinylphenylbutanone, 2-(3-bromomethyl)-2-dimethylamino-Zincing' morpholinylbenzene Ketobutyl ketone, 2, 4, bromo-bromo-yl)-2, monomethylaminomorpholinophenyl)-butanone, 2-(2-methoxybenzyl)-2-didecylamino -; ι_(4_morpholinylphenyl butanone, 2-(3-methoxybenzyl)-2-dimethylaminomorpholinophenyl)-butanone, 2-(4-methoxy) Benzoyl)-2-didecylaminomorpholinophenyl)butanone, 2-(2- mercapto-4-methoxyphenylhydrazino)_2-dimethylaminomorpholinophenyl Butanone, 2-(2-methyl-4-bromobenzyl)_2-dimethylamino, small, morpholinylphenyl)-butanone, 2-(2-bromo-4-methoxybenzene Methyl)_2_dimethylamino small (cardomorpholinylphenyl)-butyl-, 2-trans-base_2•methyl+[4_(1-methylethenyl)phenylpropane-1- The oligomer of the ketone or the like is preferably, for example, 2-methyl-helium ketone methylthiophenyl)-2-mercaptopropane oxime-ketone, 2-phenylmethyl-2-diene Aminoamino-1-(4-cylinylphenyl)butan-1-one. The above biimidazole compound may, for example, be 2,2,_bis(2-chlorophenyl)-4,4,5 , 5, - tetraphenyl double imipenone, 2, 2, bis(2,3-dichlorophenyl)_4,4,5,5,-tetraphenylbisimidazole (for example, see Japanese Patent Laid-Open No. Hei 6-75372, No. 320097 200903160^Sitting η2,,2雔Phenyl M,4',5,5,·tetra(decyloxyphenyl) double 0 m saliva, η, U, base M, 4', 5, 5, · four (Dialkyloxyphenyl) bis(also), 4,4,,5,5,-tetrakis(trialkoxyphenyl) bisimivir (for example, refer to the special public Zhao 48-38403 轳 扣 buckle shrine, JP-A-62.17, G., 1-5, 5-, 5-position, phenyl, substituted by imidazol, substituted by carboalkoxy, etc., etc., etc., preferably exemplified by two 虱benzyl M,4 ',5,5', phenylbisimidazole, 2,2, bis(2,3_-decyl)-4,4,5,5,-tetraphenylbisimidazole. • A compound of the formula 1 may be, for example, an o-ethoxycarbonyl-o-oxyimido group, a compound represented by the formula (3), and a formula (4).

, /Λ m _ one ..平椚仰.2,呤_叉(三氯曱)-6-(4-methoxyphenyl)_ι 3 _ ψ ), 3,5-dimorphine, 2,4-bis(trichloromethyl) )-6-(4-decyloxymethyl)-135-di tttfc, d, "一*,, 一井, 2,4-双(三气曱基)-6-piperine II, 2 4 -雔r 二客其,__ '又又(―气气)-6-(4-曱-oxystyrene.._ λ , again (-虱曱基)-6-(2-(5·曱基Furan-2-yl)vinyl)-1,3,5-trimorphine, 2 4 fluorene, ene, 4 _(trichloromethyl)-6-(2-(furan-2-yl)acetamidine Base)-1,3,5-triazine, 2 4-雔r di & 'also (dimethyl)-6-[2-(4-diethylamino-2- 22 320097 200903160 methyl Phenyl)vinyl]-1,3,5-three D well, 2,4_bis(trichloromethyl)_6_(2_(3,4_-methoxyphenyl)ethtyl)-1,3 In the case of the bismuth-based phosphine-based compound, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, etc. The above-mentioned benzoin-based compound may, for example, be mentioned. : benzoin, benzoin methyl ether, oxime ethyl group, benzoin isopropyl scaly, benzoin isobutyl, etc. The aforementioned benzophenone system The compound may, for example, be benzophenone, ortho-benzene, f-methyl-m-benzophenone, 4-phenylene-glycolylmethyl diphenyl sulfide, 3,3', 4,4'tetra (third Butyl peroxycarbonyl)dibenzophenone, 2,4,6-trimethylbenzophenone, etc. The above-mentioned thiaxanthene-based compound may, for example, be 2-propylene sulfide. Rhodium, 4-isopropylthioxanthone, 2, diethylthiazepine, 2,4-dichlorothiazinone, fluorene-chloro-cardiopropoxy thioxanthone, and the like. The above-mentioned oxime-based compound may, for example, be 9,1 (1), dimethoxyl, 2, ethyl-9, dimethoxyanthracene, 9,10-diethoxyanthracene, 2_ethyl_ 9,1〇_diethoxy oxime, etc. Others, also exemplified by *1〇-butyl_2_chloroσγ_, 2_ethyl_, benzoic acid (benzil), 9, i 〇 phenanthrenequinone,樟_, phenylethyl methacrylate, ferrocene compound, etc. as a photopolymerization initiator. Further, in the case of a photopolymerization initiator having a group capable of causing chain transfer, a special table 2002-544205 can be used. A photopolymerization initiator according to the above-mentioned formula (5) to (10), for example, a photopolymerization initiator having a group capable of causing chain transfer. Polymerization initiator. 320097 23 (5)200903160

?H3 C-C-h ch3 o ch3 u II

卜〇~: h2c o b(6)

(7) % hcoocf Νγ^3^4_^η3 CH3 ^H3 i.. with H2c

H3COOC7 H,, S~^CH The aforementioned photopolymerization initiation

? H2 / CH3 • C - C - N (10) C2N5 CH3 4 series can be used alone or in combination of two or more:: Well ▼ starter combined photopolymerization start aid (B-1) (Β_υ, when the photopolymerization start-up agent is used together with the photopolymerization start-up agent, the composition of the pattern is improved when the composition of the J-tree 1 is further increased in sensitivity, so that a pattern is formed by X. For example, human light, the starting aid (Β-1), for example, an amine compound, a carboxylated s material, a thiol compound, a compound represented by the formula (V), etc., the aforementioned 320097 24 200903160 The amine compound is preferably an aromatic amine compound. The amine compound may, for example, be an aliphatic amine compound such as triethanolamine, mercaptodiethanolamine or triisopropanolamine; 4-dimethylamino benzoic acid decyl ester , 4-dimethylamino benzoic acid ethyl ester, 4-didecylamino benzoic acid isoamyl ester, 4-didecylamino benzoic acid 2-ethylhexyl ester, benzoic acid 2-didecylamine Ethyl ethyl ester, hydrazine, hydrazine-dimethyl-p-toluidine, 4,4'-bis(didecylamino)benzophenone (general name: michelone), 4,4'-double (two An aromatic amine compound such as an amino)diphenyl fluorenone. The carboxylic acid compound may, for example, be phenyl thioacetic acid, methyl phenyl thioacetic acid, ethyl phenyl thioacetic acid, methyl ethyl phenyl thioacetic acid or a dimercapto group. Phenylthioacetic acid, nonyloxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, fluorenyl-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid An aromatic heteroacetic acid such as fluorenyl-naphthylglycine or naphthyloxyacetic acid. Examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, and 1,4-dimethylhydrogen. Thiophenyl, butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trishydroxypropyl propane thioglycolate, butanediol dithiopropane Acid ester, trimethylolpropane thiopropionate, trimethylolpropane thioglycolate, pentaerythritol thiopropionate, pentaerythritol thioglycolate, hydroxyethyl thiopropionate, pentaerythritol肆(3-Hexylthiobutyrate), 1,4-bis(3-hydrothiobutyloxy)butane. ,丫丫\ 13 吐N/C=CH_C-R1 3 (V) 25 320097 200903160 f In the formula (v), the aromatic ring of the ring. The X system represents a carbon number which may be substituted by a tooth atom. 6 to 12 γ is a non-oxygen atom or a sulfur atom.

Rl2 represents an alkyl group having a carbon number of Ϊ to ό. R13 represents an aryl group which may be substituted by "sub-substituted Wei 6 to an atom of i." The fluorenyl group or the south atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom having 6 to 12 carbon atoms. Examples of the aromatic ring include a benzene ring, a naphthalene ring, etc. The soil X is an aromatic ring olefin having a carbon number of 6 to 12 which may be substituted by a (tetra) group, a methylbenzene ring, a dimethylbenzene ring, or an ethyl group. Benzene ring, propyl:, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, milk, dichlorobenzene ring, silk ring, difilament ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene a ring, a naphthalene ring, a chloronaphthalene ring, a bromine ring, etc. The alkyl group having 1 to 6 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group or a 1-methyl-positive group. Propyl, 2·methyl-n-propyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2·methyl-n-butyl, 3-fluorenyl-n-butyl, U- Dimercapto-n-propyl, 1,2-dimethyl-n-propyl, 2,2-didecyl-n-propyl, n-hexyl, cyclohexyl, etc. Carbon number 1 which can also be substituted by halogen atom The alkyl group of 12 may, for example, be a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a fluorenyl group or a propyl group. 2-methyl-n-propyl, tert-butyl, n-pentyl, fluorenyl-n-butyl, 2-hydrazino-n-butyl, 3-mercapto-n-butyl, 1,1-di Base - n-propyl, ^ dimethyl-n-propyl, 2,2-dimercapto-n-propyl, n-hexyl, cyclohexyl, l gas " n-butyl, 2-chloro-n-butyl, 3 -Chloro-n-butyl, etc. 320097 26 200903160 The aryl group which may be substituted by a halogen atom, for example, phenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, chlorobromophenyl , biphenyl, chlorobiphenyl, dichlorobiphenyl, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloromethyl, bromocaline, dimoqinyl, etc. The compound represented by V) is preferably, for example, 2-(2-naphthylmethylidenylene)-3-mercaptobenzothiazoline represented by the formula (V-1), which is represented by the formula (V). -2) 2-Benzylmercapto-3-yl-naphthyl[1,2-d]thiazoline and 2-(4-benzonitrile) represented by formula (V-3)醯基亚曱基)-3-methyl-naphthalene [1,2-d] thiophene sitting scare (V-1)

(V-3) The content of the photopolymerization initiator (B) is preferably from 0.1 to 40% by mass, more preferably from 0.5 to 30% by mass, based on the total amount of the binder component (A). Further, the content of the photopolymerization initiation aid (B-1) is preferably from 0.01 to 50% by mass, more preferably from 0.1 to 40% by mass, based on the total amount of the binder component (A). 27 320097 200903160 When the total amount of the photopolymerization initiator (8) is within the above range, the photosensitive resin composition has a high sensitivity, and the strength of the pattern formed by using the above-mentioned photosensitive resin composition, or the foregoing The smoothness in the surface of the pattern has a tendency to become better, so it is better. In addition to the above, if the photopolymerization initiation aid L:1):: before the plum (4), the obtained photosensitive resin composition 2: Γ付更局' 1 The productivity of the substrate tends to be improved, so it is preferable. The photosensitive resin composition of the present invention may further contain a solvent (9). The above two doses (D) may be various organic solvents prepared in the field of photosensitive tree preforms. Such specific examples include, for example, ethylene glycol monoterpene (tetra), ethylene glycol early ethylene (tetra), ethylene glycol monopropyl sulfide, and ethylene glycol monobutylation; diethylene glycol dimercapto-, diethyl Diol diethyl: diethylene glycol dipropyl and diethylene glycol dibutyl (tetra) monoethyl alcohol monoalkyl group; methyl cellosolve acetate and ethyl cellosolve acetate Ethyl acetate; a fresh also produced sterol monoethyl acetate, propyl ketone, propyl ketone acetic acid, methoxy butyl ethoxylate Ether acetates; aromatic hydrocarbons such as benzene, methyl benzene, xylene and trimethylbenzene; ketones such as methyl ethyl ketone, propylene i, methyl amyl ketone, decyl isobutyl ketone; earth (octa) 夂 % ketone Ethanol, diol, butanol, hexanol, cyclohexanol, alcohol; refractory glycerin 320097 28 200903160 lactic acid acetaminophen, lactic acid propyl hydrazine, lactic acid butyl hydrazine, 3-ethoxypropionic acid vinegar and 3- An ester of methyl methoxypropionate; such as a ring of T _ butyl vinegar | In the above solvent, it is preferable that the solvent is, for example, a boiling point of 1 Å from the viewpoint of coatability and drying property. 〇 to 2〇〇. The organic solvent of hydrazine is preferably, for example, an alkylene glycol alkyl ether acetate or an ester, and particularly preferably, for example, propylene glycol monodecyl ether acetate or propylene glycol monoethyl ether acetam. Ethyl acetate, 3-ethoxypropionic acid ethyl acetate and 3_methoxypropionic acid methyl vinegar. These solvents (D) can be used alone or in combination of two or more. The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 4 Å to % by mass, and preferably 50 to 85% by mass based on the mass fraction of the photosensitive resin composition. . When the content of the solvent (D) is in the above-mentioned dry circumference, a spin coater, a slit and a spin coater, a slit coater (sometimes referred to as a die coater, a curtain flow coating) When the coating device such as inkjet or the like is applied, it is preferable that the coating property is improved. The photosensitive resin composition of the present invention may further contain a surfactant, a pigment dispersant, an adhesion improver, an antioxidant, an ultraviolet absorber, a photostabilizer, a sensitizer, an electron donor, and a chain transfer agent, as needed. , filler, and other additives (E). Further, the surfactant may contain at least one selected from the group consisting of a polyfluorene-based surfactant, a gas-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. The polyfluorene-based surfactant may be, for example, a trade name of T〇r叮Silicone DC 3PA ^ Toray Silicone SH7PA > Toray Silicone 320097 29 200903160 DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29 SHPA or Toray Silicone SH30PA (made by Toray 'Silicon Co., Ltd.); trade name polyether modified polyoxyxene oil SH8400 (manufactured by Toray Silicone Co., Ltd.); trade name KP321, KP 322, KP 323, KP324, KP326, KP340 or KP341 (Shin-Etsu Silicone (share) company); trade name TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 or TSF4460 (GE Toshiba Silicone Co., Ltd.). V Further, the curable resin composition of the present invention may contain another surfactant such as a propylene polymer surfactant or a vinyl polymer surfactant. The propylene polymer-based surfactant may, for example, be Disparon (trade name) OX-880'Disparon OX-881' Disparon OX-883' Disparon OX-70 'Disparon OX-77 'Disparon OX-77HF 'Disparon OX-60, Disparon OX -710, Disparon OX -720, Disparon OX r -740, Disparon OX -750, Disparon OX -8040, Disparon K.' 1970, Disparon 230, Disparon L-1980-50 'Disparon L-1982-50 ' Disparon L-1983-50 'Disparon L-1984-50 > Disparon L-1985-50, Disparon LAP-10, Disparon L-AP-20, Disparon LAP-30 or Disparon LHP-95 (Nanmoto Chemical Co., Ltd.) ); trade name BYK-352, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361 or BYK-390 (BYK Chemie, Japan company); EFKA ( Trade name) LP3778 (manufactured by Efka Chemicals Co., Ltd.). 30 320097 200903160 Vinyl polymer-based surfactants exemplified by Disparon (trade name) 1922, Disparon 1927, Disparon 1950, Disparon 951,

Disparon P-410 > Disparon P-410HF > Disparon P-420 >

Disparon P-425, Disparon PD-7 or Disparon LHP-90 (made by Nanben Chemical Co., Ltd.). As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include a polysiloxane, a fluorine-based, an ester-based, a cationic, an anionic oxime, a nonionic surfactant, and an amphoteric surfactant. These may be used alone or in combination. Use two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters. In addition to grade 3 amine modified polyurethanes, polyethyleneimine, etc., there are also trade names (Shin-Etsu Chemical Co., Ltd.), P〇lyfl〇w (Kyoei Chemical Co., Ltd.), EFT〇p (made by Tokem Products), Megafack (made by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad (Sumitomo 3M (share) system), Ashiguard, Sarfl〇n (made by Asahi Glass Co., Ltd.), Solsperse (Zeneca) (Company), EFKA I (made by EFKA Chemicals), PB821 (made by Ajinomoto Co., Ltd.), etc. Examples of the further improver include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginate (2-methoxyethoxy) decane, and n-(2-aminoethyl)-3-. Aminopropylmethyldimethoxyoxydecane, N_(2-aminoethyl)-3-aminopropyltrimethoxyoxydecane, 3-aminopropyltriethoxydecane, 3_epoxy Propoxypropyltrimethoxylate, 3_glycidoxypropylmethyl-methoxy-Xusic, 2_(3,4-epoxycyclohexyl)ethyltrimethoxylate, chlorine Propylmethyldimethoxydecane, 3' chloropropyltrimethoxydecane, % mercaptopropene oxypropyltrimethoxycarbazide, 3-nitrothiopropyltrimethoxy 320097 200903160 decane, and the like. The antioxidant may, for example, be 2,2,-sulfenyl (4-mercapto-6-t-butyl), 2,6-di-t-butylmethylphenol, Irgan® x 3114 (ciba)

Specialty Chemicals Co., Ltd.). The ultraviolet absorber can be exemplified by 2_(3_t-butylhydroxy-5•A

The chain transfer agent may, for example, be a dodecyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene. The filler may, for example, be glass, cerium oxide, aluminum oxide or the like. The photosensitive resin composition can be applied to a substrate by, for example, exposure and development to form a negative pattern. The substrate may, for example, be a transparent glass plate or a tantalum wafer, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a (iv) a long imine substrate, or a resin substrate such as a polyamine substrate. A circuit such as a TFT or a CCD, a color filter, or the like may be formed on the substrate. The layer composed of the photosensitive resin composition can be formed by, for example, a method of applying a photosensitive resin composition onto a substrate. The coating is carried out, for example, by a spin coating method, a vertical flow coating method, and a spin coating method. The light resin group is generally 1 to 6 # m. , roll coating method, slit 忒

The thickness of the photosensitive resin composition layer is one or both. ^ Then,

While irradiating radiation 320097 32 200903160 line. The pattern of the mask can be appropriately selected according to the pattern of the purpose of the hardened resin pattern. Koda ray can use the light of the § line and the i-line temple. The release of the ray is suitable, for example, using a device such as a mask aligner or a stepper. After the irradiation of the radiation, the photosensitive resin composition layer was developed. Development The photosensitive resin composition layer after exposure can be carried out by, for example, a paddle method, a dipping method, a spray method, a spray method, or the like. As the developing liquid, an aqueous alkali solution can be generally used. As the aqueous alkali solution, an aqueous solution of a basic compound may be used, and the basic compound may be an inorganic basic compound or an organic test compound. The basic compound may also be any of an inorganic or organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, potassium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, and citric acid. Potassium, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Further, specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltriammonium hydroxide, monodecylamine, dimethylamine, trimethylamine, and monoethylamine. , diethylamine, triethylamine, monoisopropylamine-isopropylamine, ethanolamine, and the like. These inorganic and organic basic compounds can be used alone or in combination of two or more. Alkalinization in the alkali imaging solution: the concentration of the substance 'is preferably 0.01 to 10% by mass'. More preferably, it is a bismuth 3 to 5 nucleating agent. The surfactant in the tartar liquid may also be a nonionic system. Any of the interface active, anionic surfactant, or cationic surfactant. 320097 33 200903160 Specific examples of the nonionic surfactant include polyoxyalkyl hydrazine, polyoxyethylene aryl aryl, and polyoxyethylene B. Chijifang test,: He: polyoxyethylene oxide derivative, oxidized ethylene/propylene oxide block copolymer: lysine fatty acid s, polyoxyethylene sorbitan fatty acid vinegar, polyoxyethylene sorbitol Alcohol fatty acid vinegar, glycerin fatty acid vinegar, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and the like. Specific examples of the anionic surfactant include, for example, higher alcoholic sulfates such as lauryl sulfate or oleyl sulfate, sodium lauryl or sodium lauryl sulfate (iv) sulfates, and the like. An alkyl aryl sulfonate such as sodium t-butyl benzoate or sodium dodecyl naphthalene sulfonate. Specific examples of the cationic surfactant include an amine salt such as stearylamine hydrochloride or lauryl trimethylammonium chloride or a fourth-order ammonium salt. These surfactants can be used alone or in combination of two or more. The concentration of the surfactant in the slave liquid is preferably in the range of 〇 J to 〇 % mass % I, preferably 0.05 to 8% by mass, more preferably 〇 1 to 5% by mass 0, and then 'photosensitivity After the resin composition layer is developed, it is washed with water, and further may be baked at 15 to 230 tons for 10 to 60 minutes as needed, or may be irradiated with ultraviolet rays having a wavelength of 200 to 300 njn. It is preferred to carry out the post-baking step when (A3) is contained. Using the photosensitive resin composition of the present invention, a hardened resin pattern can be formed on the substrate by the above steps. In the hardened resin pattern obtained by the household, it is preferable that the angle of the hardened resin of the substrate is 34 degrees, and the angle of the type of 320 320097 200903160 is less than 90 degrees. When the angle is within the above range, it is preferable to report the disconnection of the IT〇 wiring when the liquid crystal display device is formed. The hardened resin pattern has a good total displacement amount and recovery rate, and is excellent in resistance, bulkiness, and heat resistance, so that it can be used as a control liquid crystal in addition to the photo spacer used in the liquid crystal display device. The protrusion for alignment, the insulating film of the FT substrate, the insulating film of the organic EL element, and the protective film of CCD. Also, it can be used for a touch panel. Therefore, by incorporating the cured resin pattern obtained by the above method into a display device such as a liquid crystal display device, it is possible to improve the yield and to manufacture a display device of excellent quality. [Examples] The present invention is described in more detail by the following examples, but the present invention is not limited by the examples. In the example, the content and the amount and the amount of the use are indicated as the quality basis unless otherwise stated. Example 1

3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride 1 mol and pentaerythritol triacrylate 2 molar reactant (equivalent to (A1)) (MK ESTER CBX -SK02; manufactured by Shin-Nakamura Chemical Co., Ltd.) 75 parts, dipentaerythritol hexaacrylate (corresponding to (A2)) 2 parts, ΟΧΕ-Ο1 (corresponding to (B); ciba Specialty Chemicals) ι, propylene glycol 58 parts of monodecyl ether acetate, 42 parts of ethyl lactate, KBM-503 (3-methacryloxypropyltrimethoxy decane; manufactured by Shin-Etsu Chemical Co., Ltd.; followed by a modifier), 5 parts, 35 320097 200903160 A photosensitive resin composition obtained by mixing. The weight average molecular weight of the binder component (A) in the obtained photosensitive resin composition 1 is a?. The results carried out as described below are shown in Table 1. <Formation formation> On a 2 inch square glass substrate (Igle2®; manufactured by c〇rning Co., Ltd.), a photosensitive resin composition was spin-coated and pre-baked for 1 minute at 1 〇 (r). The substrate on which the photosensitive resin composition was spin-coated was separated from the patterned quartz glass mask described in each of the following evaluation items, and the optical machine (TEM-i 50RSK; Topcon) was used. It is irradiated with light at a J/cm2 exposure (365 nm basis) in an atmospheric environment. After light irradiation, the substrate is impregnated in a water-based imaging solution containing a nonionic surfactant 〇(10) _ 4%. 〇 逑 逑 逑 逑 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' After the film thickness of the type, it is 3 〇 <analytical> ° In the exposure step, 'in terms of the reticle, the light pattern formed on the same plane using the 1:1 line and the gap pattern is used, and the resolution is measured using an optical microscope. ^Graphic image. 'The minimum line width of the knife is <pattern shape> In the exposure step, the seal is two,

3 5 First cover and &quot;, about the use of the square of the one side of the square 10 A light transmission part pattern (pattern interval is 1 〇〇 ' formed on the same plane Φ 丄 丄 丄 丄 丄 丨 丨 丨 100 100 100 100 100 100 100 Z m) The pattern formed by the first cover on the ten faces is observed using a scanning electron 320097 36 200903160 microscope (S_4_; (share) manufactured by Hitachi, Ltd.). When the angle of the pattern is less than % for the pattern side wall of the substrate, it is judged to be a reverse cone when it is more than 90 degrees. Wiring the Si cone S'. When the liquid crystal display device is formed, it is difficult to introduce _ <mechanical characteristics> (total displacement amount and recovery rate). In the exposure step, the size of the translucent portion based on the size of the rim is used (the pattern interval is i (10) (four) The pattern formed by the exposure of the two masks, the line u 18//1&quot; which is in contact with the surface of the substrate, is measured using a dynamic ultra-micro hardness tester (DUH.W201; manufactured by Shimadzu Co., Ltd.) Its total displacement (# calendar) and elastic displacement (Am). The recovery rate (0/〇) is obtained from these values.

One test condition One test mode: Load-removal test Test force: l〇〇mN U Load speed: 4.41mN/sec Hold time: 5sec Lizi··cone taper (diameter 5〇//m) Recovery rate ( %): (elastic displacement amount (/ζιη) and recovery rate <solvent resistance> In the exposure step, except that the mask was not used, the same operation was performed to prepare a coating film, and the film thickness was measured. The obtained coating film was immersed in N-methylpyrrolidone at 4 ° C for 4 minutes, and the film thickness was measured, and the rate of change was determined according to the following formula. 320097 37 200903160 m)) xl〇〇 (also ♦ The film thickness before (um)/immersion (from the case where the film thickness changes from 96 to !01% is good, and the case outside the range of a is described as X.), then, the "richness" In the exposure step, in addition to the operation without using a reticle, the radish is the same as the thickness of the I film, so that the obtained coating film is at a rate of change. *, ,, 120 knives &quot;^麦' The film thickness was measured, and the film thickness change (%) was determined according to the following formula: (film thickness m after heating)) xl〇〇

Good, § has been loaded as Q. If the film thickness changes from 90 to 100%, the case of 90 is marked as X. Example 2 3,4-dicarboxy-i,2,3,4-tetrahydro-methane naphthalene succinic anhydride ymopentaerythritol tripropionate 2 molar reaction (equivalent to (4))) 55 Share. Dipentaerythritol hexaacrylate (corresponding to (A2)) 20 parts, ethylene glycol dimercapto acrylate (corresponding to (Α2-1)) 2 parts, 〇ΧΕ_〇1 (corresponding to (8); manufactured by Ciba Specialty Chemicals Parts, propylene glycol monomethyl ether acetate 58 parts, knife ethyl lactate 42 parts, ΚΒΜ · 503 (3-methacryl oxime propyl trimethoxy decane; Shin-Etsu Chemical Co., Ltd.; followed by a modifier) 5 parts of the photosensitive resin composition 2 obtained by mixing. The weight average molecular weight of the binder component (A) in the obtained precursor tree 320097 38 200903160, and the product 2 was 717. The evaluation was carried out in the same manner as in Example 1 except that the photosensitive resin composition 2 was used. The results are shown in the table. Example 3, using photosensitive resin composition 2, development, washing, and making a duv lamp The pattern and the coating film were formed and evaluated in the same manner as in the examples except that the makeup was shot at 1,000 mJ/cm 2 (254 nm). Comparative Example 1 Copolymer of methacrylic acid and benzyl methacrylate (A) Acrylic unit and benzyl sulfhydryl acrylate unit The composition has a molar ratio of 3:7, an acid value of 113, a polystyrene-equivalent weight average molecular weight (Mw) of 25,000), 55 parts, and dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Sakamoto Chemical Co., Ltd.), 40 parts, KBM-503 (3-mercapto propylene oxypropyl tridecyloxy decane; Shin-Etsu Chemical Co., Ltd.; adhesion improver) 5 parts,

Irqacure 369 (equivalent to (B), Ciba Specialty Chemicals VIII) 5 parts, 4,4'-bis(diethylamino)benzophenone (equivalent to (B)); eaB_F; Baotu Valley Chemical Industry (Manufacturing): 5 parts, 211 parts of propylene glycol monomethyl ether acetate, 211 parts of ethyl lactate, and a photosensitive resin composition 4 obtained by mixing. The weight average molecular weight of the binder component in the obtained photosensitive resin composition 4 was 14 &lt; 7 〇 〇. 320097 39 200903160 Except for the use of the photosensitive resin composition 4, the evaluation was carried out in the same manner as in the examples. table

The embodiment shown in Table 曰i! As a result of the results of the third embodiment, it was found that the average molecular weight of the binder component was the photosensitive resin of the present invention, and the resolution of the cured resin wax pattern was excellent. Further, the photosensitive resin composition (4) of the present invention is used to form a cured resin pattern 2::! The shape of the pattern is a tapered shape and is not a pattern shape as a photo spacer, and a total displacement can be obtained. The mechanical and heat resistance and solvent resistance of the amount and recovery rate are superior to the hardened resin pattern and coating film. Further, in the case of the composite 4 θ &amp; of the comparative example 1, there is a 147 nn. The tenth knife 垔 is M00 or more, and the photosensitive resin composition of the binder component (4) of 7 Å is inferior to the resolution. /, this service [industrial use possibility] The photosensitive resin composition of the present invention is excellent in resolution when it is a wax pattern, and can be hardened, sturdy, sturdy, sturdy, graphical, and mechanical. The pattern and coating film of excellent Nylon agent can be used for the light interval 320097 40 200903160, ^ m , and must be τ /71 from the heart skin. 11 excellent, so it is suitable as a light room! 'The soil layer, the film, the protrusion for controlling the alignment of the liquid crystal, the alignment of the film used for the alignment, etc., for the alignment of the film, etc. No. Simple description of the main element No symbol description of the element 320097 41

Claims (1)

200903160 X. Patent application scope: 1 · A photosensitive resin composition containing a binder component (A) and a photopolymerization initiator (B), characterized in that, in terms of the binder component (A), it contains: Photopolymerizable compound (A1) having one or more carboxyl groups and two or more photopolymerizable unsaturated bonds, and a photopolymerizable compound (A2) having no carboxyl group; weight average molecular weight of the binder component (A) It is 1,500 or less. 2. The photosensitive resin composition of the first aspect of the invention, wherein the photopolymerizable compound (A1) having one or more carboxyl groups and two or more photopolymerizable unsaturated bonds is an acid anhydride and A reactant of a compound having a hydroxyl group and two or more unsaturated double bonds. 3. The photosensitive resin composition of claim i, wherein the photopolymerizable compound (A2) having no carboxyl group contains the compound (A2-1) represented by the formula (1); r2o. R2 (1) m [In the formula (I), "R1 represents a stretching group having a carbon number of 1 to 6, R2 represents a group having a polymerizable unsaturated bond, and m represents an integer of 1 to 6]. 4. In the case of the photosensitive resin composition of the item i of the patent application, in the first aspect, there are one or more carboxyl groups and two or more polymerizable compounds (A1) which are unsatisfactory and unsaturated. The content of the phase, the 4th of the dan\jie &amp; relative to the Wei cake component (A), in terms of Berry's rate of '10 to 99 temporary 〇 / take in children &amp; Berry / 〇' The content of the light-free compound + (A2) having no slow base is from i to 9% by mass. The photosensitive resin composition of the third aspect of the invention, wherein the content of the compound (A2-1) which is not the formula (1) is relative to the photopolymerizable compound (A2) which does not have a carboxyl group, In terms of mass fraction, it is up to 7% by mass. 6. A hardened resin pattern formed by using a photosensitive resin composition as set forth in the scope of the patent application. 7. The hardened resin pattern of claim 6 wherein the hardened resin pattern is a photo spacer. 8. A method for producing a hardened resin pattern, which is coated on a substrate with a photosensitive resin composition as claimed in claim 1, after removing the solvent, 2 masks (four) shots (four) lines, and then an aqueous solution is applied After the image is developed to form a specific pattern, heating is performed. 9: The manufacturing method of the hardened tree type is to apply the photosensitive resin composition of the first item (4) of the main (4) range on the substrate, and irradiate the II ray in addition to the second test mask, and then enter the test solution. After a specific pattern, ultraviolet irradiation is performed. Shape 10. A liquid crystal display device having a resin pattern as claimed in the patent application. Gudi 6 hard 32097 43 200903160 VII. Designated representative map: There is no schema in this case (1) The representative representative of the case is: (). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R20--R1*0 — R2 4 320097