TW201426187A - Negative photosensitive resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a negative photosensitive resin composition making it possible to obtain a hardened layer having excellent characteristics in terms of high transparency, high permittivity, and low leak current and having properties that are maintained without degrading even upon being subjected to a chemical treatment or a treatment under a high temperature. The means for addressing the problem is a photosensitive resin composition containing: metal oxide particles of a metal selected from the group consisting of titanium, barium, hafnium, tantalum, tungsten, yttrium, and zirconium; (B) an alkali-soluble polyester resin having a radical polymerizable group and an aromatic ring; (C) a multi-functional (meth) acryloyl compound; and (D) a photopolymerization initiator.

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition.

In recent years, with the growth of the display industry and the touch panel industry, the importance of photosensitive transparent materials has increased, and with the low price of liquid crystal displays, the manufacturing process has been simplified, and the replacement of low-priced materials has progressed. For example, various insulating films and passivation films in the TFT [Thin FILM Transistor] manufacturing process are generally made of a high insulating inorganic material such as tantalum carbide, tantalum nitride, aluminum oxide, hafnium oxide or titanium oxide by a CVD method. Manufactured by film formation. However, since the CVD method is a high cost, research on a photosensitive organic insulating material which can be manufactured by an optical lithography method which is cheaper than the CVD method is very popular (Patent Documents 1 to 3).

In addition, as for the use of the optical member, a transparent insulating film obtained by compounding a metal oxide such as titanium oxide or zirconium dioxide with a siloxane or an acrylic resin has been studied (Patent Document 4).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2011-186069

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-43055

Patent Document 3: Japanese Patent Laid-Open Publication No. 2007-316531

Patent Document 4: Japanese Patent Laid-Open Publication No. 2011-151164

However, conventional photosensitive organic insulating materials have a lower dielectric constant and poor insulating properties than inorganic materials. Therefore, when an insulating film is used, if the initial voltage of the transistor is increased or the leakage current is increased, The problem that causes the display performance of the display to degrade is current. Such a composite material of the above metal oxide and resin is improved, but such a composite material is considered to be a problem in that the chemical resistance in the production step and the treatment at a high temperature are low, which may cause deterioration.

In view of the above, it is an object of the present invention to provide a cured film having excellent properties such as high transparency, high dielectric constant, and low leakage current without deterioration due to chemical or high-temperature treatment. A photosensitive resin composition.

As a result of intensive studies, the present inventors have found that a composition formed of an alkali-soluble polyester resin having a radical polymerizable group and an aromatic ring as a representative component can effectively solve the above problems. invention.

In other words, the photosensitive resin composition, the transparent cured film, and the thin film transistor substrate described in the following (1) to (6) are provided.

(1) A negative photosensitive resin composition comprising: (A) a metal oxide particle selected from a group consisting of titanium, tantalum, niobium, tantalum, tungsten, niobium, and zirconium, and (B) having freedom An alkali-soluble polyester resin having a base polymerizable group and an aromatic ring, (C) a polyfunctional (meth) acrylonitrile-based compound, and (D) a photopolymerization initiator.

(2) The negative photosensitive resin composition according to the above aspect, wherein the alkali-soluble polyester resin contains a chemical structure represented by the following general formula:

(R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or such substituted groups, or R ¹ and R ² Together, a cycloalkyl group having 2 to 12 carbon atoms, an aromatic ring having 5 to 12 carbon atoms, or the substituted group are formed. R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 2 to 12 carbon atoms, and carbon. The number of 6 to 20 aryl groups, or the substituted groups. The n and m groups each independently represent an integer from 0 to 10.

(3) The negative photosensitive resin composition according to any one of the above, comprising: (E) an alkoxysilane or a polyoxyalkylene having four or more alkoxy groups.

(4) A cured film obtained by using any of the above negative photosensitive resin compositions.

(5) A TFT substrate comprising the cured film described above.

(6) A method for producing a thin film transistor substrate, comprising the step of applying a negative photosensitive resin composition of any of the above, and forming a pattern by exposure and development.

According to the negative photosensitive resin composition of the present invention, it is possible to obtain a high dielectric constant without damaging the adhesion to the substrate even when immersed in the chemical, without causing deterioration of the film property due to chemical penetration. Insulating transparent insulating film. Further, a thin film transistor substrate having a transparent dielectric film having a high dielectric constant and insulating property can be produced.

1‧‧‧Substrate

2‧‧‧gate electrode

3‧‧‧ gate insulation

4‧‧‧Source/drain electrodes

5‧‧‧Source/drain electrodes

6‧‧‧P3HT film

Fig. 1 is a conceptual diagram of a method for evaluating characteristics of a TFT.

The negative photosensitive resin composition of the present invention is characterized by comprising (A) a metal oxide particle selected from a group consisting of titanium, tantalum, niobium, tantalum, tungsten, niobium and zirconium, and (B) having a radical An alkali-soluble polyester resin having a polymerizable group and an aromatic ring, (C) a polyfunctional (meth) acrylonitrile-based compound, and (D) a photopolymerization initiator.

The negative photosensitive resin composition of the present invention contains (A) metal oxide particles selected from the group consisting of titanium, tantalum, niobium, tantalum, tungsten, niobium and zirconium. The common point of the metal oxide particles is a relative dielectric constant (hereinafter also referred to as "ε _r ") of 20 or more. Here, the metal oxide particles may contain a composite metal oxide of two or more kinds of metals contained in the above metal group. Further, the metal oxide particles may be a mixture of metal oxide particles having different compositions. The relative dielectric constant of the metal oxide is, for example, a coaxial probe method capable of directly measuring a metal oxide powder, or a powder is subjected to press molding to form pellets, which are then sandwiched between two electrodes and measured. Parallel plate capacitor method, etc. These measurement methods can be measured using an impedance analyzer (such as 4294A manufactured by Agilent Co., Ltd.), an LCR meter (such as 4285A manufactured by Agilent Co., Ltd.), and a dedicated jig (8570E or 16451B/16453A manufactured by Agilent Co., Ltd.).

By containing the (A) metal oxide particles, the relative dielectric constant and insulating properties of the cured negative photosensitive resin composition, that is, the cured film, etc., are improved. Examples of the (A) metal oxide particles include titanium oxide, barium titanate, barium sulfate, cerium oxide, cerium oxide, cerium oxide, tungsten oxide, cerium oxide or zirconium oxide. From the viewpoint of the dielectric constant, titanium oxide (ε _r = 115), zirconium oxide (ε _r = 30), barium titanate (ε _r = 400), or a relative dielectric constant (ε _r ) of 20 or more is preferable. Cerium oxide (ε _r = 25). Further, in view of the development of the dispersion technique of the nanometer grade, it is more preferable to use titanium oxide or zirconium oxide as a commercially available product which can be easily obtained.

The number average particle diameter of the (A) metal oxide particles is preferably 100 nm. Lower, more preferably 50 nm or less, and particularly preferably 30 nm or less. If the particle size is small, the transparency of the cured film can be improved, and if it is smaller, the homogeneity and insulation of the cured film can be improved. The number average particle diameter is preferably 1 nm or more, more preferably 3 nm or more. If it is more than a certain size, the relative dielectric constant of the theoretical value can be exhibited while maintaining the crystal structure of the metal oxide particles, and the relative dielectric constant of the cured film or the like can be improved.

(A) The metal oxide particles may be subjected to surface modification for the purpose of improving the dispersibility and the like in the negative photosensitive resin composition. The surface modification system may be, for example, a coating using cerium oxide or a surface modifying agent using an organic compound having an alkoxyalkyl group, an isocyanate group or a carboxyl group. The above surface modifying agent is preferably polymerizable without the viewpoint of forming a covalent bond with (B) an alkali-soluble polyester resin or (C) a polyfunctional (meth) acrylonitrile-based compound by irradiation with ultraviolet rays. Saturated base.

The content of the (A) metal oxide particles in the negative photosensitive resin composition of the present invention is preferably a total component other than the organic solvent from the viewpoint of the hardness and relative dielectric constant of the cured film or the like. 10~90% by mass.

(A) When the metal oxide particles are adjusted to an appropriate particle powder, they may be pulverized or dispersed using a disperser such as a bead mill. The commercially available nanoparticle powder system may, for example, be T-BTO-020RF (manganese titanate; manufactured by Toda Industrial Co., Ltd.), UEP-100 (zirconia; manufactured by First Rare Element Chemical Industry Co., Ltd.) Or STR-100N (titanium oxide; manufactured by Nippon Chemical Industry Co., Ltd.).

Further, the (A) metal oxide particles may be obtained in the form of a dispersion dispersed in a liquid. Examples of the cerium oxide-titanium oxide particles include "Optlake" (registered trademark) TR-502, "Optlake" TR-503, "Optlake" TR-504, "Optlake" TR-513, "Optlake" TR-520, "Optlake" TR-527, "Optlake" TR-528, "Optlake" TR-529, "Optlake" TR-544, or "Optlake" TR-550 (both daily catalysts) Chemical industry (shares) system). Examples of the zirconia particle system include: "Bairaru" registered trademark Zr-C20 (average particle diameter = 20 nm; manufactured by Domus Chemical Co., Ltd.), ZSL-10A (average particle diameter = 60-100 nm; Company system), "NANOUSE" (registered trademark) OZ-30M (average particle size = 7nm; manufactured by Nissan Chemical Industries Co., Ltd.), SZR-M (manufactured by Nippon Chemical Co., Ltd.), or HXU-12OJC (Sumitomo Osaka Cement) (share) system).

The negative photosensitive resin composition of the present invention contains (B) an alkali-soluble polyester resin having a radical polymerizable group and an aromatic ring. By containing the (B) alkali-soluble polyester resin, it is possible to impart negative-type photosensitive pattern processability to the photosensitive resin composition. More specifically, if the negative photosensitive resin composition is exposed, (B) the alkali-soluble polyester resin is subjected to radical polymerization with (C) a polyfunctional (meth)acryl-based compound to form a cross-linking. The polymer can be formed by removing the non-exposed portion by subsequent development. Further, the chemical resistance of the exposed UV cured film and the cured thermosetting film can be improved. More specifically, before and after hardening, a cured film which does not impair the relative dielectric constant, the insulating property, and the adhesion can be obtained even if it is exposed to a strongly acidic or strongly basic chemical. In general, since the ester group is highly polar and highly hydrophilic, decomposition reaction such as hydrolysis is likely to occur. Therefore, when a cured film or the like made of an acrylic resin or a polyester resin is immersed in an acid or a base, it is presumed that the film is peeled off due to decomposition of the ester bond inside the cured film or the like. The mechanism of action obtained by containing (B) an alkali-soluble polyester resin having a radical polymerizable group and an aromatic ring is not clear, but it is considered that the decomposition property of the ester group and the radical polymerization property are lowered by the aromatic ring. By polymerizing the base to increase the film density, decomposition due to chemical penetration can be suppressed.

The content of the (B) alkali-soluble polyester resin in the negative photosensitive resin composition of the present invention is preferably from 1 to 80% by mass, more preferably from 5 to 50% by mass, based on the total amount of the organic solvent. If the content is more than 1% by mass, sufficient alkali developability can be obtained, It is prone to unexposed residue and surface contamination. When the content is 80% by mass or less, film peeling or the like occurs during development. The content of the (C) polyfunctional (meth) acrylonitrile compound in the negative photosensitive resin composition of the present invention is such that the hardness of the cured film or the like can be increased, and it is preferably the entire negative photosensitive resin composition. 1 to 20% by mass. Further, the total amount of the components other than the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

The alkali-soluble polyester is preferably one which is soluble in an aqueous solution of tetramethylammonium hydroxide (TMAH) at a concentration of 0.1% by mass or more at 23 °C. More preferably, it is soluble in 1% by mass or more of the TMAH aqueous solution, and particularly preferably in 2% or more of the TMAH aqueous solution.

The method for synthesizing the (B) alkali-soluble polyester resin of the present invention is preferably from the viewpoints of easy synthesis and less side reactions, preferably via, for example, (b1) a polyfunctional epoxy compound and (b2) a polycarboxylic acid. A method of a polyaddition reaction of a compound or a (b3) complex addition reaction of a polyol compound with (b4) a dianhydride. (b3) The polyol compound is preferably a (b1) polyfunctional epoxy compound and (b5) a monobasic acid containing a radical polymerizable group from the viewpoint of easily introducing a radical polymerizable group and an aromatic ring. Obtained by the reaction of the compound.

The method of the re-addition reaction of the (b1) polyfunctional epoxy compound and the (b2) polycarboxylic acid compound can be exemplified by the following method. In the presence of a catalyst, (b2) a polyfunctional carboxylic acid compound is added in an amount of 1.01 to 2 equivalents based on the (b1) polyfunctional epoxy compound to carry out a re-addition. An ester bond is formed by this reaction. Then, the terminal carboxylic acid moiety is added (b6) to the epoxy compound containing a radical polymerizable group. An acid anhydride (b7) is added to the resulting hydroxyl group. In another method, a (b1) polyfunctional epoxy compound is added in an amount of 1.01 to 2 equivalents based on the (b2) polycarboxylic acid compound in the presence of a catalyst to carry out a re-addition. An ester bond is formed by this reaction. Then, a radical polymerizable group monobasic acid compound is added (b5) to the epoxy moiety at the terminal. An acid anhydride (b7) is added to the resulting hydroxyl group.

By reacting a (b3) polyol compound with a (b4) dianhydride The method can be exemplified as the following method. The (b3) polyol compound and (b4) dianhydride are polymerized in the presence of a catalyst. An ester bond is formed by this reaction. Then, an epoxy compound containing a radical polymerizable group is added (b6) to a part of the generated carboxyl group. Further, when the (b3) polyol compound has a radical polymerizable group, an epoxy compound containing a radical polymerizable group may not be added.

Examples of the catalyst used in the addition reaction and the addition reaction include an ammonium catalyst such as tetrabutylammonium acetate; 2,4,6-tris(dimethylaminomethyl)phenol or dimethyl group. An amine-based catalyst such as benzylamine; a phosphorus-based catalyst such as triphenylphosphine; and a chromium-based catalyst such as Chromium Acetylacetonate or chromium chloride.

(b1) The polyfunctional epoxy compound is preferably a compound represented by the following general formula (1) because it can improve the insulating properties and chemical resistance of the cured film or the like.

(R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or the substituted group, or R ¹ and R ² together Forming a cycloalkyl group having 2 to 12 carbon atoms (preferably 5 to 12), an aromatic ring having 5 to 12 carbon atoms, or the substituted groups. R ³ and R ⁴ each independently represent hydrogen and carbon. a number of 2 to 12 alkyl groups, a carbon number of 6 to 20 aryl groups, or the substituted groups. The n and m groups each independently represent an integer of 0 to 10.

Examples of R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, an o-tolyl group, or a biphenyl group, or the following Show substituents.

[Chemical 3]

The cyclic structure formed by R ¹ and R ² together may be a substituent as shown below, and the cyclic structure is preferably a five to seven member ring.

(wherein the carbon of * in the formula represents the carbon in which R ¹ and R ² are bonded in the formula (1).)

(b1) The polyfunctional epoxy compound is exemplified by the compounds shown below.

(b2) The polycarboxylic acid compound may, for example, be succinic acid, maleic acid, fumaric acid, itaconic acid, citric acid, citric acid, isophthalic acid, trimellitic acid, orthobenzene Formic acid, 2,2'-biphenyldicarboxylic acid, or 4,4'-biphenyldicarboxylic acid, and it is preferable to improve the chemical resistance and insulating properties of the cured film, etc., preferably citric acid, citric acid, Isononanoic acid, trimellitic acid, pyromellitic acid, 2,2'-biphenyldicarboxylic acid, or 4,4'-biphenyldicarboxylic acid.

(b3) The polyol compound is, for example, an aliphatic alcohol compound such as ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane or pentaerythritol; 9,9-bis[4-(2-hydroxyethoxy) a compound obtained by reacting a (b1) polyfunctional epoxy compound with (b5) a radical polymerizable group-containing monobasic acid compound; or a bisphenol compound represented by the following general formula (2); An aromatic alcohol compound such as a compound obtained by reacting (b6) an epoxy compound containing a radical polymerizable group. Among them, preferred are aromatic alcohol compounds. Further, R ¹ , R ² , R ³ and R ⁴ in the general formula (2) are the same as those in the general formula (1).

(b4) The dianhydride system may, for example, be pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid Diacid anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2',3,3' -diphenyl ketone tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoromalonic anhydride, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropyl Diacid anhydride, 1,1-bis(3,4-dicarboxyphenyl)glycolic anhydride, 1,1-bis(2,3-dicarboxyphenyl)glycolic anhydride, bis(3,4-dicarboxybenzene) Methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfonic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride or 3,4, An aromatic tetracarboxylic acid dianhydride such as 9,10-fluorene tetracarboxylic acid dianhydride; butane tetracarboxylic acid dianhydride, cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Diacid anhydride, cyclohexane tetracarboxylic acid dianhydride, bicyclo [2.2.1.] heptane tetracarboxylic acid dianhydride, bicyclo [3.3.1.] tetracarboxylic dianhydride, bicyclo [3.1.1.] g-2 - ene tetracarboxylic acid dianhydride, bicyclo [2.2.2. An aliphatic tetracarboxylic dianhydride such as octane tetracarboxylic acid dianhydride or adamantane tetracarboxylic acid dianhydride; and chemical resistance of a cured film or the like The rim is preferably pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, or 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, and to improve the transparency of the cured film or the like, preferably cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane An alkyltetracarboxylic acid dianhydride or a cyclohexane tetracarboxylic acid dianhydride.

(b5) The radical polymerizable group-containing monobasic acid compound may, for example, be (meth)acrylic acid, succinic acid mono(2-(methyl)acryloxyethyl)ester, or citric acid mono(2-(A) Base) propylene oxiranyl ethyl ester, tetrahydrofurfuric acid mono(2-(methyl) propylene oxyethyl) ester or p-hydroxy styrene.

(b6) The epoxy compound containing a radical polymerizable group may, for example, be a glycidyl (meth)acrylate, a (meth)acrylic acid-α-ethylglycidylpropyl ester or a (meth)acrylic acid-α. - n-propylglycidyl propyl ester, (meth)acrylic acid-α-n-butyl epoxypropyl ester, (meth)acrylic acid-3,4-epoxybutyl ester, (meth)acrylic acid-3,4- Epoxyheptyl ester, (meth)acrylic acid-α-ethyl-6,7-epoxyheptyl ester, butyl vinyl ether, butyl allyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethylene Propyl ether, cyclohexane vinyl ether, cyclohexane allyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxybutyl allyl ether, allyl epoxidized ether, vinyl epoxidized ether, o-ethylene Benzyl epoxidized propyl ether, m-vinylbenzyl epoxidized propyl ether, p-vinylbenzyl epoxidized propyl ether, α-methyl-o-vinyl benzyl epoxidized propyl ether, α-methyl-vinyl vinyl benzyl Glycidyl ether, α-methyl-p-vinylbenzyl epoxidized propyl ether, 2,3-diepoxypropoxymethyl styrene, 2,4-diepoxypropoxymethyl styrene, 2,5-diepoxypropoxymethylstyrene, 2,6-diepoxypropoxymethylstyrene, 2,3,4-triepoxypropoxymethylstyrene , 2,3,5-triglycidoxymethylstyrene, 2,3,6-triepoxypropoxymethylstyrene, 3,4,5-triepoxypropoxymethylbenzene Ethylene or 2,4,6-triepoxypropoxymethylstyrene.

Examples of the (b7) acid anhydride include succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic acid monohydride, 2,3-biphenyldicarboxylic anhydride, and 3,4-biphenyl. Dicarboxylic anhydride, hexahydrophthalic anhydride, glutaric anhydride, 3-methylphthalic anhydride, lower Alkene dicarboxylic anhydride, cyclohexene dicarboxylic anhydride, or 3-trimethoxydecyl propyl succinic anhydride.

The negative photosensitive resin composition of the present invention contains (C) a polyfunctional (meth)acryl fluorenyl compound (that is, a compound having 2 or more acryl fluorenyl groups and/or methacryl fluorenyl groups in the molecule). By containing the (C) polyfunctional (meth) acrylonitrile-based compound, the negative photosensitive resin composition can be cured by light irradiation. Further, in the present invention, both the (B) alkali-soluble polyester resin having a radical polymerizable group and an aromatic ring and the (C) polyfunctional (meth)acryl-based compound are regarded as (B). ).

The polymerizable compound having two (meth)acryl fluorenyl groups in the molecule may, for example, be 1,3-butanediol di(meth)acrylate or 1,4-butanediol di(meth)acrylic acid. Ester, 1,6-hexanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,4-dimethyl Base-1,5-pentanediol di(meth)acrylate, butylethylpropanediol (meth)acrylate, ethoxylated-1,4-cyclohexanedimethanol di(meth)acrylate , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, oligomerization Ethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2-ethyl-2-butylbutanediol di(meth)acrylate , hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, EO modified bisphenol A di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, oligomeric propylene glycol Di(meth)acrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, 1,9-anthracene Alcohol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, tricyclodecane di(meth)acrylate, bis(2-hydroxyethyl)isotrien Polycyanate di(meth)acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, 9,9 - bis[4-(2-methylpropenyloxyethoxy)phenyl]anthracene, 9,9-bis[4-(2-methylpropenyloxyethoxy)-3-methylbenzene Base]茀, (2- Propylene methoxypropoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-propenyloxyethoxy)-3,5-dimethylphenyl]anthracene, Or 9,9-bis[4-(2-methylpropenyloxyethoxy)-3,5-dimethylphenyl]anthracene.

The polymerizable compound having three (meth)acryl fluorenyl groups in the molecule may, for example, be trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, or the like. The alkylene oxide modified tris(meth)acrylate of hydroxymethylpropane, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tris((meth)propene)醯 propyl propyl ether, glycerol tri(meth) acrylate, ginseng (2-hydroxyethyl) iso-cyanurate tri(meth) acrylate, iso-cyanuric acid oxidized alkyl modified three (Meth) acrylate, dipentaerythritol tris(meth) acrylate, tris((meth) propylene oxiranyl) isocyanurate, hydroxypivalaldehyde modified dimethylol propane (Meth) acrylate, sorbitol tri(meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate or ethoxylated glycerol triacrylate.

Examples of the polymerizable compound having four (meth)acryl fluorenyl groups in the molecule include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, and bis(trimethylol)propane IV. (Meth) acrylate, dipentaerythritol tetra(meth) acrylate, or ethoxylated pentaerythritol tetra (meth) acrylate.

The polymerizable compound having five (meth)acryl fluorenyl groups in the molecule may, for example, be sorbitol penta (meth) acrylate or dipentaerythritol penta (meth) acrylate.

The polymerizable compound having six (meth)acryl fluorenyl groups in the molecule may, for example, be oxidized by dipentaerythritol hexa(meth) acrylate, sorbitol hexa(meth) acrylate or phosphazene. The alkyl modified hexa(meth) acrylate or caprolactone modified dipentaerythritol hexa (meth) acrylate.

a polymerizable compound having seven (meth)acryl fluorenyl groups in the molecule. For example, tripentaerythritol heptaacrylate is listed.

The polymerizable compound having eight (meth)acryl fluorenyl groups in the molecule may, for example, be tripentaerythritol octaacrylate.

Commercially available (C) polyfunctional (meth) acrylonitrile-based compound, for example, "Aronix" (registered trademark) M-400, M-404, M-408, M-450, M-305 , M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-510, M-520, M-220, M-225, M-233, M -240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270 , TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905 or TO-1330 (both manufactured by Toagosei Co., Ltd.); "KAYARAD" (registered trademark) D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR- 213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TP A-320, TPA-330, KSHDDA, KS-TPGDA, or KS-TMPTA (both manufactured by Nippon Kayaku Co., Ltd.); Light Acrylate PE-4A, DPE-6A or DTMP-4A (Kyoeisha Chemical Co., Ltd.) Company system); Biscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.; a mixture of three pentaerythritol octaacrylate and tripentaerythritol heptaacrylate).

The content of the (C) polyfunctional (meth) acrylonitrile compound in the negative photosensitive resin composition of the present invention is such that the hardness of the cured film or the like is increased, and the negative photosensitive property is The entire resin composition is preferably 1 to 20% by mass. Further, the total amount of the components other than the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

The negative photosensitive resin composition of the present invention must contain (D) a photopolymerization initiator. (D) The photopolymerization initiator is preferably one which is decomposed and/or reacted by light (including short-wavelength electromagnetic waves such as ultraviolet rays) or an electron beam to generate a radical. Such a photopolymerization initiator may, for example, be 2-methyl-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Physo-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1-(2,4,6-trimethylbenzylidenephenyl)phosphine oxide, bis(2,4,6-trimethylbenzylidene)phenyl oxide Phosphine, bis(2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl)phosphine oxide, 1-phenyl-1,2-propanedione-2-( O-ethoxycarbonyl)anthracene, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzamide)], 1-phenyl-1,2-butane Keto-2-(o-methoxycarbonyl)anthracene, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)anthracene, ethyl ketone, 1-[9-ethyl-6-(2 -Methylbenzylidene)-9H-carbazol-3-yl]-,1-(O-acetamidine), 4,4-bis(dimethylamino)diphenyl ketone, 4,4- Bis(diethylamino)diphenyl ketone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, diethoxy Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin A Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenyl ketone, o-benzhydryl benzoic acid Ester, 4-phenyldiphenyl ketone, 4,4-dichlorodiphenyl ketone, hydroxydiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, alkylation Phenyl ketone, 3,3',4,4'-tetra(peroxybutylbutylcarbonyl)diphenyl ketone, 4-benzylidene-N,N-dimethyl-N-[2-( 1-oxo-2-propenyloxy)ethyl]ammonium bromide, (4-benzylidenebenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzylidene phenoxy -N,N,N-trimethyl-1-propene ammonium chloride monohydrate, 2-isopropylsulfide Ketone, 2,4-dimethylsulfide Ketone, 2,4-diethyl sulfide Ketone, 2,4-dichlorosulfide Ketone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-sulfur -2-yloxy)-N,N,N-trimethyl-1-propane ammonium chloride, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl Base-1,2-diimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, anthracene, methylphenylglyoxylate, η 5-cyclopentadienyl-η 6-isopropylphenyl-iron (1+)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis(η 5-2,4-cyclopentane Dien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, sulfur Ketone, 2-methylsulfide Ketone, 2-chlorosulfur Ketone, 4-benzylidene-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl- 2-Phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, benzylmethoxyacetal, anthracene, 2-tert-butylindole , 2-amino hydrazine, β-chloropurine, fluorenone, benzofluorenone, dibenzocycloheptanone, methylene fluorenone, 4-azidobenzylidene acetophenone, 2,6- Bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, naphthalenesulfonyl chloride, quinoline chlorination Sulfonium, N-phenylthioacridone, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylhydrazine, benzammonium peroxide; or eosin or methylene blue A photoreductive dye or a combination of a reducing agent such as ascorbic acid or triethanolamine. Among them, in order to increase the hardness of the cured film or the like, an α-aminophenyl linone compound, a decyl phosphine compound, an oxime ester compound, a diphenyl ketone compound having an amine group, or a benzoic acid group having an amine group is preferable. Acid ester compound.

The α-aminophenyl ketone compound is exemplified by 2-methyl-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Polin-4-yl-phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1. Examples of the cerium oxide phosphine compound include 2,4,6-trimethylbenzimidylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, or Bis(2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl)phosphine oxide. The oxime ester compound may, for example, be 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, 1,2-octanedione, 1-[4-(phenylthio)- 2-(O-benzhydrazide)], 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)anthracene, 1,3-diphenylpropanetrione-2-(ortho Ethoxycarbonyl) hydrazine, or ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-o-ethylidene肟). The diphenyl ketone compound having an amine group may, for example, be 4,4-bis(dimethylamino)diphenyl ketone or 4,4-bis(diethylamino)diphenyl ketone. The benzoate compound having an amine group may, for example, be ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate or ethyl p-diethylaminobenzoate.

The content of the (D) photopolymerization initiator in the negative photosensitive resin composition of the present invention is relative to the viewpoint of increasing the hardness of the cured film and preventing the residual photopolymerization initiator from eluting and improving the solvent resistance. The total amount of the components other than the solvent is preferably 0.1 to 20 parts by mass.

The negative photosensitive resin composition of the present invention preferably contains (E) an alkoxydecane or a polyoxyalkylene having four or more alkoxy groups. By containing these decane compounds, the chemical resistance of the cured film or the like and the adhesion to the metal substrate can be improved. This effect is considered to be caused not by the interaction between the alkoxyalkyl group and the substrate but by the reaction of the hydroxyl group on the surface of the metal oxide particles with the alkoxyalkyl group to form a crosslinked structure.

Examples of the alkoxydecane having 4 or more alkoxy groups include tetramethoxynonane, tetraethoxydecane, tetraethoxydecane, tetraphenoxydecane, and tetramethoxydioxane. Alkane, tetraethoxydioxane, bis(triethoxydecylpropyl)tetrasulfide, cis-(3-trimethoxydecylpropyl)isocyanate, ginseng-(3) - Triethoxydecylpropyl)isocyanurate. From the viewpoint of improving the chemical resistance of the cured film, it is preferred to carry out a reaction of a bulky 9-functional decane with a tetrafunctional decane having less steric hindrance, preferably a 4-functional decane and a hexa-functional group. a mixture of basic decanes.

The polyoxyalkylene can be obtained by subjecting a bifunctional or trifunctional alkoxydecane compound to cohydrolyzate condensation (i.e., hydrolysis and partial condensation). Polyoxane Examples of the alkoxydecane compound include dimethoxy dimethyl decane, diethoxy dimethyl decane, dimethoxy diphenyl decane, diethoxy diphenyl decane, and dihydroxy bis. Phenyl decane, dimethoxy (methyl) (phenyl) decane, diethoxy (methyl) (phenyl) decane, dimethoxy (methyl) (phenethyl) decane, dicyclopentane Dimethoxyoxane or cyclohexyldimethoxy(methyl)decane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3- Propylene oxiranyl trimethoxy decane or 3-propenyl methoxypropyl triethoxy decane, 3-trimethoxydecyl propyl succinic anhydride, 3-triethoxy decyl propyl succinic anhydride, 3- Trimethoxydecylethylethyl succinic anhydride, 3-trimethoxydecyl butyl succinic anhydride, 3-glycidoxypropyl trimethoxy decane, 3-glycidoxypropyl triethoxy decane , 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxydecane, methyltrimethoxydecane, ethyltrimethyl Oxydecane, phenyltrimethoxynonane, Ethyltrimethoxydecane, naphthyltrimethoxydecane, methyltriethoxydecane,ethyltriethoxydecane,phenyltriethoxydecane,phenethyltriethoxydecane,naphthyltrile Ethoxy decane, tetramethoxy decane or tetraethoxy decane.

The negative photosensitive resin composition of the present invention may contain a polymerization inhibitor, for example, to adjust the sensitivity to light. Examples of the polymerization inhibitor include catechol such as phenol, hydroquinone, p-methoxyphenol, benzoquinone, methoxybenzoquinone, 1,2-naphthoquinone, cresol, and p-tert-butylcatechol. Class; alkyl phenols, alkyl bisphenols, phenolthiophenes , 2,5-di-t-butylhydroquinone, 2,6-di-t-butylphenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Ester, N, N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate), 2,2'-methylenebis(4-methyl-6- Third butyl phenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol , 2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl) 4-methylphenol, 1,1,3-tris(2'-methyl-5) '-Tertibutyl-4'-hydroxyphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'-- Hydroxybenzyl)benzene, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythritol 肆[3-(3,5-di Tributyl-4-hydroxyphenyl)propionate], 2-t-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl Phenols such as acrylate, 2,4-dimethyl-6-tert-butylphenol, 2-tert-butyl-4-methoxyphenol; 6-t-butyl-m-cresol, 2,6- Di-tert-butyl-p-cresol, 2-tert-butylhydroquinone, methylene blue, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, dipropyl Copper urethane, copper dibutyl dithiocarbamate, copper dibutyl dithiocarbamate, copper salicylate, thiodipropionate, thiol benzimidazole or phosphite Or use these compounds together with an oxygen-containing gas such as air. The content of the polymerization inhibitor in the negative photosensitive resin composition of the present invention is preferably 0.000005 to 0.2% by mass, more preferably 0.00005 to 0.1% by mass based on the entire negative photosensitive resin composition. Moreover, it is preferably 0.0001 to 0.5% by mass, and more preferably 0.001 to 0.2% by mass based on the total amount of the organic solvent.

The negative photosensitive resin composition of the present invention may contain an ultraviolet absorber in order to enhance the resolution after development. The ultraviolet absorber is preferably a benzotriazole compound, a diphenylketone compound, or a trisole from the viewpoints of transparency and non-coloring property of the cured film. a compound.

Examples of the benzotriazole-based compound include 2-(2H-benzotriazol-2-yl)phenol and 2-(2H-benzotriazol-2-yl)-4,6-tripentyl group. Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)- 6-dodecyl-4-methylphenol or 2-(2'-hydroxy-5'-methylpropenyloxyethylphenyl)-2H-benzotriazole. The diphenylketone-based compound may, for example, be 2-hydroxy-4-methoxydiphenyl ketone. three The ultraviolet absorber of the compound is exemplified by 2-(4,6-diphenyl-1,3,5-three 2-yl)-5-[(hexyl)oxy]-phenol.

The negative photosensitive resin composition of the present invention may contain a solvent. The solvent is a component which can uniformly dissolve the composition, and is preferably an alcohol compound, an ester compound or an ether compound. Examples of the solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Diacetone alcohol, ethylene glycol mono-n-butyl ether, 2-ethoxyethyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-3-methylbutanol, 3- Methoxy-3-methylbutanol acetate, 3-methoxybutyl acetate, 1,3-butanediol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether Acetate, ethyl lactate, butyl lactate, ethyl acetate ethyl acetate, or γ-butyrolactone.

The negative photosensitive resin composition of the present invention may also contain a surfactant. Examples of the surfactant include a fluorene-based surfactant such as a polyfluorene-based surfactant and an organic polyoxyalkylene; a fluorine-based surfactant; polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxygen a nonionic surfactant such as ethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate; a polyoxyalkylene surfactant; a poly(meth)acrylate surfactant; or a surfactant formed of an acrylic or methacrylic polymer. Commercially available surfactants include, for example, "MEGAFAC" (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (both manufactured by Dainippon Ink Chemical Industry Co., Ltd.), or NBX. Fluorine surfactant such as -15 or FTX-218 (both manufactured by Neos); BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (both BYK-Chemie‧Japan ( )) system) and other polyoxo-based surfactants.

The negative photosensitive resin composition of the present invention may further contain an additive such as a dissolution inhibitor, a stabilizer, or an antifoaming agent, as needed.

The solid content concentration of the negative photosensitive resin composition of the present invention can be appropriately determined according to the coating method, etc., and generally, the solid content concentration is set to 1 to 50% by mass or less.

A representative method for producing the negative photosensitive resin composition of the present invention (1) is exemplified by the following method. A dispersion of (A) metal oxide particles is weighed, and a solvent is added thereto as needed and stirred. Adding (D) photopolymerization initiator to other additives in the mixture Add the agent, add a suitable solvent, and stir to dissolve. Then, (B) an alkali-soluble polyester resin and (C) a polyfunctional (meth)acryl-based compound are added, and the mixture is further stirred for 20 minutes to 3 hours. The negative photosensitive resin composition is obtained by removing the foreign matter as needed and filtering the obtained solution.

A method of forming a cured film using the negative photosensitive resin composition of the present invention will be described by way of example.

The negative photosensitive resin composition of the present invention is applied to an underlying substrate by a known method such as microgravure coating, spin coating, dip coating, shower flow coating, roll coating, spray coating or slit coating. Then, a preheating device such as a hot plate or an oven is used to perform prebaking to form a film. The prebaking is carried out at 50 to 150 ° C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably set to 0.1 to 15 μm.

After prebaking, an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (hereinafter referred to as "PLA") is used. Irradiation of light of 10 to 4000 J/m ² (converted by a wavelength of 365 nm) is performed with or without a desired mask. The exposure light source is not limited, and an ultraviolet ray such as an i-line, a g-line or an h-line, a KrF (wavelength 248 nm) laser, or an ArF (wavelength 193 nm) laser or the like can be used. Then, the film may be heated by a heating plate or an oven to perform post-exposure baking at 150 to 450 ° C for about 1 hour.

After the patterning exposure, the non-exposed portion is dissolved by development to obtain a negative pattern. The developing method is preferably a method of immersing in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. Examples of the developing solution include hydroxides containing an alkali metal; inorganic bases such as carbonates, phosphates, citrates or borates; amines such as 2-diethylaminoethanol, monoethanolamine or diethanolamine; and hydroxides. An aqueous solution of a quaternary ammonium salt such as tetramethylammonium or choline. It is preferred to use a hydrating film after development, and then dry baking at 50 to 150 ° C. Of course Thereafter, the film is subjected to heat curing at 120 to 280 ° C for 1 hour or more using a heating means such as a hot plate or an oven to obtain a cured film.

The film thickness of the obtained cured film is preferably 0.1 to 10 μm. The transmittance at a wavelength of 400 nm at a film thickness of 0.3 μm is preferably 95% or more, the leakage current is preferably 10 ^-6 A/cm ² or less, and the relative dielectric constant is preferably 6.0 or more. In addition, the "penetration rate" here means the transmittance at a wavelength of 400 nm.

The cured film obtained by curing the negative photosensitive resin composition of the present invention can be used, for example, as a protective film for a touch panel, various hard coating materials, a planarizing film for TFT, an outer protective film for a color filter, and an anti-corrosion film. Various protective films such as a reflective film and a passivation film, and an optical filter, an insulating film for a touch panel, an insulating film for TFT, a photosensitive spacer for a color filter, a gate insulating film for a TFT, etc., have high It is particularly suitable as a gate insulating film for TFTs because of its relative dielectric constant, insulating properties, chemical resistance, and resolution.

[Examples]

The invention will be more specifically described by the following examples and comparative examples, but the invention is not limited thereto.

The abbreviations for the solvents used are as follows:

DAA: Diacetone alcohol

PGMEA: propylene glycol monomethyl ether acetate

THFA: tetrahydrofurfuryl alcohol

MEK: methyl ethyl ketone

TMAH: tetramethylammonium hydroxide

Further, as the metal oxide particles, (A1) zirconium dioxide nanoparticles (SZR-K; manufactured by Seiko Chemical Co., Ltd., ε _r = 30) and titanium dioxide nanoparticles ("Optlake"TR-550; Manufactured into a company, ε _r =115), and barium titanate nanoparticles (T-BTO-020RF; Toda Industrial Co., Ltd.; average primary particle size 20 nm, ε _r = 400). Further, dispersions (A2 to A6) of metal oxide particles of the formulation shown in Table 1 were prepared.

<Synthesis Example 1> Preparation of Zirconium Dioxide Dispersion (A2)

Filled with 113 g of DAA, 1.36 g of methyltrimethoxydecane (KBM-13; manufactured by Shin-Etsu Chemical Co., Ltd.; hereinafter referred to as "Me"), 3.70 g of epoxycyclohexylpropyltrimethoxydecane (KBM-303; Shin-Etsu Chemical Co., Ltd.; hereinafter referred to as "Epo"), 4.69 g of acrylonitrile propyl trimethoxy decane (KBM-5103; manufactured by Shin-Etsu Chemical Co., Ltd.; hereinafter referred to as "Ac"), 0.99 g of phenyltrimethoxydecane (KBM) -103 (trade name); Shin-Etsu Chemical Co., Ltd.; hereinafter referred to as "Ph"), 0.021 g of phosphoric acid, and 2.70 g of purified water, and stirred at 40 ° C for 1 hour in an oil bath. Next, the oil bath temperature was set to 70 ° C, and 138 g of (A1) zirconium dioxide nanoparticles were dropped over about 30 minutes. After the end of the dropwise addition, the temperature of the oil bath was set to 120 ° C, and the stirring was stopped after the temperature in the flask reached 100 ° C for 3 hours. After the reaction was completed, the flask was chilled and cooled to normal temperature, and an anion exchange resin was added and stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a decane-modified zirconia sol (A2).

<Synthesis Example 2> Preparation of titanium oxide dispersion (A3)

14.3 g of methanol, 1.36 g of Me, 3.54 g of Epo, 4.69 g of Ac, 0.99 g of Ph, 0.021 g of phosphoric acid and 2.70 g of purified water were charged, and the mixture was stirred at 40 ° C for 1 hour in an oil bath. Next, the oil bath temperature was set to 70 ° C, and a mixture of 197 g of "Optlake" TR-550 and 111 g of DAA was dropped over about 30 minutes. After 1 hour from the end of the dropwise addition, the oil bath temperature was set to 120 ° C, and stirring was started 3 hours after the temperature in the flask reached 100 ° C, and then the heating was stopped to complete the reaction. After the reaction was completed, the flask was chilled and cooled to normal temperature, and an anion and a cation exchange resin were separately added and stirred for 10 hours. Finally, filter to remove ion exchange By changing the resin, a decane-modified titanium oxide sol (A3) was obtained.

<Synthesis Example 3> Preparation of Titanium Oxide Dispersion (A4)

14.3 g of methanol, 2.04 g of Me, 3.54 g of Epo, 4.69 g of Ac, phosphoric acid of 0.021 g, and 2.70 g of purified water were charged, and the mixture was stirred at 40 ° C for 1 hour in an oil bath. Next, the oil bath temperature was set to 70 ° C, and a mixture of 197 g of "Optlake" TR-550 and 111 g of DAA was dropped over about 30 minutes. After 1 hour from the end of the dropwise addition, the oil bath temperature was set to 120 ° C, and stirring was started 3 hours after the temperature in the flask reached 100 ° C, and then the heating was stopped to complete the reaction. After the reaction was completed, the flask was chilled and cooled to normal temperature, and an anion and a cation exchange resin were separately added and stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a decane-modified titania sol (A4).

<Synthesis Example 4> Preparation of Barium Titanate Dispersion (A5)

340 g of THFA, 5 g of decanoic acid-2-propenyloxyethyl ester (HOA-MPL; manufactured by Kyoeisha Chemical Co., Ltd.), and 97 g of barium titanate particles (T-BTO-020RF; Toda Industrial Co., Ltd.) The average primary particle size of 20 nm was mixed. Next, in a barrel of a bead mill (Ultra Apex Mill UAM-015; manufactured by Shou Industrial Co., Ltd.), 400 g of zirconia beads (made by Nikkato Co., Ltd.; YTZ ball; size) were filled. 0.05 mm), while the rotor was rotated, the mixed liquid was supplied to the drum and circulated to disperse the inorganic particles. The circumferential rate of the rotor was set to 9.5 m/s for 2 hours to obtain a barium titanate THFA sol.

The flask was charged with 131 g of the above-described barium titanate sol, 22 g ofTHFA, 14.3 g of methanol, 1.36 g of Me, 3.54 g of Epo, 4.69 g of Ac, 0.99 g of Ph, phosphoric acid of 0.021 g, and purified water of 2.70. g, stirred at 40 ° C for 1 hour in an oil bath. Next, the oil bath temperature was set to 70 ° C and stirred for 1 hour. After 1 hour, the oil bath temperature will be When the temperature was 120 ° C and the temperature in the flask reached 100 ° C, the stirring was started for 3 hours, and then the heating was stopped to complete the reaction. After the reaction was completed, the flask was chilled and cooled to normal temperature, and an anion exchange resin was added and stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a decane-modified barium titanate sol (A5).

<Synthesis Example 5> Preparation of Barium Titanate Dispersion (A6)

340 g ofTHFA, 5 g of decanoic acid-2-propenyloxyethyl ester, and 97 g of barium titanate particles were mixed. Next, 400 g of zirconia balls were filled in the barrel of the bead mill, and while the rotor was rotated, the mixed liquid was supplied to the barrel and circulated to disperse the inorganic particles. The circumferential rate of the rotor was set to 9.5 m/s for 2 hours to obtain a barium titanate THFA sol.

The flask was charged with 131 g of the above-described barium titanate sol, 22 g ofTHFA, 14.3 g of methanol, 2.04 g of Me, 3.54 g of Epo, 4.69 g of Ac, phosphoric acid of 0.021 g, and purified water of 2.70 g in an oil bath. Stir at 40 ° C for 1 hour. Next, the oil bath temperature was set to 70 ° C and stirred for about 1 hour. After 1 hour, the oil bath temperature was set to 120 ° C, and stirring was started 3 hours after the temperature in the flask reached 100 ° C, and then the heating was stopped to complete the reaction. After the reaction was completed, the flask was chilled and cooled to normal temperature, and an anion exchange resin was added and stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a decane-modified barium titanate sol (A6).

The polyester resin solutions (B1 to B7) shown in Table 2 were prepared as follows.

<Synthesis Example 6> Synthesis of Polyester Resin (B1)

The flask was charged with 264 g of PGMEA, 68 g of ethylene glycol (hereinafter referred to as "EG"), 296 g of biphenyltetracarboxylic dianhydride (hereinafter referred to as "BPTCD"), and 1.7 g of tetrabutylammonium acetate (hereinafter referred to as "BPTCD"). Hereinafter, it is called "TBAA"), and stirred at 120 ° C for 5 hours, and further added 272 g of glycidyl methacrylate (30 mass % PGMEA solution) and 2 g of tert-butylcatechol, and stirred at 120 ° C. 6 hours. After cooling to room temperature, 215 g of PGMEA was added to obtain a polyester resin B1 in the form of a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by the GPC method was Mw = 8300.

<Synthesis Example 7> Synthesis of Polyester Resin Solution (B2)

195 g of PGMEA, 92 g of bisphenol (hereinafter referred to as "BP"), 142 g of glycidyl methacrylate (hereinafter referred to as "GMA"), 1.6 g of TBAA, and 2 g of third butyl tea were charged. The phenol was stirred at 120 ° C for 6 hours. 291 g of PGMEA, 296 g of BPTCD, and 0.5 g of TBAA were charged therein, and stirred at 120 ° C for 5 hours. After cooling to room temperature, 264 g of PGMEA in PGMEA solution was added to obtain a polyester resin B2. use The weight average molecular weight in terms of polystyrene measured by the GPC method was Mw = 5,800.

<Synthesis Example 8> Synthesis of Polyester Resin Solution (B3)

The flask was filled with 491 g of PGMEA, 175 g of 9,9-bis(4-hydroxyphenyl)phosphonium (hereinafter referred to as "BPFL"), 142 g of GMA, 1.8 g of TBAA, and 2 g of the third butyl group. The tea phenol was stirred at 120 ° C for 8 hours. 210 g of PGMEA, 220 g of pyromellitic dianhydride (hereinafter referred to as "BTCD"), and 0.6 g of TBAA were placed therein, and stirred at 120 ° C for 5 hours. After cooling to room temperature, 171 g of PGMEA was added to obtain a polyester resin B2 of a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by the GPC method was Mw = 7600.

<Synthesis Example 9> Synthesis of polyester resin solution (B4)

171 g of bisphenol A glycidyl ether (hereinafter referred to as "BPPGG"), 71 g of acrylic acid (hereinafter referred to as "AcA"), 1.6 g of TBAA, 1.3 g of t-butylcatechol, and 342 g of PGMEA was stirred at 120 ° C for 9 hours. Thereto were filled with 174 g of BPTCD and 165 g of PGMEA, and stirred at 120 ° C for 5 hours. After cooling to room temperature, 242 g of PGMEA was added to obtain a polyester resin B4 of a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by the GPC method was Mw = 6,200.

<Synthesis Example 10> Synthesis of Polyester Resin Solution (B5)

The flask was charged with 461 g of 9,9-bis(4-glycidoxyphenyl)fluorene (OGSOL® PG100; manufactured by Osaka Gas Chemical Co., Ltd.), 72 g of AcA, and 1.6 g of tetrabutylammonium acetate. 1.3 g of 2,6-di-t-butylcatechol and 542 g of PGMEA were stirred at 120 ° C for 9 hours. Filled with 174g of BPTCD and 265g of PGMEA at 120°C Stir under 5 hours. After cooling to room temperature, 253 g of PGMEA was added to obtain a polyester resin B4 of a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by the GPC method was Mw = 5,700.

<Synthesis Example 11> Synthesis of Polyester Resin Solution (B6)

153 g of 1,1-bis(4-(2,3-epoxypropoxy)phenyl)-3-phenylindole (hereinafter referred to as "BEOPI") and 33 g of isodecanoic acid (hereinafter referred to as " IFA"), 1.1 g of TBAA, and 244 g of PGMEA were stirred at 110 ° C for 4 hours. After cooling to room temperature, 43 g of AcA, 1.0 g of TBAA, and 2.0 g of t-butylcatechol were added, and the mixture was stirred at 120 ° C for 5 hours. After cooling to room temperature, 123 g of hexahydrophthalic anhydride (hereinafter referred to as "HHFD") and 1.9 g of TBAA were added, and the mixture was stirred at 110 ° C for 3 hours. 108 g of GMA was added and stirred at 120 ° C for 5 hours. After cooling to room temperature, 265 g of PGMEA was added to obtain a polyester resin B6 in the form of a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by the GPC method was Mw=5000.

<Synthesis Example 12> Synthesis of Polyester Resin Solution (B7)

115 g of 1,1-bis(4-(2,3-epoxypropyloxy)phenyl)-3,5-diphenylanthracene (hereinafter referred to as "BEODPI"), 240 g of PGMEA, and 240 g of PGMEA were added to the flask. 0.4 g of tert-butylcatechol, 3.7 g of benzyltriethylammonium chloride, and 31 g of AcA were heated to 120 ° C for 3 hours. After cooling to 50 ° C or lower, 66 g of BPTCD and 0.2 g of tetrabutylammonium bromide were added, and the mixture was heated to 120 ° C, stirred for 3 hours, and then cooled to 80 ° C. Then, 9 g of trimellitic anhydride (hereinafter referred to as "TD") was added, and the temperature was raised to 120 ° C, and the mixture was stirred for 2 hours, and then cooled to 40 ° C or lower. Further, 94 g of the PGMEA solution was added, and a polyester resin B7 was obtained in the form of a PGMEA solution. The weight average molecular weight system in terms of polystyrene measured by the GPC method Mw = 5,500.

<Synthesis Example 13> Synthesis of Polyester Resin Solution (R1)

The flask was charged with 364 g of PGMEA, 68 g of EG, 296 g of BPTCD, and 1.7 g of TBAA, and stirred at 120 ° C for 5 hours. After cooling to room temperature, 31 g of PGMEA was added, and a polyester resin R1 was obtained in the form of a PGMEA solution.

<Synthesis Example 14> Synthesis of Polyester Resin Solution (R2)

The flask was charged with 364 g of PGMEA, 68 g of EG, 199 g of 1,2,3,4-butanetetracarboxylic dianhydride (BTCD), and 1.7 g of TBAA, and stirred at 120 ° C for 5 hours. After cooling to room temperature, 31 g of PGMEA was added, and a polyester resin R2 was obtained in the form of a PGMEA solution.

<Synthesis Example 15> Synthesis of Acrylic Resin Solution (R3)

In a 500 mL flask, 1 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA were charged, and then 23.0 g of methacrylic acid (MA) and 31.5 g of methacrylic acid were further charged. Benzyl ester (BMA), and 32.8 g of tricyclo[5.2.1.02,6]non-8-yl methacrylate (TCDMA). After stirring briefly at room temperature, the inside of the flask was purged with nitrogen and sufficiently nitrogen-substituted, and then heated and stirred at 70 ° C for 5 hours. Next, 12.7 g of glycidyl methacrylate (GMA), 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ° C. 4 hours. After the reaction was completed, the reaction solution was subjected to liquid separation extraction treatment with 1 equivalent of formic acid aqueous solution to remove the addition catalyst, and after drying with magnesium sulfate, PGMEA was added in such a manner that the solid content concentration was 40% by mass, depending on PGMEA. Acrylic resin R3 was obtained in the form of a solution.

<Synthesis Example 16> Synthesis of a decane resin solution (E1)

A 500 mL three-necked flask was charged with 73.25 g of dimethoxydiphenyl decane (DPhTMS) (0.30 mol), 93.72 g of 3-propenyl methoxypropyltrimethoxydecane (AcTMS) (0.40 mol). 26.26 g of 3-trimethoxydecylpropyl succinic anhydride (SucTMS) (0.1 mol), 38.89 g of phenyltrimethoxydecane (PhTMS) (0.20 mol), and 156.52 g of propylene glycol monomethyl ether Acetate. The solution was stirred while stirring at room temperature, and 2.0 g of a phosphoric acid aqueous solution of phosphoric acid was dissolved in 54.0 g of water over 30 minutes. Then, the flask was immersed in an oil bath of 40 ° C and stirred for 30 minutes, and then the oil bath was set to 70 ° C and heated for 30 minutes, and the oil bath was further heated to 110 ° C. The reaction was terminated 3 hours after the start of the temperature rise. At this time, the internal temperature of the solution rises to a temperature lower by about 5 ° C than the oil bath setting. The methanol formed in the reaction and the unconsumed water are removed by distillation. The obtained polyoxyalkylene propylene glycol monomethyl ether acetate In the solution, propylene glycol monomethyl ether acetate was added so that the polymer concentration became 50% by mass to obtain a decane resin solution (E1).

<Synthesis Example 17> Synthesis of a decane resin solution (E2)

In addition to the one originally filled in the three-necked flask, 36.06 g of dimethoxy dimethyl decane (DMeDMS) (0.30 mol), 46.86 g of 3-acryloxypropyltrimethoxy decane (0.20 mol), 13.12 g of 3-trimethoxydecylpropyl succinic anhydride (0.05 mol), 87.50 g of phenyltrimethoxydecane (0.45 mol), and 145.06 g of propylene glycol monomethyl ether acetate. The synthesis was carried out in the same manner as in Synthesis Example 16 to obtain a decane resin solution (E2).

"%" in parentheses in Table 4 indicates the mass % of the decane compound in the polymer.

The polyfunctional (meth) acrylonitrile-based compound of each of the examples and the comparative examples was dipentaerythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.), and a photoradical polymerization initiator was used. 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzamide)] ("IRGACURE" (registered trademark) OXE-01 using a compound having an oxime ester structure; Manufactured by BASF, and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetyl) "IRGACURE" (registered trademark) OXE-02; BASF system). For the surfactant, BYK-333 (manufactured by BYK-Chemie Ltd.) was used, and the polymerization inhibitor was IRGANOX245 (manufactured by BASF).

<Example 1>

Under a yellow light, 3.071 g of (A1) zirconia nanoparticles (MEK 30% by mass dispersion of zirconium dioxide nanoparticles) were diluted with 4.675 g of DAA and 0.491 g of PGMEA, and 0.0287 g of "IRGACURE" was added. (registered trademark) OXE-01, and 0.0287g of "IRGACURE" (registered trademark) OXE-02, 0.0072g of polymerization inhibitor, 0.287g of "KAYARAD" (registered trademark) (PGMEA 50 mass of dipentaerythritol hexaacrylate) % solution; manufactured by Nikko Chemical Co., Ltd., 0.300 g of a surfactant (PGMEA 1 mass% solution of BYK-333 (corresponding to a concentration of 100 ppm)), and stirred. Further, 0.736 g of a polyester resin B1 solution (45.4% by mass of PGMEA solution) was added and stirred. Next, filtration was carried out using a 0.22 μm filter to obtain a negative photosensitive resin composition. The negative photosensitive resin composition obtained was evaluated for transmittance, resolution, insulation, relative dielectric constant, and chemical resistance in accordance with the following methods. The composition of the negative photosensitive resin composition (1) obtained is shown in Table 5, and the evaluation results are shown in Table 8. In addition, the numerical values in parentheses in Table 5 represent the mass %.

(resolution evaluation)

The resin composition was spin-coated on a substrate by a spin coater (1H-360S; manufactured by MIKASA Co., Ltd.), and then heated at 90 ° C for 2 minutes using a hot plate (SCW-636; manufactured by DAINIPPON SCREEN Co., Ltd.). Prebaking was carried out to prepare a prebaked film having a film thickness of 0.40 μm. As the substrate, a glass substrate (hereinafter referred to as "ITO substrate") to which an ITO film is applied is used. For the obtained prebaked film, PLA was used, and an ultrahigh pressure mercury lamp was used as a light source, and a 2000 J/m ² exposure was performed according to a gap of 100 μm through a gray scale mask having a transmittance of 1 to 60%. Then, using an automatic developing device (AD-2000; manufactured by Takizawa Seiki Co., Ltd.), an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide (hereinafter referred to as "TMAH") was subjected to a shower development for 60 seconds, followed by rinsing with water 30. Seconds. After exposure and development, an exposure amount of a width of 1 to 1 formed by a line of 100 μm and a space pattern was set as an optimum exposure amount. The exposure amount was measured using an I-line illuminometer.

The minimum pattern size after development was measured by the optimum exposure amount, and this was set as the resolution.

(penetration rate evaluation)

The resin composition was spin-coated on a 5 cm square TEMPAX® glass substrate (manufactured by AGC TECHNO GLASS Co., Ltd.), and then pre-baked at 90 ° C for 2 minutes using a hot plate to obtain a film thickness of 0.4. Pre-baked film of ~0.6 μm. The obtained prebaked film was subjected to full exposure by 2000 J/m ² using an ultrahigh pressure mercury lamp, and then subjected to a development of a developing apparatus of 2.38% TMAH for 60 seconds, followed by rinsing with water for 30 seconds. Finally, an oven (IHPS-222; ESPEC) was baked in air at 230 ° C for 30 minutes to obtain a cured film having a film thickness of 0.3 to 0.5 μm.

For the obtained cured film, a transmittance of 400 nm was measured using an ultraviolet-visible spectrophotometer (UV-260; manufactured by Shimadzu Corporation).

(Chemical resistance evaluation before thermal hardening)

A prebaked film having a film thickness of 0.40 μm was produced in the same manner as in the evaluation of pattern workability. The obtained prebaked film was subjected to full exposure by 2000 J/m ² using an ultrahigh pressure mercury lamp, and subjected to a development of a 2.38 mass% TMAH aqueous solution for 60 seconds by an automatic developing device, followed by rinsing with water for 30 seconds. The obtained cured film was immersed in a 5.0 mass% aqueous solution of oxalic acid at room temperature for 5 minutes, and after washing with water for 1 minute, the adhesion to the ITO cured film was evaluated in accordance with JIS K5600-5-6.

More specifically, the obtained cured film was cut in the vertical and horizontal directions at intervals of 1 mm using a utility knife, and 100 square meters of 1 mm × 1 mm were obtained. Stick in a way that covers all squares Stick the celluloid adhesive tape (width = 18mm, adhesion = 3.7N/10mm), and wipe it with an eraser (JIS S6050 qualified product) to make it intimate. While holding one end of the celluloid adhesive tape, while holding it at a right angle to the substrate, it is peeled off instantaneously, and the number of remaining squares is confirmed, and the ratio of the peeled squares (that is, the peeling area ratio) is obtained. According to the following evaluation criteria, the peeling area ratio is divided into five stages, and up to 3 or more is acceptable.

5: peeling area ratio = 0%

4: peeling area ratio = <5%

3: peeling area ratio = 5 to 14%

2: peeling area ratio = 15~34%

1: peeling area ratio = 35~64%

0: peeling area ratio = 65~100%

(Chemical resistance evaluation after thermosetting)

A prebaked film having a film thickness of 0.40 μm was produced in the same manner as the pattern processability evaluation, and the obtained prebaked film was subjected to full exposure by an ultrahigh pressure mercury lamp at 2000 J/m ² , and an automatic developing device was used to carry out 60% of an aqueous solution of 2.38% TMAH. The solution was developed in seconds and then rinsed with water for 1 minute. The obtained cured film was baked at 230 ° C for 30 minutes. The sample was immersed in a 2.38 mass% TMAH aqueous solution at room temperature for 80 seconds, and another sample was immersed in a 7 mass% aqueous solution of aminoethoxyethanol at 70 ° C for 80 seconds, and each sample was washed with water. After 1 minute, the adhesion to the ITO cured film was evaluated in accordance with JIS K5600-5-6.

(Insulation evaluation)

A prebaking film having a film thickness of 0.40 μm was formed on an ITO substrate of 10 cm × 10 cm in the same manner as in the evaluation of the pattern processability, and an intermediate baking was performed at 160 ° C for 5 minutes using a hot plate to obtain an intermediate baking film. . The obtained intermediate baking film was immersed in a 5 mass% aqueous oxalic acid solution at room temperature for 5 minutes, and then washed with water for 1 minute. Then, it was baked in a 230 ° C oven for 30 minutes, immersed in a 2.38 mass % TMAH solution at room temperature for 80 seconds, and further immersed in 7 mass % of amino ethoxyethanol at 70 ° C for 80 seconds. Wash with water for 1 minute. The cured film obtained by chemical immersion was measured for film thickness (μm) by a Surfcom stylus film thickness measuring device, and then aluminum (purity of 99.99% or more) was vapor-deposited on the cured film by a vacuum deposition apparatus to an area of about 1 cm ^{2 .} The measurement sample is obtained.

Each of the electrode terminals was brought into contact with aluminum and ITO, and a leakage current (log [A/cm ² ]) after application for 15 seconds at 15 V was measured using a semiconductor measuring device (KEITHLEY 4200-SCS; manufactured by Kiethley Instruments Co., Ltd.).

(Evaluation of relative dielectric constant)

A measurement sample was prepared in the same manner as the insulation evaluation. Each electrode terminal was brought into contact with aluminum and ITO, and the electrostatic capacitance at a frequency of 1 MHz was measured by an impedance analyzer (4294A; Agilent Technologies Co., Ltd.) and a sample support frame (16451B; Agilent Technologies Co., Ltd.). ) Perform the measurement. The relative dielectric constant calculates the relative dielectric constant from the capacitance and the size of the measurement target region.

(Feature evaluation of TFT)

A TFT substrate having the structure shown in Fig. 1 was produced. On the glass substrate 1 (thickness: 0.7 mm), a metal mask was placed by a resistance heating method, and chromium having a thickness of 5 nm was vacuum-deposited, and then gold having a thickness of 50 nm was vacuum-deposited to form a gate electrode 2. Then, the negative photosensitive resin composition (1) was spin-coated as in the above (resolution evaluation), and prebaked at 90 ° C for 2 minutes using a hot plate to prepare a pre-baked film having a film thickness of 0.40 μm. Baked film. The obtained prebaked film was subjected to full exposure by 2000 J/m ² using an ultrahigh pressure mercury lamp, and subjected to a 60 second shower development with a 2.38% TMAH aqueous solution using an automatic developing device, followed by rinsing with water for 30 seconds. Finally, an oven (IHPS-222; ESPEC) was baked in air at 230 ° C for 30 minutes to obtain a gate insulating film having a film thickness of 0.3 μm, which was referred to as a gate insulating layer 3. On the substrate on which the gate insulating layer was formed, gold was vacuum-deposited so as to have a thickness of 50 nm. Next, the positive type photoresist solution was dropped, applied by a spin coater, and then dried by a hot plate at 90 ° C to form a photoresist film. The obtained photoresist film was irradiated with ultraviolet rays through a photomask using an exposure machine. Next, the substrate was immersed in an aqueous alkali solution to remove the ultraviolet ray irradiation portion, and a photoresist film patterned into an electrode shape was obtained. The obtained substrate was immersed in a gold etching solution (manufactured by Aldrich Co., Ltd., Goldetchant, standard), and the gold removed from the photoresist film was dissolved and removed. The obtained substrate was immersed in acetone, and after removing the photoresist, it was washed with pure water, and then dried at 100 ° C for 30 minutes. Accordingly, gold source/drain electrodes 4 and 5 having an electrode width (channel width) of 0.2 mm, an electrode spacing (channel length) of 20 μm, and a thickness of 50 nm were obtained.

Next, on the substrate on which the electrode was formed, poly-3-hexylthiophene (P3HT, manufactured by Aldrich Co., Ltd., stereoregularity) was applied by an inkjet method, and 150° C. and 30 were applied to a hot plate under a nitrogen stream. After a minute heat treatment, the P3HT film 6 is made into a channel layer FET. At this time, the inkjet apparatus was a simple discharge test group PIJL-1 (manufactured by Cluster Technology Co., Ltd.).

Next, in the I-V curve when the FET gate voltage is scanned from +30 to -30 V, the value of the read current I is sharply rising (Von). The measurement was carried out in the atmosphere using a semiconductor characteristic evaluation system Model 4200-SCS (manufactured by Kiethley Instruments Co., Ltd.). The evaluation results are shown in Table 8.

<Example 2 to Example 7>

The (A) metal oxide particles were changed to A2 to A7, and the (B) alkali-soluble polyester resin was changed to B2, and a negative photosensitive resin composition was obtained in the same manner as in Example 1, and was carried out and carried out. Example 1 was evaluated in the same manner. The composition of the obtained negative photosensitive resin composition is shown in Table 5, and the evaluation results are shown in Table 8.

<Example 8 to Example 12>

The (B) alkali-soluble polyester resin was changed to B3 to B7, and a negative photosensitive resin composition was obtained in the same manner as in Example 1, and the same evaluation as in Example 1 was carried out. The composition of the obtained negative photosensitive resin composition is shown in Table 6, and the evaluation results are shown in Table 8.

The values in parentheses in Table 6 indicate the mass % concentration.

<Example 13 to Example 20>

In the same manner as in Example 1, a negative photosensitive resin composition was obtained in the same manner as in Example 1 except that the (E) alkoxydecane or the polyoxyalkylene synthesized in Synthesis Examples 16 and 17 was added, and the same evaluation as in Example 1 was carried out. The composition of the obtained negative photosensitive resin composition is shown in Table 7, and the evaluation results are shown in Table 8.

The values in parentheses in Table 7 indicate the mass % concentration.

As is clear from the results of Table 8, the cured films made of the negative photosensitive resin compositions obtained in Examples 1 to 20 all satisfy the engineering characteristics required as the interlayer insulating film or the gate insulating film of the TFT. .

<Comparative Examples 1 to 3>

The (B) alkali-soluble polyester resin was changed to a polyester resin R1 polyester resin R2 or an acrylic resin R3 having no radical polymerizable group or aromatic ring structure, and negative photosensitive properties were respectively obtained in the same manner as in Example 1. The resin composition was subjected to the same evaluation as in Example 1. The composition of the obtained negative photosensitive resin composition is shown in Table 8, and the evaluation results are shown in Table 9.

The values in parentheses in Table 9 indicate the mass % concentration.

As is clear from the results of Table 10, the cured films made of the respective negative photosensitive resin compositions obtained in Comparative Examples 1 to 3 lack the chemical resistance required as the interlayer insulating film or the gate insulating film of the TFT. Sex, unable to meet the characteristics of the manufacturing process.

(industrial availability)

The cured film obtained by curing the negative photosensitive resin composition of the present invention is suitable for various hard coating films such as a gate insulating film for an TFT, an interlayer insulating film, a protective film for a touch panel, and an insulating film for a touch sensor. A planarizing film for a TFT of a liquid crystal or an organic EL display, a metal wiring protective film, an insulating film, an antireflection film, an antireflection film, an optical filter, an outer film for a color filter, a pillar, and the like.

Claims (6)

A negative photosensitive resin composition comprising: (A) a metal oxide particle of a metal selected from the group consisting of titanium, tantalum, niobium, tantalum, tungsten, niobium, and zirconium; (B) having a radical polymerization An alkali-soluble polyester resin of a base group and an aromatic ring; (C) a polyfunctional (meth) propylene fluorenyl compound; and (D) a photopolymerization initiator. The negative photosensitive resin composition of claim 1, wherein the alkali-soluble polyester resin contains a chemical structure represented by the following general formula: (R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or such substituted groups, or R ¹ and R ² Together, a cycloalkyl group having 2 to 12 carbon atoms, an aromatic ring having 5 to 12 carbon atoms, or the substituted group is formed; and R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 2 to 12 carbon atoms, and carbon. The number of 6 to 20 aryl groups, or the substituted groups; n and m systems each independently represent an integer from 0 to 10). The negative photosensitive resin composition of claim 1 or 2, which comprises (E) an alkoxysilane or a polyoxyalkylene having four or more alkoxy groups. A cured film obtained by the negative photosensitive resin composition according to any one of claims 1 to 3. A TFT substrate comprising a cured film of the fourth application of the patent application. A method for manufacturing a thin film transistor substrate includes: coating application patent scope The negative photosensitive resin composition according to any one of items 1 to 3, which is subjected to a step of forming a pattern by exposure and development.