JPWO2014080908A1 - Negative photosensitive resin composition - Google Patents

Abstract

The present invention is a negative film which can maintain a characteristic without deterioration even after chemicals and high-temperature treatment, and can obtain a cured film having excellent properties in high transparency, high dielectric constant and low leakage current. It is an object to provide a mold-type photosensitive resin composition. The solution includes 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 It is a photosensitive resin composition containing a polyfunctional (meth) acryloyl compound and (D) a photopolymerization initiator.

Description

  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 is increasing, and the simplification of the manufacturing process and the replacement with low-cost materials are progressing along with the price reduction of liquid crystal displays. For example, various insulating films and passivation films in a TFT (Thin FILM Transistor) manufacturing process are generally formed by CVD of highly insulating inorganic materials such as silicon carbide, silicon nitride, aluminum oxide, tantalum oxide, or titanium oxide. The film is manufactured by the method. However, since the CVD method is expensive, studies have been actively conducted on photosensitive organic insulating materials that can be manufactured by a photolithography method that is cheaper than the CVD method (Patent Documents 1 to 3).

  As an optical member application, a transparent insulating film obtained by combining a metal oxide such as titania or zirconia with siloxane or an acrylic resin has been studied (Patent Document 4).

JP 2011-186069 A JP 2007-43055 A JP 2007-316531 A JP 2011-151164 A

  However, the conventional photosensitive organic insulating material has a lower dielectric constant than an inorganic material and is inferior in insulating properties. Therefore, when used as an insulating film, the rising voltage of a transistor is increased, or a leakage current is increased. However, the current situation is that there is a problem that leads to a decrease in display performance of the display. Although these problems are improved if the composite material of the metal oxide and the resin described above, such a composite material has low resistance to chemicals in the manufacturing process and high-temperature processing, and deteriorates. It was regarded as a problem.

  Therefore, the present invention can provide a cured film having properties that are maintained in performance without deterioration of its characteristics even after chemical and high-temperature treatment, and has excellent properties such as high transparency, high dielectric constant, and low leakage current. It is an object of the present invention to provide a possible negative photosensitive resin composition.

  Therefore, as a result of intensive studies, the present inventors have found that a composition comprising a component including an alkali-soluble polyester resin having a radical polymerizable group and an aromatic ring is extremely effective for solving the above problems. Completed the invention.

That is, this invention provides the photosensitive resin composition, transparent cured film, and thin-film transistor substrate which were described in the following (1)-(6).
(1) (A) 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 negative photosensitive resin composition containing a polyfunctional (meth) acryloyl compound and (D) a photopolymerization initiator.
(2) The negative-type photosensitive resin composition, wherein the alkali-soluble polyester resin contains a chemical structure represented by the following general formula.

(R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or a group in which they are substituted, or R ¹ and R ^2. Together represent a cycloalkyl group having 2 to 12 carbon atoms, an aromatic ring having 5 to 12 carbon atoms or a group in which they are substituted, and R ₃ and R ₄ are each independently hydrogen, carbon 2 Represents an alkyl group of ˜12, an aryl group of 6 to 20 carbon atoms or a group in which they are substituted, and n and m each independently represent an integer of 0 to 10).
(3) (E) The negative photosensitive resin composition in any one of the above, containing an alkoxysilane or polysiloxane having 4 or more alkoxy groups.
(4) A cured film obtained from any of the above negative photosensitive resin compositions.
(5) A TFT substrate comprising the above cured film.
(6) A method for producing a thin film transistor substrate comprising a step of applying any of the above negative photosensitive resin compositions and forming a pattern through exposure and development.

  According to the negative photosensitive resin composition of the present invention, even when immersed in a chemical, the adhesion with the substrate is not impaired, the film characteristics are not deteriorated due to the penetration of the chemical, and a transparent having a high dielectric constant and insulating property is obtained. An insulating film is obtained. Further, a thin film transistor substrate having a transparent insulating film having a high dielectric constant and insulation can be manufactured.

The conceptual diagram which shows the characteristic evaluation method of TFT.

  The negative photosensitive resin composition of the present invention comprises (A) metal oxide particles of a metal selected from the group consisting of titanium, barium, hafnium, tantalum, tungsten, yttrium and zirconium, (B) a radical polymerizable group and an aromatic It contains an alkali-soluble polyester resin having a ring, (C) a polyfunctional (meth) acryloyl compound, and (D) a photopolymerization initiator.

The negative photosensitive resin composition of the present invention contains (A) metal oxide particles of a metal selected from the group consisting of titanium, barium, hafnium, tantalum, tungsten, yttrium and zirconium. These metal oxide particles have a common relative dielectric constant (hereinafter sometimes referred to as ε _r ) of 20 or more. Here, the metal oxide particles may be a composite metal oxide containing two or more metals included in the metal group. The metal oxide particles may be a mixture of metal oxide particles having different compositions. The relative dielectric constant of the metal oxide includes a coaxial probe method in which the metal oxide powder can be measured as it is, a parallel plate capacitor method in which the powder is pelletized by pressure forming and sandwiched between two electrodes, and the like. . These measurement methods can be measured by using an impedance analyzer (such as Agilent 4294A) or an LCR meter (such as Agilent 4285A) and a dedicated jig (such as Agilent 85070E or 16451B / 16453A).

By containing these (A) metal oxide particles, the relative dielectric constant and insulation of a cured negative photosensitive resin composition, that is, a cured film, and the like are improved. Examples of these (A) metal oxide particles include titanium oxide, barium titanate, barium sulfate, barium oxide, hafnium oxide, tantalum oxide, tungsten oxide, yttrium oxide, and zirconium oxide. In order to improve the relative permittivity, titanium oxide (ε _r = 115), zirconium oxide (ε _r = 30), barium titanate (ε _r = 400) or hafnium oxide having a relative permittivity (ε _r ) of 20 or more (Ε _r = 25) is more preferable. Moreover, since the dispersion | distribution technique in a nanometer level is advancing and it is easy to obtain as a commercial item, a titanium oxide or a zirconium oxide is still more preferable.

  (A) The number average particle diameter of the metal oxide particles is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less. When the particle diameter is small, the transparency of the cured film is improved, and when it is smaller, the homogeneity and insulating properties of the cured film and the like are improved. The number average particle diameter is preferably 1 nm or more, and more preferably 3 nm or more. When the size is larger than a certain size, the crystal structure of the metal oxide particles is maintained, the specific dielectric constant as expressed by the theoretical value is exhibited, and the relative dielectric constant of the cured film or the like is improved.

  (A) The metal oxide particles may be surface-modified for the purpose of improving dispersibility in the negative photosensitive resin composition. Examples of the surface modification include coating with silicon oxide and coating with a surface modifier, which is an organic compound having an alkoxysilyl group, an isocyanate group, or a carboxyl group. The surface modifier preferably has a polymerizable unsaturated group in order to form a covalent bond with (B) the alkali-soluble polyester resin or (C) the polyfunctional (meth) acryloyl compound by ultraviolet irradiation.

  The content of the (A) metal oxide particles in the negative photosensitive resin composition of the present invention is sufficient for the hardness and relative dielectric constant of the cured film, etc. It is preferable that it is 10-90 mass%.

  (A) Metal oxide particles can be pulverized or dispersed using a disperser such as a bead mill by procuring appropriate particles of powder. Examples of commercially available nanoparticle powders include T-BTO-020RF (barium titanate; manufactured by Toda Kogyo Co., Ltd.), UEP-100 (zirconium oxide; manufactured by Daiichi Rare Element Chemical Co., Ltd.) or STR-100N. (Titanium oxide; manufactured by Sakai Chemical Industry Co., Ltd.).

  The (A) metal oxide particles can also be obtained as a dispersion dispersed in a liquid. Examples of the silicon oxide-titanium oxide particles include “OPTRAIK” (registered trademark) TR-502, “OPTRAIK” TR-503, “OPTRAIK” TR-504, “OPTRAIK” TR-513, and “OPTRAIK”. "TR-520", "Optlake" TR-527, "Optlake" TR-528, "Optlake" TR-529, "Optlake" TR-544 or "Optlake" TR-550 (all of which are JGC Catalysts and Chemicals Kogyo Co., Ltd.). Zirconium oxide particles include, for example, “Vilar” registered trademark Zr-C20 (average particle size = 20 nm; manufactured by Taki Chemical Co., Ltd.), ZSL-10A (average particle size = 60-100 nm; Daiichi Rare Element Co., Ltd.) Manufactured), “Nano Youth” (registered trademark) OZ-30M (average particle size = 7 nm; manufactured by Nissan Chemical Industries, Ltd.), SZR-M (manufactured by Sakai Chemical Co., Ltd.) or HXU-120JC (Sumitomo Osaka Cement Co., Ltd.) ))).

  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. (B) By containing an alkali-soluble polyester resin, negative photosensitive pattern processability can be imparted to the photosensitive resin composition. More specifically, when the negative photosensitive resin composition is exposed, (B) the alkali-soluble polyester resin and (C) the polyfunctional (meth) acryloyl compound undergo radical polymerization and become a crosslinked polymer. A pattern can be formed by removing the non-exposed portion by subsequent development. In addition, the chemical resistance of the UV cured film after exposure and the thermoset film after curing is improved. More specifically, a cured film or the like can be obtained without impairing the relative dielectric constant, insulation, and adhesion even in the step exposed to a strong acidic or strong alkaline chemical before and after curing. . In general, since ester groups are highly polar and highly hydrophilic, they tend to cause decomposition reactions such as hydrolysis. Therefore, when a cured film or the like made of an acrylic resin or a polyester resin is immersed in an acid or alkali, film peeling or the like, which is presumed to be caused by the ester bond being decomposed inside the cured film or the like, occurs. (B) Although the mechanism of action of the effect obtained by containing an alkali-soluble polyester resin having a radically polymerizable group and an aromatic ring is not clear, the degradation of the ester group by the aromatic ring and the radically polymerizable group It is considered that the improvement of the film density by polymerization suppressed the decomposition due to the penetration of the chemical.

  The content of the (B) alkali-soluble polyester resin in the negative photosensitive resin composition of the present invention is preferably 1 to 80% by mass and more preferably 5 to 50% by mass with respect to all components other than the organic solvent. When the content is 1% by mass or more, sufficient alkali developability can be obtained, and a residue or background stain in an unexposed portion is hardly generated. When the content is 80% by mass or less, film peeling at the time of development hardly occurs. The content of the (C) polyfunctional (meth) acryloyl compound in the negative photosensitive resin composition of the present invention is 1 to the entire negative photosensitive resin composition in order to improve the hardness of the cured film and the like. 20 mass% is preferable. Moreover, it is preferable that it is 5-50 mass% with respect to all components other than an organic solvent, and it is more preferable that it is 10-40 mass%.

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

  As a method for synthesizing the (B) alkali-soluble polyester resin in the present invention, since the synthesis is easy and there are few side reactions, a polyaddition reaction between (b1) a polyfunctional epoxy compound and (b2) a polyvalent carboxylic acid compound. Alternatively, a method through (b3) a polyaddition reaction of a polyol compound and (b4) dianhydride is preferable. (B3) Polyol compound obtained by reaction of (b1) polyfunctional epoxy compound and (b5) radical polymerizable group-containing monobasic acid compound because it is easy to introduce radical polymerizable groups and aromatic rings Is preferred.

  The following method is exemplified as a method of undergoing a polyaddition reaction between (b1) a polyfunctional epoxy compound and (b2) a polyvalent carboxylic acid compound. In the presence of a catalyst, (b2) polyvalent carboxylic acid compound is polyadded by adding 1.01-2 equivalents to (b1) polyfunctional epoxy compound. The reaction produces an ester bond. Thereafter, (b6) a radical polymerizable group-containing epoxy compound is added to the terminal carboxylic acid moiety. (B7) Acid anhydride is added to the hydroxyl group to be formed. As another method, in the presence of a catalyst, 1.01-2 equivalents of (b1) polyfunctional epoxy compound is added to polyvalent carboxylic acid compound (b2) and polyadded. The reaction produces an ester bond. Thereafter, (b5) a radical polymerizable group-containing monobasic acid compound is added to the terminal epoxy site. (B7) Acid anhydride is added to the hydroxyl group to be formed.

  The following method is exemplified as a method of undergoing a polyaddition reaction between (b3) a polyol compound and (b4) dianhydride. In the presence of a catalyst, (b3) the polyol compound and (b4) dianhydride are polymerized. The reaction produces an ester bond. Thereafter, (b6) a radical polymerizable group-containing epoxy compound is added to a part of the generated carboxyl group. In addition, when the (b3) polyol compound has a radical polymerizable group, the radical polymerizable group-containing epoxy compound may not be added.

  Examples of the catalyst used for the polyaddition reaction and the addition reaction include ammonium catalysts such as tetrabutylammonium acetate; amino catalysts such as 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine; triphenylphosphine And a phosphorus catalyst such as acetylacetonate chromium or chromium chloride.

  As the (b1) polyfunctional epoxy compound, a compound represented by the following general formula (1) is preferable in order to improve insulation and chemical resistance of a cured film and the like.

(R ¹ and R ² each independently represent hydrogen, an alkyl or cycloalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms or a group in which they are substituted, or R ¹ And R ² together represent a cycloalkyl group having 2 to 12 (preferably 5 to 12) carbon atoms, an aromatic ring having 5 to 12 carbon atoms or a group in which they are substituted, and R ₃ and R ₄ are Each independently represents hydrogen, an alkyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms or a group in which they are substituted, and n and m each independently represents 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, a biphenyl group, or a substituent shown below. Is mentioned.

Examples of the cyclic structure formed by combining R ¹ and R ² include the following substituents, and the cyclic structure is preferably a 5- to 7-membered ring.

(Here, the carbon of * in the formula represents the carbon to which R ¹ and R ² were bonded in formula (1).)
(B1) As a polyfunctional epoxy compound, the compound shown below is mentioned, for example.

(B2) Examples of the polyvalent carboxylic acid compound include succinic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and 2,2′-biphenyldicarboxylic acid. Or 4,4′-biphenyldicarboxylic acid, but in order to improve chemical resistance and insulation properties of cured films, etc., phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 2,2 ′ -Biphenyl dicarboxylic acid or 4,4'-biphenyl dicarboxylic acid is preferred.

(B3) Examples of polyol compounds include aliphatic alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, or pentaerythritol, 9,9-bis [4- (2-hydroxyethoxy) phenyl]. Fluorene, (b1) a compound obtained by reaction of a polyfunctional epoxy compound and (b5) a radical polymerizable group-containing monobasic acid compound, or a bisphenol compound represented by the following general formula (2) and (b6) a radical polymerizable group An aromatic alcohol compound such as a compound obtained by reaction with the containing epoxy compound can be mentioned. Of these, aromatic alcohol compounds are preferred. Incidentally, ^{R 1,} R 2, ^{R 3} and ^{R 4} in the general formula (2) is the same as the general formula (1).

  (B4) Examples of the dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyl. Tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′ , 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) ) Hexafluoropropane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethanedioic anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethanedioic anhydride, bis (3,4-dicarboxy Enyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetra Aromatic tetracarboxylic acid anhydrides such as carboxylic acid diacid anhydride or 3,4,9,10-perylenetetracarboxylic acid anhydride, butanetetracarboxylic acid anhydride, cyclobutanetetracarboxylic acid diacid Anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1. ] Heptanetetracarboxylic dianhydride, bicyclo [3.3.1. ] Tetracarboxylic dianhydride, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic dianhydride, bicyclo [2.2.2. ] Aliphatic tetracarboxylic dianhydrides such as octane tetracarboxylic dianhydride or adamantane tetracarboxylic dianhydride may be mentioned. In order to improve chemical resistance and insulation properties of cured films, etc. Is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or 2, 2 ', 3,3'-biphenyltetracarboxylic dianhydride is preferable, and in order to improve the transparency of a cured film or the like, cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride or cyclohexanetetracarboxylic dianhydride is preferred.

  (B5) Examples of the radical polymerizable group-containing monobasic acid compound include (meth) acrylic acid, succinic acid mono (2- (meth) acryloyloxyethyl), and phthalic acid mono (2- (meth) acryloyloxyethyl). , Tetrahydrophthalic acid mono (2- (meth) acryloyloxyethyl) or p-hydroxystyrene.

  Examples of the (b6) radical polymerizable group-containing epoxy compound include glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-n-propylglycidyl (meth) acrylate, and (meth) acrylic acid α. -N-butylglycidyl, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate, butyl vinyl ether, butyl Allyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, cyclohexane vinyl ether, cyclohexane allyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxybutyl allyl ether, allyl glycidyl ether, vinyl glycidyl ether, o-bi Rubenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl Ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyl Oxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene or 2,4,6-triglycidyloxymethyl Styrene I can get lost.

  (B7) Examples of acid anhydrides include succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid monoanhydride, and 2,3-biphenyldicarboxylic acid. Acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, hexahydrophthalic acid anhydride, glutaric acid anhydride, 3-methylphthalic acid anhydride, norbornene dicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride or 3-trimethoxysilyl And propyl succinic anhydride.

  The negative photosensitive resin composition of the present invention contains (C) a polyfunctional (meth) acryloyl compound, that is, a compound having two or more acryloyl groups and / or methacryloyl groups in the molecule. By containing this (C) polyfunctional (meth) acryloyl compound, a negative photosensitive resin composition can be hardened by light irradiation. In the present invention, a substance corresponding to both (B) an alkali-soluble polyester resin having a radical polymerizable group and an aromatic ring and (C) a polyfunctional (meth) acryloyl compound is treated as (B).

  Examples of the polymerizable compound having two (meth) acryloyl groups in the molecule include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol. Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol ( (Meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligo Tylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di ( (Meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, oligopropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9 Nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate Todi (meth) acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene 9,9-bis [4- (2-methacryloyloxyethoxy) -3-methylphenyl] fluorene, (2-acryloyloxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- And acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene or 9,9-bis [4- (2-methacryloyloxyethoxy) -3,5-dimethylphenyl] fluorene.

  Examples of the polymerizable compound having three (meth) acryloyl groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and trimethylolpropane alkylene oxide-modified tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri ((meth) acryloyl Oxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate or ethoxylated glycerin triacrylate.

  Examples of the polymerizable compound having four (meth) acryloyl groups in the molecule include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetrapropionate. (Meth) acrylate or ethoxylated pentaerythritol tetra (meth) acrylate may be mentioned.

  Examples of the polymerizable compound having five (meth) acryloyl groups in the molecule include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Examples of the polymerizable compound having six (meth) acryloyl groups in the molecule include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate or caprolactone-modified diester. An example is pentaerythritol hexa (meth) acrylate.

  Examples of the polymerizable compound having seven (meth) acryloyl groups in the molecule include tripentaerythritol heptaacrylate.

  Examples of the polymerizable compound having eight (meth) acryloyl groups in the molecule include tripentaerythritol octaacrylate.

  Examples of commercially available (C) polyfunctional (meth) acryloyl compounds include “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 (all 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-55 , R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KSHDDA, KS-TPGDA or KS -TMPTA (all manufactured by Nippon Kayaku Co., Ltd.), light acrylate PE-4A, DPE-6A or DTMP-4A (manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat # 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd .; tripentaerythritol octane) Acrylate and tripentaerythritol heptaacrylate).

  The content of the (C) polyfunctional (meth) acryloyl compound in the negative photosensitive resin composition of the present invention is 1 to the entire negative photosensitive resin composition in order to improve the hardness of the cured film and the like. 20 mass% is preferable. Moreover, it is preferable that it is 5-50 mass% with respect to all components other than an organic solvent, and it is more preferable that it is 10-40 mass%.

  The negative photosensitive resin composition of this invention needs to contain (D) photoinitiator. (D) The photopolymerization initiator is preferably one that decomposes and / or reacts with light (including short-wave electromagnetic waves such as ultraviolet rays) or electron beams to generate radicals. Examples of such a photopolymerization initiator include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethyl Benzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide, 1-phenyl -1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phen Ruthio) -2- (O-benzoyloxime)], 1-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 4,4-bis (dimethylamino) benzophenone, 4 , 4-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, benzyldimethyl ketal, 1- (4-isopropylphenol) Nyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, benzoin, benzoin methyl ether Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkyl Benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) Oxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthene-2 -Iroxy) -N, N, N-trimethyl-1-propanaminium chloride, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2-biimidazole 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,1 -Phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis (η5-2, 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl- 4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt- Butyldichloroacetophenone, benzyl Toxiethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromo Combination of a photoreducing dye such as phenylsulfone, benzoyl peroxide, eosin or methylene blue with a reducing agent such as ascorbic acid or triethanolamine To be mentioned. Among them, an α-aminoalkylphenone compound, an acylphosphine oxide compound, an oxime ester compound, a benzophenone compound having an amino group, or a benzoic acid ester compound having an amino group is preferable in order to improve the hardness of a cured film or the like.

  Examples of the α-aminoalkylphenone compound include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, or bis (2,6-dimethoxybenzoyl)-(2 , 4,4-trimethylpentyl) -phosphine oxide. Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl). Oxime)], 1-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime or ethanone, 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime). Examples of the benzophenone compound having an amino group include 4,4-bis (dimethylamino) benzophenone and 4,4-bis (diethylamino) benzophenone. Examples of the benzoic acid ester compound having an amino group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate or ethyl p-diethylaminobenzoate.

  The content of the photopolymerization initiator (D) in the negative photosensitive resin composition of the present invention is sufficient for the hardness of the cured film, and prevents the residual photopolymerization initiator from elution, thereby improving the solvent resistance. In order to improve, it is preferable that it is 0.1-20 mass parts with respect to all components other than an organic solvent.

  The negative photosensitive resin composition of the present invention preferably contains (E) an alkoxysilane or polysiloxane having 4 or more alkoxy groups. By containing these silane compounds, chemical resistance such as a cured film and adhesion to a metal substrate are improved. This effect is not due to the interaction between the alkoxysilyl group and the substrate, but is thought to be due to the construction of a crosslinked structure by the reaction between the hydroxyl group on the surface of the metal oxide particles and the alkoxysilyl group.

  Examples of the alkoxysilane having four or more alkoxy groups include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, tetramethoxydisiloxane, tetraethoxydisiloxane, and bis (triethoxysilylpropyl) tetrasulfide. , Tris- (3-trimethoxysilylpropyl) isocyanurate, and tris- (3-triethoxysilylpropyl) isocyanurate. From the viewpoint of improving the chemical resistance of the cured film, a mixture of tetrafunctional silane and 9 functional silane is used in order to allow bulky 9 functional silane and tetrafunctional silane with less steric hindrance to react with each other. Is preferred.

  The polysiloxane can be obtained by cohydrolyzate condensation, that is, hydrolysis and partial condensation of a bifunctional or trifunctional alkoxysilane compound. Examples of the alkoxysilane compound constituting the polysiloxane include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dihydroxydiphenylsilane, dimethoxy (methyl) (phenyl) silane, and diethoxy (methyl) (phenyl). ) Silane, dimethoxy (methyl) (phenethyl) silane, dicyclopentyldimethoxysilane or cyclohexyldimethoxy (methyl) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Or 3-acryloxypropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl anhydride Acid, 3-trimethoxysilylethyl succinic anhydride, 3-trimethoxysilylbutyl succinic anhydride, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (3,4-epoxy (Cyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenethyltrimethoxysilane, naphthyltrimethoxysilane, methyltriethoxy Examples include silane, ethyltriethoxysilane, phenyltriethoxysilane, phenethyltriethoxysilane, naphthyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.

  The negative photosensitive resin composition of the present invention may contain a polymerization inhibitor in order to adjust the sensitivity to light, for example. Examples of the polymerization inhibitor include catechols such as phenol, hydroquinone, p-methoxyphenol, benzoquinone, methoxybenzoquinone, 1,2-naphthoquinone, cresol, pt-butylcatechol, alkylphenols, alkylbisphenols, phenothiazine, 2,5-di-t-butylhydroquinone, 2,6-di-t-butylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylene Bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'methylenebis (4-methyl-6-t-butylphenol), 4,4'methylenebis (2,6-di-) t-butylphenol), 4,4′butylidenebis (3-methyl-6-t) Butylphenol), 2,6-bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) 4-methylphenol, 1,1,3-tris (2′-methyl-5′-t-) Butyl-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], pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2- t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-dimethyl-6-t-butylphenol Phenols such as 2-t-butyl-4-methoxyphenol, 6-t-butyl-m-cresol, 2,6-di-t-butyl-p-cresol, 2-t-butylhydroquinone, methylene blue, dimethyldithiocarbamine Acid copper salt, diethyldithiocarbamic acid copper salt, dipropyldithiocarbamic acid copper salt, dibutyldithiocarbamic acid copper salt, copper dibutyldithiocarbamate, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole or phosphites And the combined use with an oxygen-containing gas. 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 with respect to the entire negative photosensitive resin composition, and 0.00005 to 0. More preferably, it is 1%. Moreover, 0.0001-0.5 mass% is preferable with respect to all components other than an organic solvent, and 0.001-0.2 mass% is more preferable.

  In order to improve the resolution after development, the negative photosensitive resin composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a benzotriazole-based compound, a benzophenone-based compound, or a triazine-based compound is preferable in order to improve transparency and non-colorability of a cured film or the like.

  Examples of benzotriazole compounds include 2- (2Hbenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, and 2- (2Hbenzotriazole). -2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol or 2- (2′- Hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole. Examples of the benzophenone-based compound include 2-hydroxy-4-methoxybenzophenone. Examples of the ultraviolet absorber of the triazine compound include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  The negative photosensitive resin composition of the present invention may contain a solvent. The solvent is preferably an alcoholic compound, an ester compound or an ether compound in order to uniformly dissolve each component of the composition. Examples of the solvent include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diacetone alcohol, ethylene glycol mononormal butyl ether, 2-ethoxyethyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-3-methylbutanol. 3-methoxy-3-methylbutanol acetate, 3-methoxybutyl acetate, 1,3-butylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl lactate, butyl lactate, ethyl acetoacetate or γ-butyrolactone Is mentioned.

  The negative photosensitive resin composition of the present invention may contain a surfactant. Examples of the surfactant include silicone surfactants, silicon surfactants such as organopolysiloxanes, fluorine surfactants, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether. Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate, polyalkylene oxide surfactants, poly (meth) acrylate surfactants, acrylic or methacrylic surfactants A surfactant made of a polymer is exemplified. Examples of commercially available surfactants include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (all manufactured by Dainippon Ink & Chemicals, Inc.) or NBX- 15 or FTX-218 (both manufactured by Neos Co., Ltd.) and the like, BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (all BYK Chemie Japan K.K.) And the like.

  The negative photosensitive resin composition of this invention may contain additives, such as a dissolution inhibitor, a stabilizer, or an antifoamer, as needed.

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

  The following method is illustrated about the typical manufacturing method of the (I) negative photosensitive resin composition of this invention. (A) A dispersion of metal oxide particles is weighed, and a solvent is added to the dispersion if necessary and stirred. To the mixture, (D) a photopolymerization initiator and other additives are added to a suitable solvent and dissolved by stirring. Thereafter, (B) an alkali-soluble polyester resin and (C) a polyfunctional (meth) acryloyl compound are added and further stirred for 20 minutes to 3 hours. In order to remove foreign substances as necessary, the obtained solution is filtered to obtain a negative photosensitive resin composition.

  An example is given and demonstrated about the formation method of the cured film using the negative photosensitive resin composition of this invention.

  The negative photosensitive resin composition of the present invention is applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating or slit coating, A film is formed by prebaking with a heating device such as an oven. Prebaking is performed at 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 μm.

After pre-baking, using an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (hereinafter referred to as PLA), light of about 10 to 4000 J / m ² (wavelength 365 nm exposure amount conversion) is applied to the desired mask. Irradiate through or without. The exposure light source is not limited, and ultraviolet rays such as i-line, g-line, or h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, or the like can be used. Then, you may perform the post-exposure baking which heats this film | membrane at 150-450 degreeC for about 1 hour using heating apparatuses, such as a hotplate or oven.

  After patterning exposure, the unexposed portion is dissolved by development, and a negative pattern can be obtained. As a developing method, a method of immersing in a developer for 5 seconds to 10 minutes by a method such as shower, dipping or paddle is preferable. Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and tetra Examples thereof include an aqueous solution containing a quaternary ammonium salt such as methylammonium hydroxide or choline. After the development, it is preferable to rinse the film with water, and then dry baking may be performed at 50 to 150 ° C. Then, a cured film is obtained by thermally curing this film at 120 to 280 ° C. for about 1 hour using a heating device such as a hot plate or an oven.

As for the film thickness of the cured film obtained, 0.1-10 micrometers is preferable. It is preferable that the transmittance of light having a wavelength of 400 nm at a film thickness of 0.3 μm is 95% or more, the leakage current is 10 ⁻⁶ A / cm ² or less, and the relative dielectric constant is 6.0 or more. Here, the transmittance refers to the transmittance at a wavelength of 400 nm.

  Cured films obtained by curing the negative photosensitive resin composition of the present invention include protective films for touch panels, various hard coat materials, flattening films for TFT, overcoats for color filters, antireflection films, passivation films, etc. It can be used for various protective films and optical filters, insulating films for touch panels, insulating films for TFTs, photo spacers for color filters, gate insulating films for TFTs, etc., but it has high relative dielectric constant, insulation, chemical resistance and resolution. Therefore, it can be particularly suitably used as a gate insulating film for TFT.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these ranges.

Abbreviations of 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 (A1) zirconia nanoparticles (SZR-K; Sakai Chemical Industry) Co., Ltd., [epsilon] _r = 30), titania nanoparticles ("Optlake"TR-550; made by Catalytic Chemicals, [epsilon] _r = 115) and barium titanate nanoparticles (T-BTO-020RF; Toda Kogyo Co., Ltd.) Manufactured; average primary particle diameter 20 nm, ε _r = 400). Moreover, the dispersion (A2-A6) of the metal oxide particle of the mixing | blending shown in Table 1 was adjusted.

<Synthesis Example 1> Preparation of zirconia dispersion (A2) 113 g of DAA, 1.36 g of methyltrimethoxysilane (KBM-13; manufactured by Shin-Etsu Chemical; hereinafter, Me), 3.70 g of epoxycyclohexylpropyltrimethoxysilane ( KBM-303; manufactured by Shin-Etsu Chemical; hereinafter referred to as Epo), 4.69 g of acryloylpropyltrimethoxysilane (KBM-5103; manufactured by Shin-Etsu Chemical; hereinafter referred to as Ac), 0.99 g of phenyltrimethoxysilane (KBM-103 (product) Name); manufactured by Shin-Etsu Chemical Co., Ltd .; Ph), 0.021 g of phosphoric acid and 2.70 g of purified water were charged and stirred in an oil bath at 40 ° C. for 1 hour. Next, the temperature of the oil bath was set to 70 ° C., and 138 g of (A1) zirconia nanoparticles were dropped over about 30 minutes. One hour after the completion of dropping, the temperature of the oil bath was set to 120 ° C., and the reaction was stopped after stirring for 3 hours after the temperature in the flask reached 100 ° C. After completion of the reaction, the flask was cooled with ice and cooled to room temperature, an anion exchange resin was added, and the mixture was stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a silane-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, phosphoric acid 0.021 g Then, 2.70 g of purified water was charged and stirred at 40 ° C. for 1 hour in an oil bath. Next, the temperature of the oil bath 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. One hour after the completion of the dropwise addition, the temperature of the oil bath was set to 120 ° C., and after the temperature in the flask reached 100 ° C., the mixture was stirred for 3 hours, and then the heating was stopped to complete the reaction. After completion of the reaction, the flask was cooled with ice and cooled to room temperature, and an anion and a cation exchange resin were added and stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a silane-modified titania sol (A3).

<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, 0.021 g of phosphoric acid and 2.70 g of purified water And stirred for 1 hour at 40 ° C. in an oil bath. Next, the temperature of the oil bath was set to 70 ° C., and a mixture of 197 g “Optlake” TR-550 and 111 g DAA was added dropwise over about 30 minutes. One hour after the completion of the dropwise addition, the temperature of the oil bath was set to 120 ° C., and after the temperature in the flask reached 100 ° C., the mixture was stirred for 3 hours, and then the heating was stopped to complete the reaction. After completion of the reaction, the flask was cooled with ice and cooled to room temperature, and an anion and a cation exchange resin were added and stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a silane-modified titania sol (A4).

Synthesis Example 4 Preparation of Barium Titanate Dispersion (A5) 340 g of THFA, 5 g of 2-acryloyloxyethyl-phthalic acid (HOA-MPL; manufactured by Kyoeisha Chemical Co., Ltd.) and 97 g of barium titanate particles (T-BTO) -020RF; Toda Kogyo Co., Ltd .; average primary particle size 20 nm) was mixed. Next, 400 g of zirconia beads (manufactured by Nikkato Co., Ltd .; YTZ ball; size φ0.05 mm) are filled in the vessel of a bead mill (Ultra Apex Mill UAM-015; manufactured by Kotobuki Industries Co., Ltd.), and the rotor is rotated. However, the mixed liquid was fed and circulated in the vessel to disperse the inorganic particles. The peripheral speed of the rotor was dispersed at 9.5 m / s for 2 hours to obtain a barium titanate THFA sol.

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

<Synthesis Example 5> Preparation of Barium Titanate Dispersion (A6) 340 g of THFA, 5 g of 2-acryloyloxyethyl-phthalic acid, and 97 g of barium titanate particles were mixed. Next, 400 g of zirconia beads were filled into the vessel of the bead mill, and the mixed liquid was fed and circulated through the vessel while rotating the rotor to disperse the inorganic particles. The peripheral speed of the rotor was dispersed at 9.5 m / s for 2 hours to obtain a barium titanate THFA sol.

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

    Polyester resin solutions (B1 to B7) shown in Table 2 were prepared by the following method.

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

<Synthesis Example 7> Synthesis of polyester resin solution (B2) 195 g of PGMEA, 92 g of biphenol (hereinafter referred to as BP), 142 g of glycidyl methacrylate (hereinafter referred to as GMA), 1.6 g of TBAA and 2 g of tert-butylcatechol were charged. , And stirred at 120 ° C. for 6 hours. Thereto, 291 g of PGMEA, 296 g of BPTCD and 0.5 g TBAA were charged and stirred at 120 ° C. for 5 hours. After cooling to room temperature, PGMEA was added as a 264 g PGMEA solution to obtain polyester resin B2. The weight average molecular weight in terms of polystyrene measured by GPC method was Mw = 5800.

Synthesis Example 8 Synthesis of Polyester Resin Solution (B3) 491 g of PGMEA, 175 g of 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter BPFL), 142 g of GMA, 1.8 g of TBAA and 2 g of tert -Butylcatechol was charged into a flask and stirred at 120 ° C for 8 hours. Thereto, 210 g of PGMEA, 220 g of pyromellitic dianhydride (hereinafter referred to as BTCD) and 0.6 g of TBAA were charged 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 as a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by 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 tert-butylcatechol and 342 g of PGMEA was charged and stirred at 120 ° C. for 9 hours. Thereto, 174 g of BPTCD and 165 g of PGMEA were charged 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 as a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by GPC method was Mw = 6200.

<Synthesis Example 10> Synthesis of polyester resin solution (B5) 461 g of 9,9-bis (4-glycidyloxyphenyl) fluorene (Ogsol PG100; manufactured by Osaka Gas Chemical Company), 72 g of AcA, 1.6 g of tetrabutylammonium Acetate, 1.3 g of 2,6-di-tert-butylcatechol and 542 g of PGMEA were charged into a flask and stirred at 120 ° C. for 9 hours. Thereto, 174 g of BPTCD and 265 g of PGMEA were charged and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 253 g of PGMEA was added to obtain a polyester resin B4 as a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by GPC method was Mw = 5700.

Synthesis Example 11 Synthesis of Polyester Resin Solution (B6) 153 g of 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindane (hereinafter referred to as BEOPI), 33 g of isophthalic acid ( Hereinafter, IFA), 1.1 g of TBAA and 244 g of PGMEA were charged and 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 tert-butylcatechol were added and 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 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 polyester resin B6 as a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by 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-diphenylindane (hereinafter referred to as BEODPI), 240 g of PGMEA , 0.4 g of tert-butylcatechol, 3.7 g of benzyltriethylammonium chloride and 31 g of AcA were added to the flask, heated to 120 ° C. and held for 3 hours. The mixture was cooled to 50 ° C. or lower, 66 g of BPTCD and 0.2 g of tetrabutylammonium bromide were added, the temperature was raised to 120 ° C., stirred for 3 hours, and then cooled to 80 ° C. Thereafter, 9 g of trimellitic anhydride (hereinafter referred to as TD) was added, the temperature was raised to 120 ° C., stirred for 2 hours, and then cooled to 40 ° C. or less. Furthermore, 94 g of PGMEA solution was added to obtain a polyester resin B7 as a PGMEA solution. The weight average molecular weight in terms of polystyrene measured by GPC method was Mw = 5500.

Synthesis Example 13 Synthesis of Polyester Resin Solution (R1) 364 g of PGMEA, 68 g of EG, 296 g of BPTCD and 1.7 g of TBAA were charged into a flask and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 31 g of PGMEA was added to obtain a polyester resin R1 as a PGMEA solution.

Synthesis Example 14 Synthesis of Polyester Resin Solution (R2) 364 g of PGMEA, 68 g of EG, 199 g of 1,2,3,4-butanetetracarboxylic dianhydride (BTCD) and 1.7 g TBAA were charged into a flask. Stir at 120 ° C. for 5 hours. After cooling to room temperature, 31 g of PGMEA was added to obtain a polyester resin R2 as 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). An additional charge of 31.5 g benzyl methacrylate (BMA) and 32.8 g tricyclo [5.2.1.02,6] decan-8-yl methacrylate (TCDMA). The mixture was stirred at room temperature for a while, and the inside of the flask was sufficiently purged with nitrogen by bubbling, 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. for 4 hours. After completion of the reaction, the reaction solution is subjected to separation / extraction treatment with 1N formic acid aqueous solution to remove the addition catalyst, dried over magnesium sulfate, PGMEA is added so that the solid content concentration is 40% by mass, and the PGMEA solution is added. As a result, an acrylic resin R3 was obtained.

Synthesis Example 16 Synthesis of Siloxane Resin Solution (E1) 73.25 g of dimethoxydiphenylsilane (DPhTMS) (0.30 mol), 93.72 g of 3-acryloxypropyltrimethoxysilane (AcTMS) (0.40 mol) ), 26.26 g 3-trimethoxysilylpropyl succinic anhydride (SucTMS) (0.1 mol), 38.89 g phenyltrimethoxysilane (PhTMS) (0.20 mol) and 156.52 g propylene glycol monomethyl Ether acetate was charged into a 500 mL three-necked flask. While stirring the solution at room temperature, an aqueous phosphoric acid solution in which 2.0 g of phosphoric acid was dissolved in 54.0 g of water was added over 30 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, 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 completed 3 hours after the start of temperature increase. At this time, the internal temperature of the solution rose to about 5 ° C. lower than the oil bath setting. Methanol produced during the reaction and water that was not consumed were removed by distillation. Propylene glycol monomethyl ether acetate was added such that the resulting polysiloxane in propylene glycol monomethyl ether acetate solution had a polymer concentration of 50% by mass to obtain a siloxane resin solution (E1).

<Synthesis Example 17> Synthesis of Siloxane Resin Solution (E2) First, what is charged into a three-necked flask is 36.06 g of dimethoxydimethylsilane (DMeDMS) (0.30 mol), 46.86 g of 3-acryloxypropyltrimethoxy. Silane (0.20 mol), 13.12 g 3-trimethoxysilylpropyl succinic anhydride (0.05 mol), 87.50 g phenyltrimethoxysilane (0.45 mol) and 144.06 g propylene glycol monomethyl A siloxane resin solution (E2) was obtained by synthesis in the same manner as in Synthesis Example 16 except that ether acetate was used.

% In parentheses in Table 4 indicates mass% of the silane compound in the polymer.

  As the polyfunctional (meth) acryloyl compound in each example and comparative example, dipentaerythritol hexaacrylate (“Kayarad” (registered trademark) DPHA; manufactured by Shin Nippon Kayaku Co., Ltd.) is used as a radical photopolymerization initiator, and an oxime ester structure 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] ("Irgacure" (registered trademark) OXE-01; manufactured by BASF) and ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) ("Irgacure" (registered trademark) OXE-02; manufactured by BASF) is used It was. BYK-333 (manufactured by Big Chemie Japan) was used as the surfactant, and IRGANOX245 (manufactured by BASF) was used as the polymerization inhibitor.

<Example 1>
Under yellow light, 3.071 g of (A1) zirconia nanoparticles (30% by weight MEK dispersion of zirconia nanoparticles) was diluted with 4.675 g DAA and 0.491 g PGMEA to give 0.0287 g “Irgacure "(R) OXE-01 and 0.0287 g of" Irgacure "(R) OXE-02, 0.0072 g of polymerization inhibitor, 0.287 g of" Kayarad "(R) (dipentaerythritol hexaacrylate PGMEA 50% by mass solution (manufactured by Shin Nippon Kayaku Co., Ltd.) and 0.300 g of a surfactant (BYK-333 1% by mass PGMEA solution (corresponding to a concentration of 100 ppm)) were added and stirred. Furthermore, 0.736 g of polyester resin B1 solution (45.4 mass% PGMEA solution) was added and stirred. Next, it filtered with a 0.22 micrometer filter, and obtained the negative photosensitive resin composition. About the obtained negative photosensitive resin composition, the transmittance | permeability, the resolution, the insulation, the relative dielectric constant, and the chemical resistance were evaluated by the following methods. The composition of the obtained negative photosensitive resin composition (1) is shown in Table 5, and the result of each evaluation is shown in Table 8. In addition, the value in the bracket | parenthesis in Table 5 shows the mass%.

(Resolution evaluation)
The resin composition was spin-coated on a substrate using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.) and then heated at 90 ° C. using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.). Prebaking was performed for 2 minutes to prepare a prebaked film having a thickness of 0.40 μm. As the substrate, a glass substrate (hereinafter referred to as ITO substrate) provided with an ITO thin film was used. The obtained pre-baked film was exposed to 2000 J / m ² with a gap of 100 μm through a gray scale mask having a transmittance of 1 to 60% using PLA as an ultrahigh pressure mercury lamp as a light source. Thereafter, using an automatic developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide (hereinafter, TMAH) solution, followed by rinsing with water for 30 seconds. did. The exposure amount that forms a 100 μm line-and-space pattern in a one-to-one width after exposure and development was defined as the optimum exposure amount. The exposure amount was measured with an I-line illuminometer.

  The minimum pattern dimension after development at the optimum exposure amount was measured and used as the resolution.

(Evaluation of transmittance)
The resin composition was spin-coated on a 5 cm square Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.) using a spin coater and then pre-baked at 90 ° C. for 2 minutes using a hot plate. A 4-0.6 μm pre-baked film was prepared. The obtained pre-baked film was exposed to 2000 J / m ^{2 on the} whole surface with an ultrahigh pressure mercury lamp, shower-developed with a 2.38% TMAH aqueous solution for 60 seconds using an automatic developing device, and then rinsed with water for 30 seconds. Finally, it was baked for 30 minutes at 230 ° C. in air using an oven (IHPS-222; manufactured by Espec Corp.) to produce a cured film having a film thickness of 0.3 to 0.5 μm.

  About the obtained cured film, the transmittance | permeability of 400 nm was measured using the ultraviolet-visible spectrophotometer (UV-260; Shimadzu Corporation Corp. make).

(Evaluation of chemical resistance before thermosetting)
A pre-baked film having a film thickness of 0.40 μm was produced by the same method as the evaluation of pattern processability. The obtained prebaked film was exposed to 2000 J / m ^{2 on the} entire surface with an ultrahigh pressure mercury lamp, shower-developed with a 2.38 mass% TMAH aqueous solution for 60 seconds using an automatic developing device, and then rinsed with water for 30 seconds. The obtained cured film was immersed in a 5.0 mass% oxalic acid aqueous solution at room temperature for 5 minutes, washed with water for 1 minute, and then evaluated for adhesion to the ITO cured film according to JIS K5600-5-6. did.

More specifically, the obtained cured film was cut vertically and horizontally at 1 mm intervals using a cutter knife to produce 100 1 mm × 1 mm squares. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was affixed so that all the squares were covered, and rubbed with an eraser (JIS S6050-passed product) to adhere. Having one end of the cellophane pressure-sensitive adhesive tape, the number of cells remaining after being peeled instantaneously while maintaining a right angle with respect to the substrate was confirmed, and the ratio of peeled cells, that is, the peeled area ratio was determined. Based on the following evaluation criteria, the peeled area ratio was classified into 5 stages, and 3 or more was regarded as acceptable.
5: Peeling area ratio = 0%
4: Peeling area ratio = <5%
3: Peeling area ratio = 5-14%
2: Peeling area ratio = 15-34%
1: Peeling area ratio = 35-64%
0: Peeling area ratio = 65-100%
(Evaluation of chemical resistance after thermosetting)
A prebaked film having a film thickness of 0.40 μm was produced by the same method as the evaluation of pattern processability, and the obtained prebaked film was exposed to 2000 J / m ² with an ultrahigh pressure mercury lamp, and 2.38 using an automatic developing device. Shower-developed with an aqueous solution of% TMAH for 60 seconds and then rinsed with water for 1 minute. The obtained cured film was baked at 230 ° C. for 30 minutes. This sample was immersed in an aqueous 2.38 mass% TMAH solution at room temperature for 80 seconds, and another sample was immersed in an aqueous 7 mass% aminoethoxyethanol solution at 70 ° C for 80 seconds, and each sample was washed with water for 1 minute. Then, the adhesion to the ITO cured film was evaluated according to JIS K5600-5-6.

(Insulation evaluation)
A 0.40 μm thick pre-baked film is formed on a 10 cm × 10 cm ITO substrate in the same manner as the pattern processability evaluation, and a middle bake is performed at 160 ° C. for 5 minutes using a hot plate. did. The obtained middle bake film was immersed in a 5 mass% oxalic acid aqueous solution at room temperature for 5 minutes and then washed with water for 1 minute. Next, it was baked in an oven at 230 ° C. for 30 minutes, immersed in a 2.38 mass% TMAH solution at room temperature for 80 seconds, further immersed in 7 mass% aminoethoxyethanol at 70 ° C. for 80 seconds, and then with water. Washed for 1 minute. The cured film obtained after immersion in chemicals was measured for film thickness (μm) with a surfcom stylus type film thickness measuring device, and then aluminum (purity 99.99% or more) on the cured film with a vacuum deposition device. Was deposited on an area of about 1 cm ² to obtain a measurement sample.

Each electrode terminal is brought into contact with aluminum and ITO, and a leakage current (log [A / cm ² ]) is measured after application for 60 seconds at 15 V using a semiconductor measuring device (KEITHLEY4200-SCS; manufactured by Keithley Instruments). did.

(Evaluation of relative dielectric constant)
A measurement sample was prepared by the same method for evaluating the insulation. Each electrode terminal is brought into contact with aluminum and ITO, respectively, and the capacitance at a frequency of 1 MHz in the measurement target region is measured with an impedance analyzer (4294A; manufactured by Agilent Technologies) and a sample holder (16451B; manufactured by Agilent Technologies). ). The relative dielectric constant was calculated as the relative dielectric constant from the dimensions of the capacitance and the measurement target region.

(TFT characteristics evaluation)
A TFT substrate having the structure shown in FIG. 1 was produced. A gate electrode 2 was formed on a glass substrate 1 (thickness 0.7 mm) by vacuum evaporation of chromium with a thickness of 5 nm and then gold with a thickness of 50 nm through a metal mask by a resistance heating method. Next, as in the above (evaluation of resolution), the negative photosensitive resin composition (1) was applied by spin coating, prebaked at 90 ° C. for 2 minutes using a hot plate, and a 0.40 μm-thick prebaked film was formed. Produced. The obtained pre-baked film was fully exposed at 2000 J / m ² with an ultrahigh pressure mercury lamp, shower-developed with a 2.38% TMAH aqueous solution for 60 seconds using an automatic developing device, and then rinsed with water for 30 seconds. Finally, baking was performed in an air at 230 ° C. for 30 minutes using an oven (IHPS-222; manufactured by Espec Corp.) to obtain a gate insulating film having a film thickness of 0.3 μm. 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, a positive resist solution was dropped and applied using a spinner, and then dried on a hot plate at 90 ° C. to form a resist film. The obtained resist film was irradiated with ultraviolet rays through a photomask using an exposure machine. Subsequently, the substrate was immersed in an alkaline aqueous solution, the ultraviolet irradiation part was removed, and a resist film patterned into an electrode shape was obtained. The obtained substrate was dipped in a gold etching solution (Goldetch, standard, manufactured by Aldrich) to dissolve and remove the portion of the gold from which the resist film was removed. The obtained substrate was immersed in acetone, the resist was removed, washed with pure water, and dried on a hot plate at 100 ° C. for 30 minutes. Thus, gold source / drain electrodes 4 and 5 having an electrode width (channel width) of 0.2 mm, an electrode interval (channel length) of 20 μm, and a thickness of 50 nm were obtained.

  Next, poly-3-hexylthiophene (P3HT, manufactured by Alducci, regioregular) is applied to the substrate on which the electrodes are formed by an inkjet method, and heat treatment is performed on a hot plate at 150 ° C. for 30 minutes in a nitrogen stream. Thus, an FET having the P3HT film 6 as a channel layer was manufactured. At this time, a simple discharge experiment set PIJL-1 (manufactured by Cluster Technology Co., Ltd.) was used for the ink jet apparatus.

  Next, in the IV curve when the gate voltage of the FET was swept from +30 to -30V, the value (Von) at which the value of the current I suddenly rose was read. The measurement was performed in the atmosphere using a semiconductor characteristic evaluation system 4200-SCS type (manufactured by Keithley Instruments Co., Ltd.). The evaluation results are shown in Table 8.

<Example 2 to Example 7>
The negative photosensitive resin composition was obtained in the same manner as in Example 1, except that (A) the metal oxide particles were changed to A2 to A7 and (B) the alkali-soluble polyester resin was changed to B2, respectively. Evaluation similar to 1 was performed. Table 5 shows the composition of the obtained negative photosensitive resin composition, and Table 8 shows the evaluation results.

<Example 8 to Example 12>
(B) In place of the alkali-soluble polyester resins B3 to B7, negative photosensitive resin compositions were obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. Table 6 shows the composition of the obtained negative photosensitive resin composition, and Table 8 shows the evaluation results.

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

<Example 13 to Example 20>
(E) A negative photosensitive resin composition was obtained in the same manner as in Example 1 by adding alkoxysilane or the polysiloxane synthesized in Synthesis Examples 16 and 17, and evaluated in the same manner as in Example 1. . Table 7 shows the composition of the obtained negative photosensitive resin composition, and Table 8 shows the evaluation results.

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

  As is apparent from the results in Table 8, the cured film obtained from each of the negative photosensitive resin compositions obtained in Examples 1 to 20 has the process characteristics required as an interlayer insulating film or a gate insulating film of TFT. It was something to satisfy.

<Comparative Examples 1-3>
(B) A negative photosensitive resin in the same manner as in Example 1, except that the alkali-soluble polyester resin is replaced with a polyester resin R1, a polyester resin R2 or an acrylic resin R3 having a structure having no radical polymerizable group or aromatic ring. Each composition was obtained and evaluated in the same manner as in Example 1. Table 8 shows the composition of the obtained negative photosensitive resin composition, and Table 9 shows the evaluation results.

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

  As is clear from the results in Table 10, the cured film obtained from each of the negative photosensitive resin compositions obtained in Comparative Examples 1 to 3 has chemical resistance required as an interlayer insulating film or a gate insulating film of TFT. However, the characteristics that could withstand the manufacturing process were not satisfied.

  Cured films obtained by curing the negative photosensitive resin composition of the present invention include various hard coat films such as TFT gate insulating films, interlayer insulating films, and touch panel protective films, insulating films for touch sensors, liquid crystals and organic films. It is suitably used for a TFT flattening film, a metal wiring protective film, an insulating film, an antireflection film, an antireflection film, an optical filter, an overcoat for a color filter, a column material, etc. for EL displays.

1: Substrate 2: Gate electrode 3: Gate insulating layer 4: Source / drain electrode 5: Source / drain electrode

Claims (6)

(A) 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,
A negative photosensitive resin composition comprising (C) a polyfunctional (meth) acryloyl compound and (D) a photopolymerization initiator. The negative photosensitive resin composition according to claim 1, wherein the alkali-soluble polyester resin includes a chemical structure represented by the following general formula.

(R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or a group in which they are substituted, or R ¹ and R ^2. Together represent a cycloalkyl group having 2 to 12 carbon atoms, an aromatic ring having 5 to 12 carbon atoms or a group in which they are substituted, and R ³ and R ⁴ are each independently hydrogen, carbon 2 Represents an alkyl group of ˜12, an aryl group of 6 to 20 carbon atoms or a group in which they are substituted, and n and m each independently represent an integer of 0 to 10.)   (E) The negative photosensitive resin composition of Claim 1 or 2 containing the alkoxysilane or polysiloxane which has a 4 or more alkoxy group.   The cured film obtained from the negative photosensitive resin composition in any one of Claims 1-3.   A TFT substrate comprising the cured film according to claim 4.   The manufacturing method of a thin-film transistor substrate provided with the process of apply | coating the negative photosensitive resin composition in any one of Claims 1-3, and forming a pattern through exposure and image development.

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