JP2013083996A - Touch panel member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a touch panel member provided with a molybdenum-containing metal wiring covered with a cured film of an alkali developable negative photosensitive resin composition which has excellent pattern processability to form into a cured film having high hardness, high transparency, and excellent resistance to moist heat by UV curing and thermal curing.SOLUTION: A touch panel member is provided with a molybdenum-containing metal wiring covered with a cured film of a negative photosensitive resin composition which contains (A) alkali-soluble resin having a carboxylic acid equivalent in the range of 200 g/mol to 1,400 g/mol, (B) a photopolymerization initiator, (C) a polyfunctional monomer, (D) a zirconium compound.

Description

  The present invention relates to a touch panel member.

  Currently, hard coat materials are used for various purposes, and are used for improving the surface hardness of, for example, containers for automobile parts, cosmetics, sheets, films, optical disks, thin displays, and the like. Properties required for the hard coat material include heat resistance, weather resistance, adhesiveness, etc. in addition to hardness and scratch resistance.

  A representative example of the hard coat material is a radical polymerization type UV curable hard coat (see, for example, Non-Patent Document 1), and the constitution thereof is a polymerizable group-containing oligomer, monomer, photopolymerization initiator, and other additives. It is. The oligomer and the monomer are radically polymerized by UV irradiation to crosslink and obtain a high hardness film. This hard coat material has the advantage that the time required for curing is short and the productivity is improved, and a negative photosensitive material by a general radical polymerization mechanism can be used, and the production cost is low.

  However, since there are many organic components, the hardness and scratch resistance are low compared to other hard coat materials, and there is a problem that cracks are caused due to volume shrinkage due to UV curing.

  The capacitive touch panel, which has been attracting attention in recent years, is one of the uses of hard coat materials. The capacitive touch panel has a structure having a pattern made of ITO (Indium Tin Oxide) or metal (silver, molybdenum, aluminum, etc.) on glass. In order to protect this ITO and metal, a film having high hardness, transparency, and heat-and-moisture resistance is required. However, it is difficult to achieve both of these performances, and a hard coat material that solves this problem has been demanded.

  As an organic hard coat material, a UV curable coating composition containing a polymerizable group-containing oligomer, monomer, photopolymerization initiator and other additives is known. Such a composition has pattern processability and can provide a cured film having high hardness and transparency. However, there was a problem in heat and humidity resistance.

  As a technique for improving the heat and moisture resistance, a method of adding a metal chelating agent to siloxane is known (see Patent Document 1). This is considered to be a mechanism in which titanium or zirconium chelating agent promotes cross-linking of siloxane and improves wet heat resistance.

  In addition, there has been reported an example of imparting negative photosensitivity by introducing a polymerizable functional group using a metal chelating agent as a siloxane polymerization catalyst (see, for example, Patent Document 2).

  In addition, negative photosensitive materials containing organometallic compounds have been reported (Patent Document 3).

JP 07-331173 A Japanese Patent Laid-Open No. 2008-203605 Japanese Unexamined Patent Publication No. 2007-308688

Noboru Ohara et al., “Material Design / Coating Technology and Improvement of Hardness in Hard Coat Films Focusing on Plastic Substrates”, Technical Information Association, April 28, 2005, p. 301

  In the technique of Non-Patent Document 1, since there are many organic components, there is a problem that hardness and scratch resistance are low compared to other hard coat materials, and cracks due to volume shrinkage due to UV curing occur.

  In the technique of Patent Document 1, the resin is limited to siloxane having a hydrophobic main chain and side chain. For example, the effect on a hydrophilic resin such as a siloxane having a carboxyl group in the side chain and a carboxyl group-containing resin is not known. is not.

  In the technique of Patent Document 2, the silanol group content is small in order to suppress cross-linking of siloxane during pre-baking, and it is difficult to develop with an alkaline aqueous solution.

  In the technique of Patent Document 3, baking is performed to form a metal film, and no organic component remains. Therefore, it is not certain what effect the organometallic compound has on the resin component.

  As described above, although there is a demand for a negative photosensitive material having high hardness, high transparency, and high heat-and-moisture resistance and capable of pattern processing with an alkali developer, the technology has not been established so far.

  It is an object of the present invention to provide a negative photosensitive resin composition that is excellent in pattern processability, is high in hardness and high in transparency by UV curing and thermal curing, and gives a cured film excellent in moist heat resistance and capable of alkali development. And

  That is, an object of the present invention is (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol, (B) a photopolymerization initiator, (C) a polyfunctional monomer, (D) zirconium. This is achieved by a touch panel member that includes a cured film of a negative photosensitive resin composition containing a compound, and in which the molybdenum-containing metal wiring is protected by the cured film.

  The negative photosensitive resin composition used in the present invention is preferably a composition for forming a cured film.

  The negative photosensitive resin composition used in the present invention is preferably a composition for forming a protective film.

  In the negative photosensitive resin composition used in the present invention, (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol is an acrylic resin having an ethylenically unsaturated bond. preferable.

  In the negative photosensitive resin composition used in the present invention, (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol is a polysiloxane having an ethylenically unsaturated bond. preferable.

  In the negative photosensitive resin composition used in the present invention, the (D) zirconium compound is preferably zirconium oxide particles having an average particle size of 100 nm or less.

  In the negative photosensitive resin composition used in the present invention, the (D) zirconium compound is preferably any one or more of the compounds represented by the general formula (1).

(R ¹ represents hydrogen, an alkyl group, an aryl group, an alkenyl group and a substituted product thereof, and R ² and R ³ represent hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group and a substituted product thereof. ¹ , R ² and R ³ may be the same or different, and n represents an integer of 0 to 4.)

  The negative photosensitive resin composition used in the present invention is excellent in pattern processability, and can obtain a cured film having high hardness and high transparency by UV curing and thermal curing, and excellent moisture and heat resistance.

It is a schematic top view after each process in manufacture of a touch panel member. It is a schematic sectional drawing showing a touch panel member.

  The negative photosensitive resin composition used in the present invention comprises (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol, (B) a photopolymerization initiator, and (C) a polyfunctional monomer. (D) A zirconium compound is contained.

  The negative photosensitive resin composition used in the present invention is preferably a composition for forming a cured film. The cured film refers to a film obtained by curing with light and / or heat without passing through a step of removing all resin components by baking or stripping solution treatment. Although there is no restriction | limiting in particular in the usage method of this cured film, For example, various kinds, such as a protective film for touchscreens, a hard-coat material, a flattening film for TFT, an overcoat for color filters, a passivation film, an antireflection film, a metal wiring protective film Examples include protective films, various insulating films such as a touch panel insulating film, a TFT insulating film, and an interlayer insulating film, an optical filter, a photo spacer for a color filter, and a microlens. Among these, since it has high hardness, transparency, and heat-and-moisture resistance, it is preferably used as a protective film. The protective film means a cured film used for the purpose of protecting various base materials. There is no restriction | limiting in particular in the usage method of this protective film, What was mentioned above is mentioned as a specific example.

  The negative photosensitive resin composition used in the present invention contains (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol. The carboxylic acid equivalent represents the weight of the resin necessary to obtain 1 mol amount of carboxyl groups, and the unit is g / mol. When the carboxylic acid equivalent of the alkali-soluble resin exceeds 1,400 g / mol, the negative photosensitive resin composition has poor alkali solubility (developability), and a good pattern cannot be formed. Even if it is possible, there are problems that the residue after development cannot be suppressed, or that the type of developer is required to be largely restricted. On the other hand, when the carboxylic acid equivalent of the alkali-soluble resin is less than 200 g / mol, it is not possible to suppress film loss in the exposed area, and in addition to poor moisture and heat resistance, the resolution is also poor. By being in this range, it becomes possible to form good patterns under various development conditions.

  Further, the alkali-soluble resin (A) having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less used in the negative photosensitive resin composition used in the present invention has an ethylenically unsaturated double bond group. Thereby, a crosslinking density can be improved and the hardness of a cured film can be improved. The preferable range of the carboxylic acid equivalent is 300 g / mol or more and 1200 g / mol or less, more preferably 400 g / mol or more and 800 g / mol or less.

  (A) Examples of the alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less include polysiloxane, acrylic resin, polyimide, polyamic acid, and polyamide. (A) In the alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less, at least a part of the hardness of the cured film is that an ethylenically unsaturated double bond group is introduced. Is preferable for increasing the height. Of these polymers, polysiloxanes and acrylic resins are more preferred because of the ease of introduction of ethylenically unsaturated double bond groups. Moreover, you may contain 2 or more types of these polymers.

  (A) Although a preferable example is given as an alkali-soluble resin whose carboxylic acid equivalent is 200 g / mol or more and 1,400 g / mol or less, it is not limited to this.

  The polysiloxane is preferably obtained by hydrolyzing an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group and condensing the hydrolyzate. Moreover, in order to adjust a carboxylic acid equivalent, it is preferable to use another organosilane compound simultaneously. Especially, since the hardness of the obtained cured film becomes high, it is preferable to use the organosilane compound which has an ethylenically unsaturated bond.

  The conditions for the hydrolysis reaction can be appropriately set. For example, after adding an acid catalyst and water to the organosilane compound in a solvent over 1 to 180 minutes, the reaction is performed at room temperature to 110 ° C. for 1 to 180 minutes. It is preferable. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 30 ° C. or higher and 105 ° C. or lower.

  The hydrolysis reaction is preferably performed in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferable. The preferred content of these acid catalysts is preferably 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the total organosilane compound used in the hydrolysis reaction. By controlling the amount of the acid catalyst within the above range, it can be easily controlled so that the hydrolysis reaction proceeds as necessary and sufficiently.

  The conditions for the condensation reaction are, for example, after obtaining a silanol compound by hydrolysis of an organosilane compound as described above, and then reacting the reaction solution by heating it at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours. It is preferable. In order to increase the degree of polymerization of the polysiloxane, reheating or a base catalyst may be added. Further, after hydrolysis according to the purpose, an appropriate amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

  Examples of the polysiloxane having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol and having an ethylenically unsaturated bond include, for example, an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group and an ethylenically unsaturated bond. What is obtained by hydrolyzing an organosilane compound having a water content and condensing the hydrolyzate is preferred.

  Examples of the organosilane compound having a carboxyl group include 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilyl entangled acid, 4-dimethylmethoxysilyl entangled acid, 4-dimethylethoxysilyl entangled acid, 5-trimethoxysilyl valeric acid, 5-triethoxysilyl valeric acid, 5-dimethylmethoxysilyl valeric acid, 5- Examples thereof include dimethylethoxysilyl valeric acid.

  Examples of the organosilane compound having a dicarboxylic anhydride group include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, 3- Dimethylethoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropylcyclohexyl dicarboxylic acid anhydride, 3-triethoxysilylpropylcyclohexyl dicarboxylic acid anhydride, 3-dimethylmethoxysilylpropylcyclohexyl dicarboxylic acid anhydride, 3-dimethylethoxysilyl Propylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, - like dimethyl triethoxysilylpropyl anhydride.

  Examples of other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and 3-aminopropyltriethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycy Doxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxy Ethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxy Butyltriethoxysilane, γ-g Sidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, 3- (3,4-epoxycyclohexyl) propyltri Methoxysila 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, glycine Sidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-g Sidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, trifluoromethyltrimethoxysilane, triflu B methyltriethoxysilane, trifluoropropyl trimethoxysilane, and trifluoropropyl triethoxy silane. In addition, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styryltrimethoxysilane, styryl Triethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-methacryloyl Propylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxy Orchids, .gamma. acrylate by the like acryloyl propyl methyl diethoxy silane, can be easily introduced an ethylenically unsaturated double bond group.

The carboxylic acid equivalent of polysiloxane can be calculated by measuring the acid value after calculating the silanol group / carboxyl group ratio in the polysiloxane by ¹ H-NMR.

  When the polysiloxane has an ethylenically unsaturated double bond group, the content is not particularly limited, but the double bond equivalent is preferably 150 g / mol or more and 10,000 g / mol or less. By being in the above range, both hardness and crack resistance can be achieved at a high level. The double bond equivalent can be calculated by measuring the iodine value.

  The weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 1,000 or more and 100,000 or less in terms of polystyrene measured by gel permeation chromatography (GPC). By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good.

  As an acrylic resin, what carried out radical polymerization of (meth) acrylic acid and (meth) acrylic acid ester is preferable. There are no particular restrictions on the radical polymerization catalyst, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are generally used.

  The conditions for radical polymerization can be appropriately set. For example, in a solvent, (meth) acrylic acid, (meth) acrylic acid ester and a radical polymerization catalyst are added, and the inside of the reaction vessel is sufficiently filled by bubbling or vacuum degassing. It is preferable to carry out the reaction at 60 ° C. or higher and 110 ° C. or lower for 30 to 300 minutes after nitrogen substitution. Moreover, you may use chain transfer agents, such as a thiol compound, as needed.

  (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, (meth) acrylic acid cyclohexenyl, (meth) acrylic acid 4-methoxycyclohexyl, (meth) acrylic acid 2-cyclopropyloxycarbonylethyl, (meth) acrylic acid 2-cyclopentyloxycarbonylethyl, (meth) acrylic acid 2-Cyclohexyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexenyloxycarbonylethyl, (meth) acrylic acid 2- (4-methoxycyclohexyl) oxycarbonylethyl, (meth) acrylic acid norbornyl, (meth) acrylic Isobornyl, tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 1-methyladamantyl (meth) acrylate, etc. are used. It is done. You may copolymerize aromatic vinyl compounds, such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, (alpha) -methylstyrene.

  As an acrylic resin having an carboxylic acid equivalent of 200 g / mol to 1,400 g / mol and having an ethylenically unsaturated bond, for example, (meth) acrylic acid and (meth) acrylic acid ester are subjected to radical polymerization, What is obtained by addition reaction of an epoxy compound having a saturated double bond group is preferred. There is no particular limitation on the catalyst used for the addition reaction of the epoxy compound having an ethylenically unsaturated double bond group, and a known catalyst can be used. For example, dimethylaniline, 2,4,6-tris (dimethylaminomethyl) ) Amino catalysts such as phenol and dimethylbenzylamine, tin catalysts such as tin (II) 2-ethylhexanoate and dibutyltin laurate, titanium catalysts such as titanium (IV) 2-ethylhexanoate, triphenylphosphine, etc. And phosphorus-based catalysts such as acetylacetonate chromium and chromium chloride. Examples of the epoxy compound having an ethylenically unsaturated double bond group 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, allylglycidyl Ether, vinyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α -Methyl-p-vinylbenzylglyci 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, 2,4,6-triglycidyloxymethyl Styrene or the like is used.

  When the acrylic resin has an ethylenically unsaturated double bond group, the content thereof is not particularly limited, but the double bond equivalent is preferably 150 g / mol or more and 10,000 g / mol or less. By being in the above range, both hardness and crack resistance can be achieved at a high level. The double bond equivalent can be calculated by measuring the iodine value.

  The weight average molecular weight (Mw) of the acrylic resin is not particularly limited, but is preferably 2,000 or more and 200,000 or less in terms of polystyrene measured by gel permeation chromatography (GPC). By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good.

  In the negative photosensitive resin composition used in the present invention, the content of (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less is not particularly limited, and the desired film thickness and application However, it is generally 10 wt% or more and 60 wt% or less in the solid content of the negative photosensitive resin composition.

  The negative photosensitive resin composition used in the present invention contains (B) a photopolymerization initiator. (B) The photopolymerization initiator is preferably one that decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals.

  Specific examples include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine- 4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoylphenylphosphine 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- (phenylthio) -2- (O-benzoy Oxime)], 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- (0-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-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-Isopropylphenyl) -2-hydroxy-2-methyl Propan-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, alkylated benzophenone, 3,3 ', 4 4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanami Umbromide, (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-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloro Acridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphor -Quinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis (η5-2,4-cyclopentadiene-1- Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, di Benzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl Acetal, anthra Non, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, 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 tetrabrominated carbon, tribromophenylsulfone, peroxy Examples thereof include a combination of a photoreducible dye such as benzoyl oxide, eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. Two or more of these may be contained.

  Among these, in order to further increase the hardness of the cured film, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having amino groups, or benzoic acid ester compounds having amino groups are preferable.

  Specific 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, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like. Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2 , 4,4-trimethylpentyl) -phosphine oxide. Specific examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -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- (0-acetyloxime) and the like. Specific examples of the benzophenone compound having an amino group include 4,4-bis (dimethylamino) benzophenone and 4,4-bis (diethylamino) benzophenone. Specific examples of the benzoic acid ester compound having an amino group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like.

  In the negative photosensitive resin composition used in the present invention, the content of the (B) photopolymerization initiator is not particularly limited, but is 0.1 wt% or more and 20 wt% in the solid content of the negative photosensitive resin composition. % Or less is preferable. By setting it as the said range, hardening can fully be advanced and elution of the residual polymerization initiator etc. can be prevented and solvent resistance can be ensured.

  The negative photosensitive resin composition used in the present invention contains (C) a polyfunctional monomer. Polymerization of the polyfunctional monomer (C) proceeds with the photopolymerization initiator (B) by light irradiation, and the exposed portion of the negative photosensitive resin composition used in the present invention is insolubilized in the aqueous alkali solution. A pattern can be formed. The polyfunctional monomer refers to a compound having at least two ethylenically unsaturated double bonds in the molecule, and is not particularly limited, but a polyfunctional monomer having a (meth) acryl group that is easily radically polymerized is used. preferable. The double bond equivalent of the (C) polyfunctional monomer is preferably 80 g / mol or more and 400 g / mol or less from the viewpoint of sensitivity and hardness.

(C) Examples of polyfunctional monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1 9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol Methacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, 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-methacryloyloxy) Ethoxy) -3-methylphenyl] fluorene, (2-acryloyloxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4 -(2-acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) -3,5-dimethylphenyl] fluorene, and the like.
Among these, from the viewpoint of improving sensitivity, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, and the like are preferable. From the viewpoint of improving hydrophobicity, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene Etc. are preferable.

  In the negative photosensitive resin composition used in the present invention, the content of the polyfunctional monomer (C) is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application, but the negative photosensitive resin composition The solid content is generally 10 wt% or more and 60 wt% or less.

  The negative photosensitive resin composition used in the present invention contains (D) a zirconium compound. (D) Moisture heat resistance of the cured film obtained improves by containing a zirconium compound. The alkali-soluble resin having a carboxyl group is poor in wet heat resistance because it is hydrophilic derived from a carboxyl group, but the wet heat resistance of the cured film is improved by containing (D) a zirconium compound. So far, it has been known that some zirconium compounds have an effect of improving heat and moisture resistance with respect to polysiloxane (see Patent Document 1), but in this known example, the side chain of polysiloxane is limited to hydrophobic groups. As a result, the resulting cured film is also hydrophobic, so the effect of having a hydrophilic group such as a carboxyl group was not clear. In the present invention, not only polysiloxane but also a carboxyl group-containing alkali-soluble resin, which is a hydrophilic resin, has been found for the first time that the moisture and heat resistance of a cured film is improved by containing (D) a zirconium compound. Although its detailed mechanism is not clear, (D) a zirconium compound reacts with (A) a plurality of carboxyl groups of an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol. It is considered that the wet heat resistance of the resulting cured film is improved by forming a crosslinked structure and improving the film density and at the same time reducing the hydrophilicity derived from the carboxyl group. (D) Although there will be no restriction | limiting in particular if a zirconium compound is a compound containing a zirconium atom, For example, the compound represented by the zirconium oxide particle | grains whose average particle diameter is 100 nm or less, and General formula (1) is preferable. The average particle diameter of the zirconium oxide particles is more preferably 40 nm or less. By setting the average particle diameter of the zirconium oxide particles to 100 nm or less, white turbidity of the obtained cured film can be prevented.

(R ¹ represents hydrogen, an alkyl group, an aryl group, an alkenyl group and a substituted product thereof, and R ² and R ³ represent hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group and a substituted product thereof. ¹ , R ² and R ³ may be the same or different, and n represents an integer of 0 to 4.)
Here, the average particle diameter means the median diameter determined from the particle size distribution measured by the Coulter method.

  Zirconium oxide particles having an average particle size of 100 nm or less can use commercially available products. As specific examples, “Vilal Zr-C20 (trade name)” (average particle size 20 nm, manufactured by Taki Chemical Co., Ltd.), “Nanouse OZ-30M (trade name)” (average particle diameter 7 nm) (manufactured by Nissan Chemical Industries, Ltd.), “ZSL-10T (trade name)” (average particle diameter 15 nm), “ZSL-10A (trade name)” "(Average particle size 70 nm)" (above, manufactured by Daiichi Rare Element Chemical Co., Ltd.).

In the general formula (1), R ¹ includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a phenyl group, a vinyl group, and the like. Among these, n-propyl group, n-butyl group and phenyl group are preferable since the compound is stable. R ² and R ³ are hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, phenyl group, vinyl group, methoxy group, ethoxy group N-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, benzyloxy group and the like. Among them, a methyl group, a t-butyl group, a phenyl group, a methoxy group, and an ethoxy group are preferable because they are easily synthesized and the compound is stable.

  Examples of the compound represented by the general formula (1) include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetrasecondary butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra (2,2,6, 6-tetramethyl-3,5-heptanedionate), zirconium tetramethyl acetoacetate, zirconium tetraethyl acetoacetate, zirconium tetramethyl malonate, zirconium tetraethyl malonate, zirconium tetrabenzoyl acetonate, zirconium tetradibenzoyl methacrylate, zirconium Mononormal butoxyacetylacetonate bis (ethylacetoacetate), zirconium mononormalbutoxy Tylacetoacetate bis (acetylacetonate), zirconium mononormal butoxytriacetylacetonate, zirconium mononormalbutoxytriacetylacetonate, zirconium dinormalbutoxybis (ethylacetoacetate), zirconium dinormalbutoxybis (acetylacetonate), Zirconium dinormal butoxy bis (ethyl malonate), zirconium di normal butoxy bis (benzoyl acetonate), zirconium di normal butoxy bis (dibenzoyl methacrylate) and the like. Among these, from the viewpoint of solubility in various solvents and / or stability of the compound, zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra (2,2,6,6-tetra Methyl-3,5-heptanedionate), zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetraethylacetoacetate, zirconium dinormalbutoxybis (ethylacetoacetate) and zirconium mononormalbutoxyacetylacetonatebis (ethylacetoacetate) ) Is preferred.

  In the negative photosensitive resin composition used in the present invention, the content of the (D) zirconium compound is not particularly limited, but in the case of zirconium oxide particles having an average particle diameter of 100 nm or less, the negative photosensitive resin composition The solid content is preferably 1 wt% or more and 60 wt% or less, and in the case of other (D) zirconium compounds, the solid content of the negative photosensitive resin composition is preferably 0.1 wt% or more and 10 wt% or less. By being in the above-mentioned range, both transparency and wet heat resistance can be achieved at a high level.

  The negative photosensitive resin composition used in the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability of the resin composition is improved, and the resolution after development is improved. The content of the polymerization inhibitor is preferably 0.01 wt% or more and 1 wt% or less in the solid content of the negative photosensitive resin composition.

  Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, 4-methoxyphenol and the like.

  The negative photosensitive resin composition used in the present invention may contain an ultraviolet absorber. By containing an ultraviolet absorber, the light resistance of the resulting cured film is improved, and the resolution after development is improved in applications that require pattern processing. The ultraviolet absorber is not particularly limited and known ones can be used, but benzotriazole compounds, benzophenone compounds, and triazine compounds are preferably used in terms of transparency and non-coloring properties.

  Examples of ultraviolet absorbers for benzotriazole compounds include 2- (2Hbenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2 And '-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole. Examples of the ultraviolet absorber of the benzophenone 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 used in the present invention may contain a solvent. A compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferably used in that each component can be dissolved uniformly and the transparency of the resulting coating film can be improved. Two or more of these may be used. A compound having a boiling point of 110 ° C. or more and 250 ° C. or less under atmospheric pressure is more preferable. By setting the boiling point to 110 ° C. or higher, drying proceeds moderately at the time of coating, and a good coating without uneven coating can be obtained. On the other hand, when the boiling point is 250 ° C. or lower, the amount of residual solvent in the film can be reduced, and film shrinkage during thermosetting can be further reduced, so that better flatness can be obtained.

  Specific examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 ° C. or more and 250 ° C. or less under atmospheric pressure include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl- 2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Examples include glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol. Among these, diacetone alcohol is preferable from the viewpoint of storage stability, and propylene glycol mono t-butyl ether is particularly preferably used from the viewpoint of step coverage.

  Specific examples of the cyclic compound having a carbonyl group and having a boiling point of 110 ° C. or more and 250 ° C. or less under atmospheric pressure include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, Examples include cyclohexanone and cycloheptanone. Among these, γ-butyrolactone is particularly preferably used.

  Moreover, the negative photosensitive resin composition used by this invention may contain solvents other than the above. For example, ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone, etc. Ketones; amides such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3 -Acetates such as methoxybutyl acetate.

  There is no restriction | limiting in particular in content of a solvent, According to the application | coating method etc., arbitrary amounts can be used. For example, when film formation is performed by spin coating, it is common to use 50 wt% or more and 95 wt% or less of the entire negative photosensitive resin composition.

  The negative photosensitive resin composition used in the present invention may contain various curing agents that accelerate the curing of the resin composition or facilitate the curing. The curing agent is not particularly limited and known ones can be used. Specific examples include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, and methylolated melamine. Derivatives, methylolated urea derivatives and the like. Two or more of these may be contained. Of these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used because of the stability of the curing agent and the processability of the obtained coating film.

  Since curing of polysiloxane is promoted by acid, when polysiloxane is used in the negative photosensitive resin composition used in the present invention, it may contain a curing catalyst such as a thermal acid generator. The thermal acid generator is not particularly limited and known ones can be used. Various onium salt compounds such as aromatic diazonium salts, sulfonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenium salts, and sulfonic acid esters. And halogen compounds.

  The negative photosensitive resin composition used in the present invention may contain various surfactants such as various fluorosurfactants and silicone surfactants in order to improve the flowability at the time of coating. There is no particular limitation on the type of the surfactant, and for example, “Megafac (registered trademark)” “F142D (trade name)”, “F172 (trade name)”, “F173 (trade name)”, “F183 (trade name) ”,“ F445 (product name) ”,“ F470 (product name) ”,“ F475 (product name) ”,“ F477 (product name) ”(above, manufactured by Dainippon Ink & Chemicals, Inc.),“ NBX ” -15 (trade name) "," FTX-218 (trade name) "(manufactured by Neos Co., Ltd.) and other fluorine-based surfactants," BYK-333 (trade name) "," BYK-301 (trade name) " ”,“ BYK-331 (product name) ”,“ BYK-345 (product name) ”,“ BYK-307 (product name) ”,“ BYK-352 (product name) ”(manufactured by Big Chemie Japan Co., Ltd.) Silicone surfactants such as polyalkylene oxide Surfactants, poly (meth) acrylate surfactant, or the like can be used. Two or more of these may be used.

  The negative photosensitive resin composition used in the present invention may contain additives such as a dissolution inhibitor, a stabilizer, and an antifoaming agent as necessary.

  There is no restriction | limiting in particular in the solid content density | concentration of the negative photosensitive resin composition used by this invention, Arbitrary amounts of a solvent and a solute can be used according to a coating method. For example, when a film is formed by spin coating as will be described later, the solid concentration is generally 5 wt% or more and 50 wt% or less.

  The typical manufacturing method of the negative photosensitive resin composition used by this invention is demonstrated below.

  For example, after (B) a photopolymerization initiator, (D) a zirconium compound and other additives are added to an arbitrary solvent and dissolved by stirring, (A) the carboxylic acid equivalent is 200 g / mol or more and 1,400 g / The alkali-soluble resin and (C) polyfunctional monomer which are less than mol are added and further stirred for 20 minutes to 3 hours. 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 used by this invention.

  The negative photosensitive resin composition used in 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, slit coating, etc. Pre-bake with a heating device such as oven. Pre-baking is performed in the range of 50 ° C. to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 μm to 15 μm.

After pre-baking, using an exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (hereinafter referred to as PLA), light of about 10 to 4,000 J / m ² (wavelength 365 nm exposure amount conversion) is desired Irradiate through or without the mask. The exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used. Then, you may perform the post-exposure baking which heats this film | membrane for about 1 hour in 150-450 degreeC with heating apparatuses, such as a hotplate and oven.

Negative photosensitive resin composition used in the present invention, it is preferable sensitivity at exposure by the PLA is 100 J / ^{m 2} or more 4,000J / ^{m 2} or less. The sensitivity in the patterning exposure by the PLA is determined by the following method, for example. The composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater, and prebaked at 120 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 2 μm. The prepared film was exposed to an ultrahigh pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (“PLA-501F (trade name)” manufactured by Canon Inc.), and then an automatic developing apparatus (Takizawa Sangyo ( Paddle development with a 0.4 wt% tetramethylammonium hydroxide aqueous solution for an arbitrary time using “AD-2000 (trade name)” manufactured by Co., Ltd., followed by rinsing with water for 30 seconds. In the formed pattern, an exposure amount for resolving a 30 μm line-and-space pattern with a one-to-one width is obtained as sensitivity.

  After patterning exposure, the exposed portion is dissolved by development, and a negative pattern can be obtained. As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, and then dry baking may be performed in the range of 50 ° C. to 150 ° C. Thereafter, this film is thermally cured by a heating device such as a hot plate or an oven in the range of 120 ° C. or higher and 280 ° C. or lower for about 1 hour to obtain a cured film.

  The cured film obtained from the negative photosensitive resin composition used in the present invention has a zirconium atom content of 0.02 wt% to 7.5 wt%, a carbon atom content of 25 wt% to 80 wt%, and a silicon atom content. Is preferably 0.5 wt% or more and 20 wt% or less. By being in the above range, the transmittance, hardness, and heat and humidity resistance can be maintained in a well-balanced manner. Further, the resolution is preferably 20 μm or less. Although there is no restriction | limiting in particular in the film thickness of a cured film, 0.1 to 15 micrometers is preferable. Further, it is preferable that the hardness is 4H or more and the transmittance is 90% or more at a film thickness of 1.5 μm. The transmittance refers to the transmittance at a wavelength of 400 nm. The hardness and transmittance can be adjusted by selecting the exposure amount and the thermosetting temperature.

  The cured film obtained by curing the negative photosensitive resin composition used in the present invention is a protective film for a touch panel, various hard coat materials, a flattening film for TFT, an overcoat for a color filter, an antireflection film and the like. It can be used for films, optical filters, touch sensor insulating films, TFT insulating films, color filter photo spacers, and the like. Among these, since it has high hardness and transparency, it can be suitably used as a protective film for a touch panel. Examples of the touch panel system include a resistive film type, an optical type, an electromagnetic induction type, and a capacitance type. Since especially high hardness is calculated | required by an electrostatic capacitance type touch panel, the cured film of this invention can be used suitably.

Furthermore, since the cured film obtained by curing the negative photosensitive resin composition used in the present invention has high moisture and heat resistance, it can be suitably used as a metal wiring protective film. By forming on the metal wiring, it is possible to prevent deterioration (such as a decrease in conductivity) due to corrosion of the metal. The metal to be protected is not particularly limited, and examples thereof include copper, silver, aluminum, chromium, molybdenum, titanium, ITO, IZO (indium zinc oxide), AZO (aluminum-added zinc oxide), and ZnO ₂ . In particular, it can be suitably used in touch panel members containing molybdenum. The touch panel member here is a glass or film substrate provided with an electrode and an insulating film and / or a protective film, and refers to a member that can be used as a sensor substrate for a touch panel.

Although there is no restriction | limiting in particular in the preparation methods of a touchscreen member, For example, the following methods are mentioned. A transparent electrode thin film is formed on a glass substrate with an arbitrary film thickness, a resist material is patterned by a photolithography technique, a chemical solution etching with an etching solution of the transparent electrode, and a resist stripping step with a stripping solution are performed. A glass substrate on which a transparent electrode forming a part of the shaft electrode is patterned is produced (FIG. 1-a). Examples of the transparent electrode include metal oxides such as ITO, IZO, AZO, ZnO ₂ and tin antimonic acid, or thin films of metals such as gold, silver, copper, and aluminum. These transparent conductive electrodes can be formed by conventional methods such as physical methods such as vacuum deposition, sputtering, ion plating, ion beam deposition, and chemical vapor deposition. Subsequently, a cured film obtained from the negative photosensitive resin composition used in the present invention is formed as a transparent insulating film at a portion intersecting with an electrode to be formed later (FIG. 1-b). Thereafter, the connection wiring to the IC driver and the Y-axis electrode conduction wiring are formed through the resist pattern processing, etching, and resist stripping steps after forming the electrode thin film with an arbitrary film thickness (FIG. 1-c). Examples of the electrode include molybdenum, molybdenum / aluminum / molybdenum laminated film (MAM), molybdenum-niobium alloy, chromium, titanium, titanium / aluminum / titanium laminated film (TAT), aluminum and the like in addition to the transparent electrode material. Can be mentioned. Finally, a transparent protective film is formed on a portion other than the connection portion with the IC driver at the end of the substrate (the upper left portion and the lower right portion of FIG. 1-c), and the curing obtained from the negative photosensitive resin composition used in the present invention. A touch panel member is obtained by using a film. FIG. 2 is a cross-sectional view of the touch panel member manufacturing example.

The present invention will be described below with reference to examples thereof, but the embodiment of the present invention is not limited to these examples.
(Synthesis Example 1: Synthesis of polysiloxane solution (i))
In a 500 mL three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropyl succinic acid, 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane and 185.08 g of diacetone alcohol (hereinafter referred to as DAA) were charged, immersed in an oil bath at 40 ° C. An aqueous phosphoric acid solution in which 391 g (0.2 wt% with respect to the charged monomer) was dissolved was added over 10 minutes with a dropping funnel. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 120 g of methanol and water as by-products were distilled. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (i). In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 8,000 (polystyrene conversion). The carboxylic acid equivalent was 620 g / mol.
(Synthesis Example 2: Synthesis of polysiloxane solution (ii))
In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 13.12 g (0.05 mol) of 3-trimethoxysilylpropyl succinic acid, Charge 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane and 174.74 g of DAA, soak in an oil bath at 40 ° C. and stir in water 54.9 g with 0.379 g of phosphoric acid (based on the charged monomers) Then, an aqueous solution of phosphoric acid in which 0.2 wt% was dissolved was added with a dropping funnel over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 110 g of methanol and water as by-products were distilled. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (ii). In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 6,000 (polystyrene conversion). The carboxylic acid equivalent was 1,190 g / mol.
(Synthesis Example 3: Synthesis of polysiloxane solution (iii))
In a 500 mL three-necked flask, 27.24 g (0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 65.58 g (0.25 mol) of 3-trimethoxysilylpropyl succinic acid, Charge 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane and 198.02 g of DAA, soak in an oil bath at 40 ° C. and stir and stir in 0.45 g of phosphoric acid in 58.5 g of water (based on the charged monomers). Then, an aqueous solution of phosphoric acid in which 0.2 wt% was dissolved was added with a dropping funnel over 10 minutes. Subsequently, when heated and stirred under the same conditions as in Synthesis Example 1, a total of 130 g of methanol and water as by-products were distilled. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (iii). In addition, it was 7,000 (polystyrene conversion) when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC. The carboxylic acid equivalent was 280 g / mol.
(Synthesis Example 4: Synthesis of polysiloxane solution (iv))
In a 500 mL three-necked flask, 34.05 g (0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 41.66 g (0.20 mol) of 3-trimethoxysilylbutyric acid, γ- Charge 82.04 g (0.35 mol) of acryloylpropyltrimethoxysilane and 182.22 g of DAA, soak in an oil bath at 40 ° C. and stir in water 54.0 g with 0.395 g of phosphoric acid (0 to the charged monomer). .2 wt%) was added over 10 minutes with a dropping funnel. Next, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 120 g of methanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (iv). In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 8,000 (polystyrene conversion). The carboxylic acid equivalent was 640 g / mol.
(Synthesis Example 5: Synthesis of polysiloxane solution (v))
In a 500 mL three-necked flask, 68.10 g (0.50 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, and 143.37 g of 3-methyl-3-methoxybutanol (hereinafter referred to as MMB) An aqueous phosphoric acid solution in which 0.167 g of phosphoric acid (0.1 wt% with respect to the charged monomer) was dissolved in 54.0 g of water was added over 10 minutes with a dropping funnel while being immersed in an oil bath at 40 ° C. and stirred. . Next, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 120 g of methanol and water as by-products were distilled out. To the obtained polysiloxane MMB solution, MMB was added so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (v). In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 8,000 (polystyrene conversion). The carboxylic acid equivalent was 0 g / mol. This Synthesis Example 5 is an embodiment described in Patent Document 1.
(Synthesis Example 6: Synthesis of acrylic resin solution (a))
A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of propylene glycol methyl ether acetate (hereinafter PGMEA). Thereafter, 23.0 g of methacrylic acid, 31.5 g of benzyl methacrylate, and 32.8 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred at room temperature for a while. After sufficiently purging with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 12.7 g of glycidyl methacrylate, 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 to obtain an acrylic resin solution ( a) was obtained. PGMEA was added to the obtained acrylic resin solution (a) so that the solid content concentration was 40 wt%. The weight average molecular weight of the acrylic resin was 18,000, and the carboxylic acid equivalent was 560 g / mol.
(Synthesis Example 7: Synthesis of acrylic resin solution (b))
A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 16.8 g of methacrylic acid, 34.4 g of benzyl methacrylate, and 36.9 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred at room temperature for a while. After sufficiently purging with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 11.9 g of glycidyl methacrylate, 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 to obtain an acrylic resin solution ( b). PGMEA was added to the obtained acrylic resin solution (b) so that the solid content concentration was 40 wt%. The weight average molecular weight of the acrylic resin was 13,000, and the carboxylic acid equivalent was 890 g / mol.
(Synthesis Example 8: Synthesis of acrylic resin solution (c))
A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA. Thereafter, 33.9 g of methacrylic acid, 34.4 g of benzyl methacrylate, and 36.9 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. After sufficiently purging with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 14.0 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution ( c). PGMEA was added to the obtained acrylic resin solution (c) so that the solid content concentration was 40 wt%. The weight average molecular weight of the acrylic resin was 24,000, and the carboxylic acid equivalent was 340 g / mol.
(Synthesis Example 9: Synthesis of acrylic resin solution (d))
A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA. Thereafter, 8.24 g of methacrylic acid, 35.5 g of benzyl methacrylate, and 45.5 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred at room temperature for a while. After sufficiently purging with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 10.7 g of glycidyl methacrylate, 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 to obtain an acrylic resin solution ( d). PGMEA was added to the obtained acrylic resin solution (d) so that the solid content concentration was 40 wt%. The weight average molecular weight of the acrylic resin was 9,000, and the carboxylic acid equivalent was 4,600 g / mol.
(Synthesis Example 10: Synthesis of acrylic resin solution (e))
A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA. Thereafter, 69.5 g of methacrylic acid, 7.9 g of benzyl methacrylate, and 9.9 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. After sufficiently purging with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 12.8 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution ( e). PGMEA was added to the obtained acrylic resin solution (e) so that the solid content concentration was 40 wt%. The acrylic resin had a weight average molecular weight of 40,000 and a carboxylic acid equivalent of 140 g / mol.

  Table 1 summarizes the compositions of Synthesis Examples 1 to 9.

The evaluation methods in each example and comparative example are shown below.
(1) Transmittance measurement The produced negative photosensitive resin composition was applied to a 5 cm square Tempax glass substrate (Asahi Techno Glass plate) and a spin coater (Mikasa) “1H-360S (trade name). ) "), Spin for 10 seconds at 500 rpm, spin for 4 seconds at 1,000 rpm, and then apply hot plate (" SCW-636 (trade name) "manufactured by Dainippon Screen Mfg. Co., Ltd.)) And prebaked at 90 ° C. for 2 minutes to produce a film having a thickness of 2 μm. The prepared film was exposed using a parallel light mask aligner (hereinafter referred to as PLA) (“PLA-501F (trade name)” manufactured by Canon Inc.) as an ultrahigh pressure mercury lamp as a light source, and an oven (“IHPS manufactured by ESPEC Corporation) was used. -222 ") and cured in air at 230 ° C for 1 hour to produce a cured film having a thickness of 1.5 µm.

About the obtained cured film, the transmittance | permeability of 400 nm was measured using the ultraviolet-visible spectrophotometer "UV-260 (brand name)" (made by Shimadzu Corp.). The film thickness was measured at a refractive index of 1.55 using “Lambda Ace STM-602 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd. The same applies to the film thickness described below.
(2) Measurement of hardness Pencil hardness was measured according to JIS K 5600-5-4 (1999) for a cured film having a film thickness of 1.5 μm obtained by the method described in (1) above.
(3) Moisture and heat resistance After a cured film is produced on a glass having a molybdenum sputtered film by the method described in (1) above, an oven at a temperature of 85 ° C. and a humidity of 85% (ESPEC Corporation, “EX-111 (product) Name) ")) and after being tested for 300 hours, the degree of discoloration of molybdenum was evaluated. Further, a glass substrate with only a molybdenum sputtered film was also tested at the same time, and the following determination was made as an index of the degree of discoloration before and after the test.

  5: Discoloration is not seen in molybdenum under the cured film before and after the test.

  4: Before and after the test, the molybdenum under the cured film was discolored by about 10% compared to the case where the cured film was not covered with the cured film.

  3: Before and after the test, the molybdenum under the cured film was discolored by about 20% as compared to the case where the cured film was not covered with the cured film.

  2: Before and after the test, the molybdenum under the cured film was discolored by about 40% compared to the case where the cured film was not covered with the cured film.

1: Before and after the test, the molybdenum under the cured film was discolored by about 60% or more compared to the case where the cured film was not covered with the cured film.
(4) Pattern workability (4-1) Sensitivity Rotate negative photosensitive resin composition A on a silicon wafer for 10 seconds at 500 rpm using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.). After spin coating at 1,000 rpm for 4 seconds, the film was pre-baked at 90 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.). A pre-baked film having a thickness of 2 μm was produced. The obtained pre-baked film was exposed with a gap of 100 μm through a gray scale mask for sensitivity measurement using PLA as an ultrahigh pressure mercury lamp as a light source. Thereafter, using an automatic developing device (“AD-2000 (trade name)”, manufactured by Takizawa Sangyo Co., Ltd.), a 0.4 wt% (or 2.38 wt%) aqueous solution of tetramethylammonium hydroxide (hereinafter, TMAH). For 90 seconds and then rinsed with water for 30 seconds.

After exposure and development, the exposure amount for forming a 30 μm line-and-space pattern with a one-to-one width (hereinafter referred to as the optimum exposure amount) was defined as sensitivity. The exposure was measured with an I-line illuminometer.
(4-2) Resolution The minimum pattern size after development at the optimum exposure amount was measured.
(4-3) Residue after development After patterning on a silicon wafer by the method described in (4-1) above, determination was made as follows according to the degree of unmelted unexposed portion.

  5: There is no unsolved residue by visual observation, and there is no residue in a fine pattern of 50 μm or less even by microscopic observation.

  4: There is no unsolved residue visually, and there is no residue in the pattern of 50 μm or more in the microscopic observation, but there is a residue in the pattern of 50 μm or less.

  3: Although there is no unsolved residue visually, there is a residue in a pattern of 50 μm or more in microscopic observation.

  2: Visually, there is unsolved residue at the substrate end (thick film portion).

1: Visually, there is unsolved residue in the whole unexposed part.
Example 1
Under a yellow light, 0.277 g of 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (“Irgacure OXE-01 (trade name)” manufactured by Ciba Specialty Chemicals) Dissolved in DAA2.846g, PGMEA2.317g, zirconium dinormalbutoxybis (ethyl acetoacetate) (70wt% 1-butanol solution) ("Orgachix ZC-580 (trade name)", manufactured by Matsumoto Fine Chemical) 0.227g, 0.2000 g of PGMEA 1 wt% solution (corresponding to a concentration of 100 ppm) of “BYK-333 (trade name)” (manufactured by Big Chemie Japan Co., Ltd.), which is a silicone-based surfactant, 1 wt% PGMEA solution of 4-t-butylcatechol .661 g was added and stirred. Then, 5.538 g of PGMEA 50 wt% solution of dipentaerythritol hexaacrylate (“Kayarad (registered trademark)” DPHA (trade name), manufactured by Shin Nippon Kayaku) and 6.923 g of polysiloxane solution (i) were added. And stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (S-1). About the obtained negative photosensitive resin composition (S-1), the transmittance | permeability, hardness, heat-and-moisture resistance, and pattern workability were evaluated by the said method.
(Example 2)
A negative photosensitive resin composition (S-2) was obtained in the same manner as in Example 1 except that the polysiloxane solution (ii) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (S-2). However, a 2.38 wt% TMAH aqueous solution was used as the developer.
(Example 3)
A negative photosensitive resin composition (S-3) was obtained in the same manner as in Example 1 except that the polysiloxane solution (iii) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-3).
Example 4
A negative photosensitive resin composition (S-4) was obtained in the same manner as in Example 1 except that the polysiloxane solution (iv) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-4).
(Example 5)
2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907 (trade name)” manufactured by Ciba Specialty Chemicals) under a yellow light 0.503 g, 4,4-bis 0.026 g of (diethylamino) benzophenone (“EAB-F (trade name)” manufactured by Hodogaya Chemical Co., Ltd.) is 3.030 g of DAA, 2.515 g of PGMEA, 0.227 g of “ZC-580 (trade name)”, silicone type Surfactant BYK-333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 100 ppm) and 4-t-butylcatechol (1 wt% PGMEA solution) 1.588 g were added and stirred. Thereto, 5.294 g of “DPHA” (50 wt% PGMEA solution) and 6.617 g of polysiloxane solution (i) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (S-5). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-5).
(Example 6)
Instead of Irgacure OXE-01, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) ("Irgacure OXE-02 ( Product name) “Ciba Specialty Chemicals” was used in the same manner as in Example 1 to obtain a negative photosensitive resin composition (S-6). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-6).
(Example 7)
Negative-type photosensitivity is obtained in the same manner as in Example 1 except that tripentaerythritol octaacrylate (“V # 802 (trade name)”, manufactured by Osaka Organic Chemical Co., Ltd.) is used instead of “DPHA (trade name)”. Resin composition (S-7) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-7).
(Example 8)
Instead of “DPHA (trade name)”, “V # 802 (trade name)” (50% PGMEA solution) 3.323 g and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (“BPEFA”) (Trade name) ”, manufactured by Osaka Gas Chemical Co., Ltd. (50 wt% PGMEA solution) Except for using 2.215 g, a negative photosensitive resin composition (S-8) was obtained in the same manner as in Example 1. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-8).
Example 9
Under yellow light, “OXE-01 (trade name)” 0.277 g, DAA 2.846 g, PGMEA 2.016 g, “Nanouse OZ-30M (trade name)” (methanol solution, solid content = 30.9 wt%) 0 538 g, BYK-333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 100 ppm) and 1.661 g of 4-t-butylcatechol (1 wt% PGMEA solution) which are silicone surfactants were added and stirred. "DPHA (trade name)" (50% PGMEA solution) 5.538 g and polysiloxane solution (i) 6.923 g were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (S-9). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-9).
(Example 10)
Under a yellow light, “OXE-01 (trade name)” 0.239 g, DAA 3.410 g, PGMEA 0.846 g, “Nanouse OZ-30M (trade name)” (methanol solution, solid content = 30.9 wt%) 3 0.098 g, BYK-333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 100 ppm) and 1.436 g of 4-t-butylcatechol (1 wt% PGMEA solution) which are silicone surfactants were added and stirred. 4.DPHA (trade name) (50% PGMEA solution) 4.787 g and polysiloxane solution (i) 5.984 g were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (S-10). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-10).
(Example 11)
Instead of 0.538 g of “Nanouse OZ-30M (trade name)”, it is the same as in Example 9 except that 0.831 g of “Viral Zr-C20 (trade name)” (methanol solution, solid content = 20 wt%) is used. And a negative photosensitive resin composition (S-11) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-11).
(Example 12)
Under a yellow light, “OXE-01 (trade name)” 0.277 g, DAA 2.846 g, PGMEA 2.388 g, zirconium tetraacetylacetonate (“Nashem Zirconium (trade name)”, manufactured by Nippon Chemical Industry Co., Ltd.) 166 g, 0.2000 g (corresponding to a concentration of 100 ppm) of BYK-333 (1 wt% PGMEA solution) which is a silicone-based surfactant, and 1.661 g of 4-t-butylcatechol (1 wt% PGMEA solution) were added and stirred. “DPHA (trade name)” (50 wt% PGMEA solution) 5.538 g and polysiloxane solution (i) 6.923 g were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (S-12). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-12).
(Example 13)
A negative photosensitive resin composition (S-13) was obtained in the same manner as in Example 12 except that the addition amount of nursem zirconium was 0.017 g. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-13).
(Example 14)
A negative photosensitive resin composition (S-14) was obtained in the same manner as in Example 12 except that the amount of nursem zirconium added was 0.323 g. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-14).
(Example 15)
A negative photosensitive resin composition (S-13) was obtained in the same manner as in Example 12 except that zirconium tetrapropoxide was used instead of nasem zirconium. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-13).
(Example 16)
A negative photosensitive resin composition (S-14) was obtained in the same manner as in Example 12 except that zirconium tetraphenoxide was used instead of nasem zirconium. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-14).
(Example 17)
A negative photosensitive resin composition (S--) was prepared in the same manner as in Example 12 except that zirconium tetra (2,2,6,6-tetramethyl-3,5-heptanedionate) was used instead of nasem zirconium. 15) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-15).
(Example 18)
A negative photosensitive resin composition (S-16) was obtained in the same manner as in Example 12 except that zirconium tetramethyl malonate was used instead of nasem zirconium. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-16).
(Example 19)
A negative photosensitive resin composition (S-17) was obtained in the same manner as in Example 12 except that zirconium tetrabenzoyl acetonate was used instead of nasem zirconium. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-17).
(Example 20)
A negative photosensitive resin composition (S-18) was obtained in the same manner as in Example 12 except that zirconium mono-normal butoxyacetylacetonate bis (ethyl acetoacetate) was used instead of nasem zirconium. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-18).
(Example 21)
A negative photosensitive resin composition (S-19) was obtained in the same manner as in Example 12 except that dichlorobis (η5-cyclopentadienyl) zirconium was used instead of nasemzirc. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-19).
(Example 22)
A negative photosensitive resin composition (S-20) was obtained in the same manner as in Example 12 except that bis (η5-cyclopentadienyl) zirconium chloride hydride was used instead of nasemzirc. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-20).
(Example 23)
A negative photosensitive resin composition (S-21) was obtained in the same manner as in Example 12 except that zirconocene bis (trifluoromethanesulfonate) tetrahydrofuran adduct was used instead of nasem zirconium. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-21).
(Example 24)
A negative photosensitive resin composition (A-1) was prepared in the same manner as in Example 1 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-1).
(Example 25)
A negative photosensitive resin composition (A-2) was prepared in the same manner as in Example 2 except that the acrylic resin solution (b) was used instead of the polysiloxane solution (ii) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-2). However, a 2.38 wt% TMAH aqueous solution was used as the developer.
(Example 26)
A negative photosensitive resin composition (A-3) was prepared in the same manner as in Example 3 except that the acrylic resin solution (c) was used instead of the polysiloxane solution (iii) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-3).
(Example 27)
A negative photosensitive resin composition (A-4) was prepared in the same manner as in Example 5 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-4).
(Example 28)
A negative photosensitive resin composition (A-5) was prepared in the same manner as in Example 6 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-5).
(Example 29)
A negative photosensitive resin composition (A-6) was prepared in the same manner as in Example 7 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was further added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-6).
(Example 30)
A negative photosensitive resin composition (A-7) was prepared in the same manner as in Example 8 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-7).
(Example 31)
A negative photosensitive resin composition (A-8) was prepared in the same manner as in Example 9 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-8).
(Example 32)
A negative photosensitive resin composition (A-9) was prepared in the same manner as in Example 10 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-9).
(Example 33)
A negative photosensitive resin composition (A-10) was prepared in the same manner as in Example 11 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was further added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-10).
(Example 34)
A negative photosensitive resin composition (A-11) was prepared in the same manner as in Example 12 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-11).
(Example 35)
A negative photosensitive resin composition (A-12) was prepared in the same manner as in Example 13 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-12).
(Example 36)
A negative photosensitive resin composition (A-13) was prepared in the same manner as in Example 14 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was further added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-13).
(Example 37)
A negative photosensitive resin composition (A-14) was prepared in the same manner as in Example 15 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-14).
(Example 38)
A negative photosensitive resin composition (A-15) was prepared in the same manner as in Example 16 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was further added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-15).
(Example 39)
A negative photosensitive resin composition (A-16) was prepared in the same manner as in Example 17 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-16).
(Example 40)
A negative photosensitive resin composition (A-17) was prepared in the same manner as in Example 18 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-17).
(Example 41)
A negative photosensitive resin composition (A-18) was prepared in the same manner as in Example 19 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-18).
(Example 42)
A negative photosensitive resin composition (A-19) was prepared in the same manner as in Example 20 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-19).
(Example 43)
A negative photosensitive resin composition (A-20) was prepared in the same manner as in Example 21 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-20).
(Example 44)
A negative photosensitive resin composition (A-21) was prepared in the same manner as in Example 22 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-20).
(Example 45)
A negative photosensitive resin composition (A-22) was prepared in the same manner as in Example 23 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-20).
(Example 46)
A touch panel member was produced according to the following procedure.
(1) Production of ITO Using a sputtering apparatus HSR-521A (manufactured by Shimadzu Corporation) on a glass substrate having a thickness of about 1 mm, RF power is 1.4 kW, and the degree of vacuum is 6.65 × 10 ⁻¹ Pa. By sputtering for 1 minute, an ITO film having a film thickness of 150 nm and a surface resistance of 15Ω / □ is formed, and a positive photoresist (“OFPR-800” manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied at 80 ° C. Pre-baked for 20 minutes to obtain a resist film having a thickness of 1.1 μm. The resulting film was exposed to a pattern using an ultra-high pressure mercury lamp through a mask using PLA, then shower-developed with a 2.38 wt% TMAH aqueous solution for 90 seconds using an automatic developing device, and then rinsed with water for 30 seconds. Thereafter, the ITO was etched by immersing in a 40 ° C. HCl / HNO ₃ / H ₂ O = 18 / 4.5 / 77.5 (weight ratio) mixed solution for 80 seconds, and a 50 ° C. stripping solution (Nagase Chemtex ( The photoresist was removed by treating with "N-300") for 120 seconds to produce a glass substrate having a patterned transparent electrode having a thickness of 200 angstroms.
(2) Preparation of transparent insulating film Using the negative photosensitive resin composition (A-1) on the obtained glass substrate, a transparent insulating film was prepared according to the procedure of the above-described evaluation method.
(3) Preparation of Molybdenum / Aluminum / Molybdenum Multilayer (MAM) Wiring Molybdenum and aluminum are used as targets on the obtained glass substrate, and H ₃ PO ₄ / HNO ₃ / CH ₃ COOH / H ₂ O is used as an etchant. = 65/3/5/27 (weight ratio) A MAM wiring was prepared by the same procedure as (1) except that a mixed solution was used.
(4) Production of Transparent Protective Film Using the negative photosensitive resin composition (A-1) on the obtained glass substrate, a transparent protective film was produced according to the procedure of the evaluation method described above.

When a continuity test of the connecting portion was performed using a tester, current continuity was confirmed.
(Comparative Example 1)
A resin composition (H-1) was obtained in the same manner as in Example 1 except that the acrylic resin solution (d) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. . Here, the carboxylic acid equivalent of the acrylic resin solution (d) was 4,600 g / mol. Evaluation was performed in the same manner as in Example 1 using the obtained resin composition (H-1). Since the unexposed portion was not dissolved in the 2.38 wt% TMAH aqueous solution and pattern processing could not be performed, other evaluations were performed without development.
(Comparative Example 2)
A resin composition (H-2) was obtained in the same manner as in Example 1 except that the acrylic resin solution (e) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. . Here, the carboxylic acid equivalent of the acrylic resin solution (e) was 140 g / mol. Evaluation was performed in the same manner as in Example 1 using the obtained resin composition (H-2).
(Comparative Example 3)
Under yellow light, PGMEA 4.740 g, “ZC-580 (trade name)” 0.249 g, silicone surfactant BYK-333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 100 ppm), 4 1.742 g of t-butylcatechol (1 wt% PGMEA solution) was added and stirred. “DPHA (trade name)” (50 wt% PGMEA solution) 5.806 g and acrylic resin solution (a) 7.258 g were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the resin composition (H-3). This resin composition (H-3) does not contain a photopolymerization initiator. Evaluation was performed in the same manner as in Example 1 using the obtained resin composition (H-3). In addition, since both the exposed part and the unexposed part were soluble in 0.4 wt% TMAH aqueous solution and pattern processing could not be performed, the other evaluations were performed without development.
(Comparative Example 4)
Under yellow light, “OXE-01 (trade name)” 0.277 g, PGMEA 3.778 g, “ZC-580 (trade name)” 0.237 g, BYK-333 (1 wt% PGMEA) which is a silicone surfactant Solution) 0.2000 g (corresponding to a concentration of 100 ppm) and 4-tert-butylcatechol (1 wt% PGMEA solution) 1.661 g were added and stirred. Acrylic resin solution (a) 13.846g was added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the resin composition (H-4). This resin composition (H-4) contains no polyfunctional monomer. Evaluation was performed in the same manner as in Example 1 using the obtained resin composition (H-4).
(Comparative Example 5)
Under a yellow light, 0.285 g of “OXE-01 (trade name)”, PGMEA 4.990 g, a silicone surfactant BYK-333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 100 ppm), 4- 1.709 g of t-butylcatechol (1 wt% PGMEA solution) was added and stirred. “DPHA (trade name)” (50 wt% PGMEA solution) 5.696 g and acrylic resin solution (a) 7.120 g were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the resin composition (H-5). This resin composition (H-5) does not contain a zirconium compound. Evaluation was performed in the same manner as in Example 1 using the obtained resin composition (H-5).
(Comparative Example 6)
Under a yellow light, “OXE-01 (trade name)” 0.285 g, PGMEA 2.262 g, DAA 2.846 g, silicone surfactant BYK-333 (1 wt% PGMEA solution) 0.2000 g (concentration to 100 ppm) 1), 4-tert-butylcatechol (1 wt% PGMEA solution) 1.709 g was added and stirred. “DPHA (trade name)” (50 wt% PGMEA solution) 5.696 g and polysiloxane solution (i) 7.120 g were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the resin composition (H-6). This resin composition (H-6) does not contain a zirconium compound. Evaluation was performed in the same manner as in Example 1 using the obtained resin composition (H-6).
(Comparative Example 7)
A negative photosensitive resin composition (H-7) was obtained in the same manner as in Example 1 except that the polysiloxane solution (v) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (H-7). In addition, the unexposed part did not melt | dissolve in 0.4 wt% TMAH aqueous solution.

1: Glass substrate 2: Transparent electrode 3: Transparent insulating film 4: Wiring electrode 5: Transparent protective film

  The cured film obtained by curing the negative photosensitive resin composition used in the present invention includes various hard coat films such as a protective film for a touch panel, an insulating film for a touch panel, and a planarizing film for a TFT of a liquid crystal or organic EL display. It is suitably used for metal wiring protective films, insulating films, antireflection films, antireflection films, optical filters, color filter overcoats, pillar materials, and the like.

Claims (5)

(A) Negative photosensitivity containing an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol, (B) a photopolymerization initiator, (C) a polyfunctional monomer, and (D) a zirconium compound. A touch panel member comprising a cured film of a resin composition, wherein the molybdenum-containing metal wiring is protected by the cured film. (A) The touch panel member according to claim 1, wherein the alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less is an acrylic resin having an ethylenically unsaturated bond. (A) The touch panel member according to claim 1 or 2, wherein the alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol to 1,400 g / mol is a polysiloxane having an ethylenically unsaturated bond. The touch panel member according to any one of claims 1 to 3, wherein the zirconium compound is zirconium oxide particles having an average particle diameter of 100 nm or less. (D) The touch panel member according to any one of claims 1 to 4, wherein the zirconium compound is at least one of the compounds represented by the general formula (1).
(R ¹ represents hydrogen, an alkyl group, an aryl group, an alkenyl group and a substituted product thereof, and R ² and R ³ represent hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group and a substituted product thereof. ¹ , R ² and R ³ may be the same or different, and n represents an integer of 0 to 4.)