JP5671936B2 - Negative photosensitive resin composition and cured film using the same - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition and a cured film using the same.

  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.

    The capacitive touch panel, which has been attracting attention in recent years, is one of the uses of hard coat materials. The structure of the capacitive touch panel has a protective film for protecting a metal insulating film and an element by forming a wiring with ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) on glass. The properties required for this insulating film and protective film include transparency and adhesiveness, photosensitivity for circuit connection, high hardness that does not cause scratches in the modularization process, and acid and alkali used in the subsequent process. The chemical resistance which can endure a process is mentioned, The photosensitive hard-coat material which satisfies these is calculated | required. However, it has been difficult to achieve both of these performances.

  Examples of the photosensitive organic hard coat material include negative photosensitive materials as described above containing a polymerizable group-containing alkali-soluble resin, a monomer, a photopolymerization initiator, and other additives. Such a composition has pattern processability and can provide a cured film having high hardness and transparency. However, since it has an acidic group, it interacts with acid and alkali, and there is a problem in chemical resistance.

  As a method for improving chemical resistance, particularly acid resistance, a method using a basic silane coupling agent is known (see Patent Document 1). However, the hardness of the resin used is not sufficient, and the resistance to the ITO etchant used for touch panel manufacture is not certain. In addition, a method has been reported in which adhesion is maintained even after chemical treatment by significantly improving adhesion with a compound having an isocyanurate skeleton and an imidosilane compound and / or an oxetane compound (see Patent Document 2).

JP 2010-072518 A JP 2010-152302 A

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

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

  The present invention includes (A) an alkali-soluble resin having a carboxyl group (B) a photoradical polymerization initiator, (C) a polyfunctional monomer, and (D) any one or more of the following general formulas (1) to (3). A negative photosensitive resin composition containing a silane coupling agent having a functional group of (A), wherein the alkali-soluble resin having a carboxyl group is (a-1) a poly having a carboxyl group and a radical polymerizable group It is a negative photosensitive resin composition which is an acrylic resin obtained by reacting an acrylic resin having siloxane and / or (a-2) carboxyl group with a mono-substituted epoxy compound having a radical polymerizable group.

(R ^{1 to} R ⁴ and R ⁶ are any one of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. R ⁵ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.)

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

  The negative photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin having a carboxyl group (B) a photoradical polymerization initiator, (C) a polyfunctional monomer, and (D) the following general formulas (1) to (3) ) Containing a silane coupling agent having one or more functional groups, and (A) an alkali-soluble resin having a carboxyl group is (a-1) a polysiloxane having a carboxyl group and a radical polymerizable group, and (A-2) An acrylic resin obtained by reacting an acrylic resin having a carboxyl group with a monosubstituted epoxy compound having a radical polymerizable group.

(R ^{1 to} R ⁴ and R ⁶ are any one of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. R ⁵ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.)
The negative photosensitive resin composition of the present invention contains (A) an alkali-soluble resin having a carboxyl group. In addition, (A) the alkali-soluble resin having a carboxyl group comprises (a-1) a polysiloxane having a carboxyl group and a radical polymerizable group and / or (a-2) an acrylic resin having a carboxyl group and a radical polymerizable group. It is an acrylic resin obtained by reacting with a monosubstituted epoxy compound. By containing the component (a-1) and / or (a-2), it becomes soluble in an alkaline developer, and the hardness of the cured film obtained can be improved.

  (A-1) As a polysiloxane having a carboxyl group and a radical polymerizable group, for example, an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group and an organosilane compound having a radical polymerizable group are hydrolyzed, What is obtained by condensing the hydrolyzate is preferred. Moreover, the other organosilane compound which does not have a carboxyl group and / or a dicarboxylic anhydride group, or a radically polymerizable group can be used simultaneously as needed.

  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. Is preferred. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 30 to 105 ° C.

  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 to 5 parts by weight with respect to 100 parts by weight of the total organosilane compound used during 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.

  The solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent. Specific examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3- Alcohols such as methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol di Ethers such as chill ether, ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; dimethylformamide, dimethylacetamide Amides such as; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, lactic acid Acetates such as ethyl and butyl lactate; toluene, xylene, hexane, cyclohexane, etc. Aromatic or aliphatic hydrocarbons, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, and the like dimethyl sulfoxide. Diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono t-butyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, γ-butyrolactone and the like are preferably used.

  When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the reaction. 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.

  The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the total organosilane compound. By making the quantity of a solvent into the said range, it can control easily so that a hydrolysis reaction may progress sufficiently and necessary.

  The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of silane atoms.

  Examples of the organosilane compound having a carboxyl group include 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, and 4-trimethoxysilylbutyric acid. 4-triethoxysilyl entangling acid, 4-dimethylmethoxysilyl entangling acid, 4-dimethylethoxysilyl entangling acid, 5-trimethoxysilyl valeric acid, 5-triethoxysilyl valeric acid, 5-dimethylmethoxysilyl valeric acid, 5 -Linear aliphatic carboxylic acids such as dimethylethoxysilylvaleric acid, 6-trimethoxysilylcaproic acid, 6-triethoxysilylcaproic acid, 6-dimethylmethoxysilylcaproic acid, 6-dimethylethoxysilylcaproic acid, 4 -(3-Trimethoxysilylop Fatty substances such as poxy) cyclohexanecarboxylic acid, 4- (3-triethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3-dimethylmethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3-dimethylethoxysilylpropoxy) cyclohexanecarboxylic acid Cycloaliphatic carboxylic acids and 4- (3-trichlorosilylpropoxy) benzoic acid, 4- (3-trimethoxysilylpropoxy) benzoic acid, 4- (3-triethoxysilylpropoxy) benzoic acid, 4- (3 Examples include mono-containing aromatic carboxylic acids such as -dimethylmethoxysilylpropoxy) benzoic acid and 4- (3-dimethylethoxysilylpropoxy) benzoic 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, 4- (2-trimethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-triethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride 4- (2-dimethylmethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-dimethylethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-trimethoxy Silylpropyl) cyclohexyl-1,2-dicarboxylic anhydride 3- (3-triethoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-dimethylmethoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-dimethylethoxy Silylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-trimethoxysilylethyl) phthalic anhydride, 4- (2-triethoxysilylethyl) phthalic anhydride, 4- (2-dimethyl) Methoxysilylethyl) phthalic anhydride, 4- (2-dimethylethoxysilylethyl) phthalic anhydride, 3- (3-trimethoxysilylpropyl) phthalic anhydride, 3- (3-triethoxysilylpropyl) phthal Acid anhydride, 3- (3-dimethylmethoxysilylpropyl) phthalic anhydride, 3- (3-dimethylethoxy Rirupuropiru) and the like phthalic anhydride.

  Examples of the radical polymerizable group of the organosilane compound having a radical polymerizable group include a vinyl group, an α-methylvinyl group, an allyl group, a styryl group, and a (meth) acryloyl group. Of these, a (meth) acryloyl group is preferred. By using a (meth) acryloyl group, the hardness of the cured film and the sensitivity during pattern processing can be further improved. The (meth) acryloyl group represents a methacryloyl group or an acryloyl group.

  Specific examples of the organosilane compound having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi (methoxyethoxy) silane, Allyltrimethoxysilane, allyltriethoxysilane, allyltri (methoxyethoxy) silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi (methoxyethoxy) silane, styryltrimethoxysilane, styryltriethoxysilane, styryltri (methoxyethoxy) Silane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, styrylmethyldi (methoxyethoxy) silane, γ-acryloyl group Pyrtrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-acryloylpropyltri (methoxyethoxy) silane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-methacryloylpropyltri (methoxyethoxy) silane , Γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-methacryloylpropyl (methoxyethoxy) silane, and the like. Two or more of these may be used. Among these, from the viewpoint of further improving the hardness of the cured film and the sensitivity during pattern processing, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltri Ethoxysilane is preferred.

  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.

  (A-1) Although there is no restriction | limiting in particular in the carboxylic acid equivalent of the polysiloxane which has a carboxyl group and a radically polymerizable group, 200-1400 g / mol is preferable and 400-1000 g / mol is more preferable. The carboxylic acid equivalent of the polysiloxane can be calculated by measuring the acid value after calculating the silanol group / carboxyl group ratio in the polysiloxane by 1H-NMR.

  (A-1) The content of the radically polymerizable group of the polysiloxane having a carboxyl group and a radically polymerizable group, so-called double bond equivalent, is not particularly limited, but is preferably 150 to 10,000 g / mol. 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.

  (A-1) The weight average molecular weight (Mw) of the polysiloxane having a carboxyl group and a radical polymerizable group is not particularly limited, but is 1,000 to 100 in terms of polystyrene measured by gel permeation chromatography (GPC). , 000 is preferable. 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.

  (A-2) An acrylic resin having a carboxyl group of an acrylic resin obtained by reacting an acrylic resin having a carboxyl group with a monosubstituted epoxy compound having a radical polymerizable group is not particularly limited, but ethylene having a carboxyl group Preferred is one obtained by radical polymerization of at least one of a reactive monomer and a monomer such as a (meth) acrylic acid ester, a vinyl aromatic compound, an amide unsaturated compound and other vinyl compounds. 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 to 110 ° C. for 30 to 300 minutes after nitrogen substitution. Moreover, you may use chain transfer agents, such as a thiol compound, as needed.

  Examples of the ethylenic monomer having a carboxyl group include (meth) acrylic acid, itaconic acid, maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (Meth) acryloyloxyethylphthalic acid and the like.

  Examples of the (meth) acrylic acid ester that is a copolymerization monomer 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-cyclohexylenylcarbonyl, (meth) acrylic acid 2- (4-methoxycyclohexyl) oxycarbonylethyl, (meth) acrylic acid norborni , Isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl (meth) acrylate Examples include methyl and 1-methyladamantyl (meth) acrylate. Examples of the vinyl aromatic compound include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene. Examples of the amide unsaturated compound include (meth) acrylamide, N-methylolacrylamide, N-vinylpyrrolidone and the like. Other vinyl compounds include (meth) acrylonitrile, allyl alcohol, vinyl acetate, cyclohexyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, 2-hydroxy vinyl ether, 4-hydroxy Examples include vinyl ether.

  There is no particular limitation on the catalyst used for the addition reaction of the monosubstituted epoxy compound having a radical polymerizable group, and a known catalyst can be used. For example, dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol Amino-based catalysts such as dimethylbenzylamine, tin-based catalysts such as tin 2-ethylhexanoate (II) and dibutyltin laurate, titanium-based catalysts such as titanium 2-ethylhexanoate (IV), and triphenylphosphine Phosphorus catalysts and chromium catalysts such as acetylacetonate chromium and chromium chloride are used.

  Examples of the monosubstituted epoxy compound having a radical polymerizable group include glycidyl (meth) acrylate, 2- (glycidyloxy) ethyl (meth) acrylate, 3- (glycidyloxy) propyl (meth) acrylate, (meth ) 4- (glycidyloxy) butyl acrylate, 4,5-epoxypentyl (meth) acrylate, (meth) acrylic acid-5,6-epoxyhexyl, (meth) acrylic acid-6,7-epoxyheptyl, allyl Glycidyl 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-vinyl Glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4 -Triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-tri Glycidyloxymethylstyrene or the like is used. Among these, glycidyl (meth) acrylate, 2- (glycidyloxy) ethyl (meth) acrylate, 3- (glycidyloxy) propyl (meth) acrylate, and 4- (glycidyloxy) butyl (meth) acrylate are It is preferable because the reaction of the epoxy group is easy to control and the reactivity of the radical polymerizable group is high.

  (A-2) Although there is no particular limitation on the carboxylic acid equivalent of the acrylic resin obtained by reacting the acrylic resin having a carboxyl group and the monosubstituted epoxy compound having a radical polymerizable group, 200 to 1400 g / mol is preferable, More preferably, it is 400-1000 g / mol. The carboxylic acid equivalent of the acrylic resin can be calculated by measuring the acid value.

  (A-2) The double bond equivalent of an acrylic resin obtained by reacting an acrylic resin having a carboxyl group with a monosubstituted epoxy compound having a radical polymerizable group is not particularly limited, but is 150 to 10,000 g / mol. It is preferable that 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.

  (A-2) The weight average molecular weight (Mw) of an acrylic resin obtained by reacting an acrylic resin having a carboxyl group with a monosubstituted epoxy compound having a radical polymerizable group is not particularly limited, but gel permeation chromatography ( It is preferably 1,000 to 100,000 in terms of polystyrene measured by 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 of the present invention, the content of (A) the alkali-soluble resin having a carboxyl group is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application. 10 to 60 wt% in the solid content of the resin composition is common.

  The negative photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. (B) Any photopolymerization initiator may be used as long as it 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, bis (2,4,6-trimethylbenzoyl) -phenylphos Fin oxide, 2,4,6-trimethylbenzoylphenylphosphine 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-ben) Iloxime)], 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- Tylpropan-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] benzenemeta Minium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propaminium 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- Chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, can Furquinone, 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, Anne Laquinone, 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, 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 and the like. 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 of the present invention, the content of the (B) photoradical polymerization initiator is not particularly limited, but is 0.1 to 20 wt% in the solid content of the negative photosensitive resin composition. Part. By setting it as the said range, radical hardening can fully be advanced and elution of the residual radical polymerization initiator etc. can be prevented and solvent resistance can be ensured.

  The negative photosensitive resin composition of the present invention contains (C) a polyfunctional monomer. Polymerization of the (C) polyfunctional monomer proceeds by radicals generated from the (B) photoradical polymerization initiator by light irradiation, and the exposed portion of the negative photosensitive resin composition of the present invention is insolubilized in the aqueous alkali solution. A negative pattern can be formed. The polyfunctional monomer means a compound having at least two ethylenically unsaturated double bonds in the molecule, and is not particularly limited, but considering the ease of radical polymerization, a (meth) acryl group Polyfunctional monomers having are preferred. Moreover, it is preferable from the point of a sensitivity and hardness that the double bond equivalent of (C) polyfunctional monomer is 80-400 g / mol.

  (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 of the present invention, the content of the (C) polyfunctional monomer is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application. 10 to 60 parts by weight in the solid content is common.

  The negative photosensitive resin composition of this invention contains the silane coupling agent which has any 1 or more types of functional groups among (D) following general formula (1)-(3). By containing these silane coupling agents, resistance to acidic and alkaline chemicals can be improved.

In the formula, R ^{1 to} R ⁴ and R ⁶ are hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Represents either. R ⁵ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

  Specific examples of the compound represented by the general formula (1) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 4-aminobutyltrimethoxysilane, 4- Aminobutyltriethoxysilane, 4-aminobutylmethyldimethoxysilane, 5-aminopentyltrimethoxysilane, 5-aminopentyltriethoxysilane, 5-aminopentylmethyldimethoxysilane, N-2- (aminoethyl) -3-amino Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane N-phenyl-3-amino B pills triethoxysilane, etc. N- phenyl-3-aminopropyl methyl dimethoxy silane. Among them, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxy Silane is preferable because it has a high effect of improving chemical resistance.

  Specific examples of the compound represented by the general formula (2) include 3-triethoxysilyl-N- (1-methylethylidene) propylamine and 3-triethoxysilyl-N- (1-methylpropylidene) propylamine. 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 3-triethoxysilyl-N- (α-methylbenzylidene) propylamine, 3-triethoxysilyl-N- (cyclopentylidene ) Propylamine, 3-triethoxysilyl-N- (cyclohexylidene) propylamine, 4-triethoxysilyl-N- (1-methylethylidene) butylamine, 4-triethoxysilyl-N- (1-methylpropylidene) ) Butylamine, 4-triethoxysilyl-N- (1,3-dimethylbutylidene) butylamine, - triethoxysilyl -N- (alpha-methyl benzylidene) butylamine and 4-triethoxysilyl -N- (cyclopentylidene) butylamine. Among them, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 3-triethoxysilyl-N- (α-methylbenzylidene) propylamine, 3-triethoxysilyl-N- (cyclopentylidene) ) Propylamine is preferred in terms of the stability of the compound.

  Specific examples of the compound represented by the general formula (3) include 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-phenylureidopropyltrimethoxysilane, 3-phenylureidopropyltriethoxysilane, Examples include 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, 4-phenylureidobutyltrimethoxysilane, and 4-phenylureidobutyltriethoxysilane. Among these, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane are preferable because they have a high effect of improving chemical resistance.

  In the negative photosensitive resin composition of the present invention, the content of the component (D) is not particularly limited, but from 0.01 parts by weight with respect to 100 parts by weight of the sum of the components (A) and (C). 10 parts by weight is preferable, and 0.5 to 5 parts by weight is more preferable.

The negative photosensitive resin composition of the present invention may contain (E) a silane compound having an oxetanyl group. (E) By containing the silane compound which has an oxetanyl group, the chemical resistance of a cured film further improves. The (E) silane compound having an oxetanyl group is preferably a compound having one or more oxetanyl groups per silane atom.
(E) Specific examples of the silane compound having an oxetanyl group include a compound represented by the following general formula (4) or a condensate thereof. There is no restriction | limiting in particular in the method of obtaining a condensate, For example, the method similar to the synthesis method of the above-mentioned polysiloxane can be used. Furthermore, a known ether exchange reaction with a hydroxyl group-containing oxetane compound represented by the following general formula (6) by heat condensation by a known method without hydrolysis of the compound represented by the following general formula (5) The compound obtained by can be mentioned.

Si (R ⁷ ) _x (OR ⁸ ) _4-x (4)
In the general formula (4), the plurality of ^{R 7} and ^{R 8} may be the same or different, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms And an organic group having an alkylcarbonyl group having 2 to 7 carbon atoms or an oxetanyl group. However, at least one of R ⁷ and R ⁸ is an organic group having an oxetanyl group. x represents an integer of 0 to 3.

Si (R ⁹ ) _y (OR ¹⁰ ) _4-y (5)
In the general formula (5), R ⁹ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R ¹⁰ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms. y represents an integer of 0-2.

In the general formula (6), R ^{12 to} R ¹⁷ represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having a hydroxyl group, or a phenyl group. However, at least one of R ^{12 to} R ¹⁷ is an alkyl group having a hydroxyl group.

  Specific examples of the compound represented by the general formula (4) include 3-[(3-ethyloxetane-3-yl) methoxy] propyltrimethoxysilane, 3-[(3-ethyloxetane-3-yl). Methoxy] propyltriethoxysilane, 3-[(3-ethyloxetane-3-yl) methoxy] propyltriacetoxysilane, 3-[(3-ethyloxetane-3-yl) methoxy] propylmethyldimethoxysilane, 3- [ (3-ethyloxetane-3-yl) methoxy] propylmethyldiethoxysilane, 3-[(3-ethyloxetane-3-yl) methoxy] propylmethyldiacetoxysilane, 3-[(3-ethyloxetane-3- Yl) methoxy] propyldimethylmethoxysilane, 3-[(3-ethyloxetane-3-yl) methoxy] Propyldimethylethoxysilane, 3-[(3-ethyloxetane-3-yl) methoxy] propyldimethylacetoxysilane, (3-ethyloxetane-3-yl) methoxytrimethoxysilane, (3-ethyloxetane-3-yl) ) Methoxytriethoxysilane, bis [(3-ethyloxetane-3-yl) methoxy] dimethoxysilane, bis [(3-ethyloxetane-3-yl) methoxy] diethoxysilane, tris [(3-ethyloxetane-3 -Yl) methoxy] methoxysilane, tris [(3-ethyloxetane-3-yl) methoxy] ethoxysilane, and the like. Of these, those having a hydrolyzable methoxy group are preferred.

  Specific examples of the compound represented by the general formula (5) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltriacetoxysilane, propyltrimethoxysilane, propyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxy Examples thereof include silane and diphenyldiethoxysilane. Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane are preferred because of their ether exchange reactivity.

  Specific examples of the hydroxyl group-containing oxetane compound represented by the general formula (6) include (3-methyloxetane-3-yl) methanol, (3-ethyloxetane-3-yl) methanol because of its easy synthesis. 2-hydroxymethyloxetane is preferred.

  Examples of commercially available compounds represented by the general formula (4) include TMSOX (trade name) and TESOX (shipped product) (above, manufactured by Toagosei Co., Ltd.). As a commercial item of the condensate of the compound represented by the general formula (4), OX-SQ (trade name), OX-SQ-H (trade name), OX-SQ-SI20 (trade name) (above, Toa Gosei Co., Ltd.). As a commercial product of a compound obtained by the reaction of the heat condensate of the compound represented by the general formula (5) and the hydroxyl group-containing oxetane compound represented by the general formula (6), OXT-191 (trade name) ( Toa Gosei Co., Ltd.).

  The negative photosensitive resin composition of the present invention may contain a zirconium compound. By containing a zirconium compound, the heat-and-moisture resistance of the resulting cured film is improved. The zirconium compound is not particularly limited as long as it is a compound containing a zirconium atom, but for example, zirconium oxide particles having an average particle diameter of 100 nm or less and a compound represented by the general formula (7) are preferable. More preferably, the average particle size is 40 nm or less. If the average particle size exceeds 100 nm, the resulting cured film may become cloudy, which is not preferable.

(R ¹⁸ represents hydrogen, an alkyl group, an aryl group, an alkenyl group and a substituent thereof, and R ¹⁹ and R ²⁰ represent hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group and a substituent thereof. ¹⁸ , R ¹⁹ and R ²⁰ may be the same or different, and n represents an integer of 0 to 4.)
Zirconium oxide particles having an average particle size of 100 nm or less may be commercially available products. Specific examples thereof include “Vilal Zr-C20 (trade name)” (average particle size = 20 nm, manufactured by Taki Chemical Co., Ltd.). , “Nanouse OZ-30M (trade name)” (average particle size = 7 nm) (manufactured by Nissan Chemical Industries, Ltd.), “ZSL-10T (trade name)” (average particle size = 15 nm), “ZSL-10A ( Product name) "(average particle size = 70 nm) (above, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.).

In the general formula (7), R ¹⁸ includes hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, phenyl group, vinyl group and the like. Among these, n-propyl group, n-butyl group and phenyl group are preferable since the compound is stable. R ¹⁹ and R ²⁰ 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 (7) 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.

  Although there is no restriction | limiting in particular in content of a zirconium compound in the negative photosensitive resin composition of this invention, 0.1-10 wt% is preferable in solid content of a negative photosensitive resin composition. 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 of the present invention may contain an ultraviolet absorber. By containing the ultraviolet absorber, the light resistance of the resulting cured film is improved, and the resolution after development is improved. 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 of 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. Moreover, the compound whose boiling point under atmospheric pressure is 110-250 degreeC 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 a boiling point of 110 to 250 ° C. 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 glycol mono Examples include 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 to 250 ° C. under atmospheric pressure include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, And cycloheptanone. Among these, γ-butyrolactone is particularly preferably used.

  Moreover, the negative photosensitive resin composition of 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, the amount is generally 50 to 95 parts by weight of the entire negative photosensitive resin composition.

  The negative photosensitive resin composition of 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 an acid, the negative photosensitive resin composition of the present invention 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 acids Examples thereof include esters and halogen compounds.

  The negative photosensitive resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants in order to improve flowability during 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) ) ”“ F444 (product name) ”,“ F445 (product name) ”,“ F470 (product name) ”,“ F475 (product name) ”,“ F477 (product name) ”(Dai Nippon Ink Chemical Co., Ltd. Co., Ltd.), “NBX-15 (trade name)”, “FTX-218 (trade name)” (manufactured by Neos Co., Ltd.), etc., “BYK-333 (trade name)”, “ Silicone such as “BYK-301 (trade name)”, “BYK-331 (trade name)”, “BYK-345 (trade name)”, “BYK-307 (trade name)” (manufactured by BYK Japan KK) Surfactants, polyalkylene oxide surfactants Agent, or the like can be used poly (meth) acrylate surfactants. Two or more of these may be used.

  The negative photosensitive resin composition of 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 of this invention, Arbitrary amounts of a solvent and a solute can be used according to a coating method. For example, when the film is formed by spin coating as described later, the solid content concentration is generally 5 to 50 wt%.

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

  For example, (B) a radical photopolymerization initiator, (D) a silane coupling agent and other additives are added to an arbitrary solvent and dissolved by stirring, and then (A) a carboxylic acid equivalent is 200 to 1400 g / mol. The alkali-soluble resin and (C) polyfunctional monomer 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 of this invention.

  The negative photosensitive resin composition of the present invention is applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, Pre-bake with a heating device such as an oven. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm.

After pre-baking, using an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA), light of about 10 to 4000 J / m ² (wavelength 365 nm exposure equivalent) is passed through the desired mask. Irradiate with or without intervention. 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 in the range of 150-450 degreeC for about 1 hour with heating apparatuses, such as a hotplate and oven.

The negative photosensitive resin composition of the present invention preferably has a sensitivity of 100 to 4000 J / m ² when exposed to PLA. 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, followed by dry baking in the range of 50 to 150 ° C. Thereafter, this film is thermally cured in a range of 120 to 280 ° C. for about 1 hour with a heating device such as a hot plate or oven to obtain a cured film.

  The cured film obtained from the negative photosensitive resin composition of 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 of 0.1. It is preferable that it is 5 wt%-20 wt%. By being in the above range, the transmittance, hardness, and heat and humidity resistance can be maintained in a well-balanced manner. The resolution is preferably 20 μm or less. Although there is no restriction | limiting in particular in the film thickness of a cured film, 0.1-15 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.

  Cured films obtained by curing the negative photosensitive resin composition of the present invention include various protective films such as touch panel protective films, various hard coat materials, TFT flattening films, color filter overcoats, and antireflection films. Further, it can be used for optical filters, insulating films for touch sensors, insulating films for TFTs, photo spacers for color filters, 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.

  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, 3-trimethoxysilylpropyl Charge 26.23 g (0.10 mol) of succinic acid, 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane, and 180.56 g of DAA (diacetone alcohol), and immerse in an oil bath at 40 ° C. and stir. However, a phosphoric acid aqueous solution in which 0.401 g of phosphoric acid (0.2 part by weight based on the charged monomer) was dissolved in 55.8 g of water was added with a dropping funnel over 10 minutes. 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 out. To the obtained DAA solution of polysiloxane, DAA was added 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 5000 (polystyrene conversion).

Synthesis Example 2 Synthesis of Polysiloxane Solution (ii) In a 500 mL three-necked flask, 34.05 g (0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 4-trimethoxysilylbutyric acid 41.66 g (0.20 mol), 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane, and 182.22 g of DAA were charged and immersed in an oil bath at 40 ° C., and phosphorus was added to 54.0 g of water while stirring. An aqueous phosphoric acid solution in which 0.395 g of acid (0.2 wt% with respect to the charged monomer) was dissolved 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, it was 6000 (polystyrene conversion) when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC.

Synthesis Example 3 Synthesis of Polysiloxane Solution (iii) In a 500 mL three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl A mixture of 26.23 g (0.10 mol) of succinic acid, 56.79 g (0.35 mol) of allyltrimethoxysilane and 157.25 g of DAA (diacetone alcohol) was placed in an oil bath at 40 ° C. A phosphoric acid aqueous solution in which 0.341 g of phosphoric acid (0.2 parts by weight with respect to the charged monomer) was dissolved in 0.8 g was added with a dropping funnel over 10 minutes. 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 out. 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 5500 (polystyrene conversion).

Synthesis Example 4 Synthesis of polysiloxane solution (iv) In a 500 mL three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 59.49 g (0.30 mol) of phenyltrimethoxysilane, and γ-acryloylpropyltrimethoxy 82.04 g (0.35 mol) of silane and 174.65 g of DAA (Diacetone Alcohol) were charged, immersed in an oil bath at 40 ° C. and stirred with stirring at 54.0 g of water and 0.378 g of phosphoric acid (based on the charged monomers). An aqueous solution of phosphoric acid in which 0.2 part by weight was dissolved was added with a dropping funnel over 10 minutes. 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 out. 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, it was 4500 (polystyrene conversion) when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC.

Synthesis Example 5 Synthesis of polysiloxane solution (v) In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl Charge 26.23 g (0.10 mol) of succinic acid and 166.03 g of DAA (diacetone alcohol), soak in an oil bath at 40 ° C. and stir and stir in 55.8 g of water with 0.391 g of phosphoric acid (based on the charged monomers). An aqueous solution of phosphoric acid in which 0.2 part by weight was dissolved was added with a dropping funnel over 10 minutes. 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 out. 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, it was 6000 (polystyrene conversion) when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC.

Synthesis Example 6 Synthesis of acrylic resin solution (A) A 500 ml flask was charged with 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 23.26 g of methacrylic acid, 31.46 g of benzyl methacrylate, and 32.80 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, 12.69 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 ( 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 (A) was 24,000.

Synthesis Example 7 Synthesis of Acrylic Resin Solution (B) A 500 ml flask was charged with 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 21.92 g of methacrylic acid, 29.90 g of benzyl methacrylate and 31.18 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, 17.00 g of 4- (glycidyloxy) butyl acrylate, 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. As a result, an acrylic resin solution (B) was obtained. 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 (B) was 23000.

Synthesis Example 8 Synthesis of Acrylic Resin Solution (C) A 500 ml flask was charged with 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 6.33 g of methacrylic acid, 34.56 g of benzyl methacrylate, and 48.65 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, 10.46 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) was obtained. 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 (C) was 22,000. Moreover, when the solid content acid value of the acrylic resin solution (C) was measured (based on JIS K5601-2-1), it was less than 0.5 mgKOH / g, and it was confirmed that no carboxyl group remained.

Synthesis Example 9 Synthesis of Acrylic Resin Solution (D) A 500 ml flask was charged with 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA. Thereafter, 15.69 g of methacrylic acid, 37.45 g of benzyl methacrylate, and 46.86 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, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added 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 (C) was 25000.

  The evaluation methods in each example and comparative example are shown below. 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). ) ") For 10 seconds at 500 rpm, spin for 4 seconds at 1000 rpm, and then hot plate (" SCW-636 (trade name) "manufactured by Dainippon Screen Mfg. Co., Ltd.)) Pre-baking was performed 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 K5600-5-4 (1999)" about the cured film having a film thickness of 1.5 m obtained by the method described in (1) above.

(3) Pattern workability (3-1) 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 1000 rpm for 4 seconds, prebaking was performed at 90 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.), and the film thickness was 2 μm. A pre-baked film was prepared. 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. After that, using an automatic developing device (“AD-2000 (trade name)”, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with 0.045 wt% potassium hydroxide aqueous solution for 90 seconds, followed by rinsing 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.

(3-2) Resolution The minimum pattern size after development at the optimum exposure amount was measured.
(4) Evaluation of ITO adhesiveness A cured film having a film thickness of 1.5 μm is formed on a glass substrate (hereinafter referred to as “ITO substrate”) whose ITO is sputtered on the surface in the same manner as in the method described in (1) above. The adhesion between ITO and the cured film was evaluated according to JIS “K5600-5-6 (established on April 20, 1999)”.
On the ITO surface on the glass substrate, 11 parallel straight lines of 11 vertical and horizontal directions were drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm × 1 mm were produced. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is applied to the cut cured film surface, and it is rubbed with an eraser (JIS S6050 passed product) to hold it, hold one end of the tape, and make a right angle to the plate. The remaining number of squares when they were kept and peeled instantaneously was visually evaluated. Judgment was made as follows according to the peeled area of the cells, and 3 or more was judged as acceptable.
5: Peel area = 0%
4: Peel area = <5%
3: Peel area = 5-14%
2: Peel area = 15-34%
1: Peeling area = 35% -64%
0: peeling area = 65% to 100%
(5) Chemical treatment method (5-1) Acid treatment method The ITO substrate having the cured film prepared in (4) was mixed at HCl / HNO3 / H2O = 18/4/78 (weight ratio) at 35 ° C. Treated in aqueous solution for 80 seconds. About the board | substrate after a process, it evaluated adhesiveness like (4).

(5-2) Alkali treatment method The ITO substrate having the cured film prepared in (4) was treated for 5 minutes in a 60 ° C. solution mixed with monoethanolamine / diethylene glycol monobutyl ether = 30/70 (weight ratio). . About the board | substrate after a process, it evaluated adhesiveness like (4).

Example 1
1,81-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (“Irgacure OXE-01 (trade name)” manufactured by Ciba Specialty Chemicals) under a yellow light 0.281 g ( 5.0 parts by weight) is dissolved in 2.788 g of DAA and 1.989 g of PGMEA, and 0.2000 g of a PGMEA 1 wt% solution of “BYK-333 (trade name)” (manufactured by BYK Japan) is a silicone surfactant. (Corresponding to a concentration of 100 ppm), 1.85 g (0.3 parts by weight) of a 1 wt% PGMEA solution of 4-t-butylcatechol, and 0.421 g (1.5 parts by weight) of a 20 wt% PGMEA solution of 3-aminopropyltrimethoxysilane Added and stirred. Thereto, 5.616 g (50 parts by weight) of a PGMEA 50 wt% solution of dipentaerythritol hexaacrylate (“Kayarad (registered trademark)” DPHA (trade name), manufactured by Shin Nippon Kayaku), polysiloxane solution (i) 7 0.020 g (50 parts by weight) was 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, pattern workability, and ITO adhesiveness 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).

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
Negative photosensitive resin composition (S-4), which was carried out in the same manner as in Example 1 except that N-2- (aminoethyl) -3-aminopropyltriethoxysilane was used instead of 3-aminopropyltrimethoxysilane. Got. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-4).

Example 5
A negative photosensitive resin composition (S) was prepared in the same manner as in Example 1 except that 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine was used instead of 3-aminopropyltrimethoxysilane. -5) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-5).

Example 6
Negative photosensitive resin composition (S-6), which is carried out in the same manner as in Example 1 except that 3-triethoxysilyl-N- (α-methylbenzylidene) propylamine is used instead of 3-aminopropyltrimethoxysilane. Got. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-6).

Example 7
A negative photosensitive resin composition (S-7) was obtained in the same manner as in Example 1 except that 3-ureidopropyltrimethoxysilane was used instead of 3-aminopropyltrimethoxysilane. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-7).

Example 8
A negative photosensitive resin composition (S-8) was obtained in the same manner as in Example 1 except that 3-phenylureidopropyltriethoxysilane was used instead of 3-aminopropyltrimethoxysilane. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-8).

Example 9
Under a yellow light, 0.266 g (5.0 parts by weight) of “Irgacure OXE-01 (trade name)” was dissolved in 3.012 g of DAA and 0.969 g of PGMEA, and (3-ethyloxetane-3-yl) methanol and silane 1.595 g (6.0 parts by weight) of a PGMEA 20 wt% solution of a tetraol condensate (“OXT-191 (trade name)” manufactured by Toagosei Co., Ltd.), a PGMEA 1 wt% solution of “BYK-333 (trade name)” 2000 g (corresponding to a concentration of 100 ppm), 1.595 g (0.3 parts by weight) of a 4-wt-butylcatechol PGMEA solution, 0.399 g (1.5 parts by weight) of a PGMEA 20 wt% solution of 3-aminopropyltrimethoxysilane Was added and stirred. Thereto, 5.317 g (50 parts by weight) of a PGMEA 50 wt% solution of “DPHA (trade name)” and 6.647 g (50 parts by weight) of a polysiloxane solution (i) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (S-9). The obtained negative photosensitive resin composition (S-9) was evaluated in the same manner as in Example 1.

Example 10
Implemented except that 3-[(3-ethyloxetane-3-yl) methoxy] propyltriethoxysilane (“TESOX (trade name)”, manufactured by Toagosei Co., Ltd.) was used instead of “OXT-191 (trade name)” In the same manner as in Example 9, a negative photosensitive resin composition (S-10) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-10).

Example 11
Instead of “OXT-191 (trade name)”, a hydrolytic condensate of 3-[(3-ethyloxetane-3-yl) methoxy] propyltriethoxysilane (“OX-SQ (trade name)”, manufactured by Toagosei Co., Ltd. ) Was used in the same manner as in Example 9 to obtain a negative photosensitive resin composition (S-11). 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, 0.281 g (5.0 parts by weight) of “Irgacure OXE-01 (trade name)” was dissolved in 4.777 g of PGMEA, and 0.2000 g of a 1 wt% PGMEA solution of “BYK-333 (trade name)” ( (Corresponding to a concentration of 100 ppm), 1.85 g (0.3 parts by weight) of a 1 wt% PGMEA solution of 4-t-butylcatechol, and 0.421 g (1.5 parts by weight) of a 20 wt% PGMEA solution of 3-aminopropyltrimethoxysilane , Stirred. Thereto, 5.616 g (50 parts by weight) of a PGMEA 50 wt% solution of “DPHA (trade name)” and 7.020 g (50 parts by weight) of an acrylic resin solution (A) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (A-1). The obtained negative photosensitive resin composition (A-1) was evaluated in the same manner as in Example 1.

Example 13
Except having used an acrylic resin solution (B) instead of an acrylic resin solution (A), it carried out similarly to Example 12 and obtained the negative photosensitive resin composition (A-2). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-2).

Example 14
Negative photosensitive resin composition (A-3), which was carried out in the same manner as in Example 12 except that N-2- (aminoethyl) -3-aminopropyltriethoxysilane was used instead of 3-aminopropyltrimethoxysilane. Got. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-3).

Example 15
A negative photosensitive resin composition (A) was prepared in the same manner as in Example 12 except that 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine was used instead of 3-aminopropyltrimethoxysilane. -4) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (S-5).

Example 16
Negative photosensitive resin composition (A-5), which was carried out in the same manner as in Example 12 except that 3-triethoxysilyl-N- (α-methylbenzylidene) propylamine was used instead of 3-aminopropyltrimethoxysilane. Got. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-5).

Example 17
A negative photosensitive resin composition (A-6) was obtained in the same manner as in Example 12 except that 3-ureidopropyltrimethoxysilane was used instead of 3-aminopropyltrimethoxysilane. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-6).

Example 18
A negative photosensitive resin composition (A-7) was obtained in the same manner as in Example 12 except that 3-phenylureidopropyltriethoxysilane was used instead of 3-aminopropyltrimethoxysilane. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-7).

Example 19
Under a yellow light, 0.266 g (5.0 parts by weight) of “Irgacure OXE-01 (trade name)” was dissolved in 3.981 g of PGMEA, and 1.595 g of a 20 wt% PGMEA solution of “OXT-191 (trade name) (6 0.0 part by weight), 0.2000 g (corresponding to a concentration of 100 ppm) of a PGMEA 1 wt% solution of “BYK-333 (trade name)”, 1.595 g (0.3 parts by weight) of a PGMEA 1 wt% solution of 4-t-butylcatechol, 0.399 g (1.5 parts by weight) of a PGMEA 20 wt% solution of 3-aminopropyltrimethoxysilane was added and stirred. To this, 5.317 g (50 parts by weight) of a PGMEA 50 wt% solution of “DPHA (trade name)” and 6.647 g (50 parts by weight) of an acrylic resin solution (A) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (A-8). The obtained negative photosensitive resin composition (A-8) was evaluated in the same manner as in Example 1.

Example 20
Except having used "TESOX (brand name)" instead of "OXT-191 (brand name)", it carried out like Example 19 and obtained the negative photosensitive resin composition (A-9). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-9).

Example 21
Except having used "OX-SQ (brand name)" instead of "OXT-191 (brand name)", it carried out similarly to Example 19 and obtained the negative photosensitive resin composition (A-10). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-10).

Comparative Example 1
Under a yellow light, 0.285 g (5.0 parts by weight) of “Irgacure OXE-01 (trade name)” was dissolved in 2.728 g of DAA and 2.262 g of PGMEA, and a 1 wt% PGMEA solution of “BYK-333 (trade name)” 0.2000 g (corresponding to a concentration of 100 ppm) and 1.709 g (0.3 parts by weight) of a 1 wt% PGMEA solution of 4-t-butylcatechol were added and stirred. Thereto, 5.696 g (50 parts by weight) of a PGMEA 50 wt% solution of “DPHA (trade name)” and 7.120 g (50 parts by weight) of a polysiloxane solution (i) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (H-1). The obtained negative photosensitive resin composition (H-1) was evaluated in the same manner as in Example 1.

Comparative Example 2
Except having used polysiloxane solution (iv) instead of polysiloxane solution (i), it carried out similarly to Example 1 and obtained the negative photosensitive resin composition (H-2). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (H-2).

Comparative Example 3
A negative photosensitive resin composition (H-3) 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-3).

Comparative Example 4
Under a yellow light, 0.285 g (5.0 parts by weight) of “Irgacure OXE-01 (trade name)” was dissolved in 4.990 g of PGMEA, and 0.2000 g of a 1 wt% PGMEA solution of “BYK-333 (trade name)” ( (Corresponding to a concentration of 100 ppm), 1.709 g (0.3 parts by weight) of a 4-wt-butylcatechol PGMEA 1 wt% solution was added and stirred. Thereto, 5.696 g (50 parts by weight) of a PGMEA 50 wt% solution of “DPHA (trade name)” and 7.120 g (50 parts by weight) of an acrylic resin solution (A) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (H-4). The obtained negative photosensitive resin composition (H-4) was evaluated in the same manner as in Example 1.

Comparative Example 5
A negative photosensitive resin composition (H-5) was obtained in the same manner as in Example 12 except that the acrylic resin solution (C) was used instead of the acrylic resin solution (A). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (H-5).

Comparative Example 6
Except having used an acrylic resin solution (D) instead of an acrylic resin solution (A), it carried out similarly to Example 12 and obtained the negative photosensitive resin composition (H-6). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (H-6).

  The cured film obtained by curing the negative photosensitive resin composition of the present invention includes various hard coat films such as a protective film for a touch panel, an insulating film for a touch sensor, 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 (3)

(A) an alkali-soluble resin having a carboxyl group, (B) a photoradical polymerization initiator, (C) a polyfunctional monomer , ( D) one or more functional groups of the following formulas (1) to (3) A negative photosensitive resin composition comprising a silane coupling agent having (E) a silane compound having an oxetanyl group , wherein (A) an alkali-soluble resin having a carboxyl group is (a-1) a carboxyl group and a radical Negative photosensitive resin composition which is an acrylic resin obtained by reacting a polysiloxane having a polymerizable group and / or (a-2) an acrylic resin having a carboxyl group and a mono-substituted epoxy compound having a radical polymerizable group .

(R ^{1 to} R ⁴ and R ⁶ are any one of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. R ⁵ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.) Protective film for a touch panel having a cured film obtained by curing the resin compositions of claim 1 Symbol placement. Touch panel insulating film having a cured film obtained by curing the resin compositions of claim 1 Symbol placement.