JP5821481B2 - Negative photosensitive resin composition and protective film and touch panel member using the same - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition, a protective film using the same, and a touch panel member.

In recent years, capacitive touch panels have attracted attention with the spread of smartphones and tablet terminals. The sensor substrate of the capacitive touch panel has wiring in which ITO (Indium Tin Oxide) or metal (silver, molybdenum, aluminum, etc.) is patterned on glass, and in addition, an insulating film, ITO and A structure having a protective film for protecting a metal is common. In general, the protective film is formed of high-hardness inorganic SiO ₂ , SiNx, a photosensitive transparent material, or the like (see, for example, Patent Document 1), and the insulating film is often formed of a photosensitive transparent material. However, inorganic materials are formed by high-temperature deposition of SiO ₂ or SiNx by CVD (Chemical Vapor Deposition), and the number of processes increases because pattern processing is performed using resist. was there. Furthermore, it was not possible to obtain a touch panel with high reliability, such as poor heat and heat resistance and corrosion of the underlying metal wiring. In addition, although the photosensitive transparent material can be expected to reduce costs by reducing the number of processes, it has insufficient hardness and has a problem in heat and humidity resistance like inorganic materials. Also, the same photosensitive transparent material is used as the insulating film, but there is a problem that outgas is generated in the subsequent ITO film forming process and the resistance value of ITO is increased. Therefore, there is a need for a photosensitive transparent material that has high hardness, excellent transparency, heat resistance, and moist heat resistance and that can be patterned.

  As a photosensitive transparent material, a UV curable coating composition containing an alkali-soluble polymer, a monomer, a photopolymerization initiator and other additives is known. Such a composition is used, for example, for a color filter overcoat material and a spacer material, and also for a color resist by using a colorant (see, for example, Patent Documents 2 and 3). In addition, the application range such as an interlayer insulating film and a solder resist is wide (see, for example, Patent Documents 4 and 5).

  Polyfunctional epoxy compounds have been studied as a method for improving the properties of these compositions. Patent Document 3 has been confirmed to contribute to improving chemical resistance, Patent Document 4 to improving heat resistance, and Patent Document 5 to improving exposure sensitivity. On the other hand, with respect to the heat and moisture resistance, the above Patent Document 4 suggests an improvement by a biphenyl novolac structure-containing acrylic resin or the like.

JP 2007-279819 A JP 2006-30809 A JP 2010-24434 A JP 2011-75923 A JP 2007-233184 A

  Although the importance of moisture and heat resistance is known as in Patent Document 4, it is only enough to evaluate whether or not the appearance of the cured film changes, and how the underlying metal protected before and after the test changes. It was not examined from the viewpoint.

  The present inventors have focused on moisture and heat resistance in terms of suppressing the corrosion of the base metal. As described above, the present inventors have high hardness, high transparency, high heat resistance, and high moisture and heat resistance that suppress the corrosion of the base metal. No technology has been established so far for negative photosensitive transparent materials that can be patterned with an alkaline developer.

  It is an object of the present invention to provide a negative photosensitive resin composition capable of alkali development that provides a cured film having high hardness, high transparency, high heat resistance, and high moisture and heat resistance that suppresses corrosion of the base metal. To do.

  In order to solve the above-mentioned problems, the present inventors have confirmed that Patent Document 3 contributes to improving chemical resistance, Patent Document 4 to improve heat resistance, and Patent Document 5 to improve exposure sensitivity. However, as a result of diligent investigation focusing on polyfunctional epoxy compounds that have not been studied so far in terms of high moisture and heat resistance to suppress corrosion of the base metal, specific polyfunctional epoxy compounds are It has been found that it contributes to high moisture and heat resistance that suppresses corrosion.

    The object of the present invention is (A) a carboxyl group-containing acrylic resin, (B) a photopolymerization initiator, (C) a polyfunctional monomer, (D) having four or more aromatic rings and three bonds with the aromatic ring. This is achieved by a negative photosensitive resin composition containing a polyfunctional epoxy compound having quaternary carbon.

  The object of the present invention is achieved by a metal wiring protective film obtained by curing the above-mentioned negative photosensitive resin composition.

  The object of the present invention is achieved by a touch panel member that includes a cured film of the negative photosensitive resin composition described above, and in which the molybdenum-containing metal wiring is protected by the cured film.

  The negative photosensitive resin composition of the present invention preferably contains (E) an isocyanate compound.

  In the negative photosensitive resin composition of the present invention, the (E) isocyanate compound is preferably (e-1) an isocyanate group-containing silane compound.

  In the negative photosensitive resin composition of the present invention, (A) the carboxyl group-containing acrylic resin is preferably an acrylic resin obtained by copolymerizing styrene.

The negative photosensitive resin composition of the present invention is a cured film having excellent pattern processability, high hardness, high transparency, high heat resistance by UV curing and heat curing, and high moisture and heat resistance that suppresses corrosion of the base metal. Can be obtained.

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 of the present invention comprises (A) a carboxyl group-containing acrylic resin, (B) a photopolymerization initiator, (C) a polyfunctional monomer, (D) four or more aromatic rings and an aromatic ring. A polyfunctional epoxy compound having a quaternary carbon having three or more bonds to (E) and an isocyanate compound.

  The negative photosensitive resin composition of the present invention contains (A) a carboxyl group-containing acrylic resin. By containing a carboxyl group, development with an alkaline aqueous solution becomes possible. Although there is no restriction | limiting in particular in the carboxylic acid equivalent of this acrylic resin, Preferably it is 200 g / mol or more and 1400 g / mol or less, More preferably, it is 300 g / mol or more and 1200 g / mol or less, More preferably, it is 400 g / mol or more. 800 g / mol or less. 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 is in such a range, a residue after development of the negative photosensitive resin composition with an alkaline aqueous solution can be suppressed and film loss in the exposed area can be suppressed, and a good pattern can be formed.

  Moreover, it is preferable from the point of exposure sensitivity and cured film hardness that the ethylenically unsaturated double bond group is introduce | transduced into at least one part of (A) carboxyl group-containing acrylic resin. By having an ethylenically unsaturated double bond group, curing at the time of exposure is promoted and sensitivity is improved, and a crosslink density after thermosetting is improved and hardness of the cured film can be improved. (A) Although there is no restriction | limiting in particular in the double bond equivalent of a carboxyl group-containing acrylic resin, It is preferable that it is 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.

  (A) Although a preferable example is given below as a carboxyl group-containing acrylic resin, it is not limited to this. (A) As a carboxyl group-containing acrylic resin, what carried out radical polymerization of the carboxyl group and / or acid anhydride group containing (meth) acrylic compound and other (meth) acrylic acid ester is preferable. Moreover, it is preferable to copolymerize styrene. The moisture and heat resistance of the cured film obtained by copolymerizing styrene is improved, and the corrosion resistance of the metal when used as a protective film is improved. 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, a carboxyl group and / or an acid anhydride group-containing (meth) acrylic compound, other (meth) acrylic acid ester and a radical polymerization catalyst are added in a solvent. It is preferable to react at 60 to 110 ° C. for 30 to 300 minutes after sufficiently purging the inside of the reaction vessel with nitrogen by bubbling or vacuum degassing. When an acid anhydride group-containing (meth) acrylic compound is used, it is preferable to add a theoretical amount of water and react at 30 to 60 ° C. for 30 to 60 minutes. Moreover, you may use chain transfer agents, such as a thiol compound, as needed.

  As the (meth) acrylic compound containing a carboxyl group and / or an acid anhydride group, (meth) acrylic acid, (meth) acrylic anhydride, itaconic acid, itaconic anhydride, succinic acid mono (2-acryloyloxyethyl) , Mono (2-acryloyloxyethyl) phthalate, mono (2-acryloyloxyethyl) tetrahydrophthalate, and the like.

  (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 Isobonyl, (meth) acrylic acid tricyclodecanyl, (meth) acrylic acid tetracyclodecanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid adamantyl, (meth) acrylic acid adamantyl methyl, (meth) acrylic Acid 1-methyladamantyl and the like are used.

  You may copolymerize aromatic vinyl compounds, such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, (alpha) -methylstyrene. Of these, styrene is preferred. By copolymerizing styrene, the heat resistance and moist heat resistance of the resulting cured film are improved.

  (A) When the carboxyl group-containing acrylic resin has an ethylenically unsaturated bond, as the acrylic resin, for example, a carboxyl group and / or an acid anhydride group-containing (meth) acrylic compound and (meth) acrylic ester are radically polymerized. Thereafter, those obtained by addition reaction of an epoxy compound having an ethylenically unsaturated double bond group are 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-based catalysts such as phenol and dimethylbenzylamine, tin-based catalysts such as tin 2-ethylhexanoate (II) and dibutyltin laurate, titanium-based catalysts such as titanium 2-ethylhexanoate (IV), triphenylphosphine 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.

  (A) The weight average molecular weight (Mw) of the carboxyl group-containing acrylic resin is not particularly limited, but may be 2,000 or more and 200,000 or less in terms of polystyrene measured by gel permeation chromatography (GPC). 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.

  In the negative photosensitive resin composition of the present invention, the content of the (A) carboxyl group-containing acrylic resin is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application. When the sum of the acrylic resin and (C) polyfunctional monomer is 100 parts by weight, it is generally 10 parts by weight or more and 70 parts by weight or less.

  The negative photosensitive resin composition of 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-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 (B) the photopolymerization initiator is not particularly limited, but the sum of (A) the carboxyl group-containing acrylic resin and (C) the polyfunctional monomer is 100 parts by weight. In this case, the amount is preferably 0.1 parts by weight or more and 20 parts by weight or less. 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 of 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 of the present invention is insolubilized in an aqueous alkaline solution, resulting in a negative 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. Moreover, it is preferable from the point of a sensitivity and hardness that the double bond equivalent of (C) polyfunctional monomer is 80 g / mol or more and 400 g / mol or less.

  (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 polyfunctional monomer (C) is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application. (A) A carboxyl group-containing acrylic resin And (C) 10 parts by weight or more and 60 parts by weight or less are common when the sum of the polyfunctional monomers is 100 parts by weight.

The negative photosensitive resin composition of the present invention contains (D) a polyfunctional epoxy compound having a quaternary carbon having four or more aromatic rings and three or more bonds with the aromatic rings. By containing the epoxy compound, the heat resistance of the resulting cured film, as well as the heat and moisture resistance that suppresses corrosion of the underlying metal, are improved.
Although there is no restriction | limiting in particular in the epoxy equivalent of a polyfunctional epoxy compound, Preferably it is 600 g / mol or less, More preferably, it is 300 g / mol or less. By being in this range, the degree of cross-linking during thermosetting is improved, and a cured film having high wet heat resistance can be obtained.

  As a polyfunctional epoxy compound, the compound of following formula (1)-(14) is mentioned, for example.

(R ^{1 to} R ⁶ , R ^{7 to} R ¹⁰ , R ^{11 to} R ¹³ , R ^{14 to} R ¹⁷ , R ^{18 to} R ²¹ each independently represents hydrogen, fluorine, a methyl group, an ethyl group, or a cyclohexyl group. M and n represent an integer of 0 to 10.)

Among these, the ones that are particularly effective for improving the heat and moisture resistance are the formulas (1), (2), (6), and (7).
, (8), (9) and (10), which are preferred.

  In the negative photosensitive resin composition of the present invention, (D) the content of the polyfunctional epoxy compound having quaternary carbon having four or more aromatic rings and three or more bonds with the aromatic rings is not particularly limited. However, when the sum of (A) carboxyl group-containing acrylic resin and (C) polyfunctional monomer is 100 parts by weight, 0.1 parts by weight, 20 parts by weight or less Is more preferably 1 part by weight or more and 15 parts by weight or less, and further preferably 3 parts by weight or more and 10 parts by weight or less.

  The negative photosensitive resin composition of the present invention preferably contains (E) an isocyanate compound. (E) The heat-and-moisture resistance of the cured film obtained by containing an isocyanate compound improves. The isocyanate compound includes a blocked isocyanate compound. Further, (E) the isocyanate compound is more preferably (e-1) an isocyanate group-containing silane compound. (E-1) Adhesion on various substrates is improved by being an isocyanate group-containing silane compound.

  (E-1) Examples of the isocyanate group-containing silane compound include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, N- ( 2-isocyanatoethyl) -3-aminopropyltrimethoxysilane, N- (2-isocyanatoethyl) -3-aminopropyltriethoxysilane, N- (2-isocyanatoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-isocyanatoethyl) -3-aminopropylmethyldiethoxysilane and the like. Among these, 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropylmethyldiethoxysilane are preferable from the viewpoint of storage stability in the composition.

  (E-1) As isocyanate compounds other than isocyanate group-containing silane compounds, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis (isocyanate methyl) benzene, 1,3-bis (isocyanate methyl) ) Cyclohexane, norbornane diisocyanate, naphthalene-1,5-diisocyanate, polymethylene polyphenyl polyisocyanate, 2-isocyanate ethyl (meth) acrylate, (meth) acrylic acid 2- (0- [1′-methylpropylideneamino] carboxy Amino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate, 1,1- (bis (meth) acryloyloxime Le) and ethyl isocyanate. Among these, from the viewpoint of hardness, 2-isocyanatoethyl (meth) acrylate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (Meth) acrylate is preferably 1,3-bis (isocyanatomethyl) cyclohexane or norbornane diisocyanate from the viewpoints of transparency and heat resistance.

  In the negative photosensitive resin composition of the present invention, (D) the content of the polyfunctional epoxy compound having quaternary carbon having four or more aromatic rings and three or more bonds with the aromatic rings is not particularly limited. However, when the sum of (A) the carboxyl group-containing acrylic resin and (C) the polyfunctional monomer is 100 parts by weight, 0.1 parts by weight or more and 20 parts by weight The following is preferable, more preferably 1 part by weight or more and 15 parts by weight or less, and further preferably 3 parts by weight or more and 8 parts by weight or less.

  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.

  The negative photosensitive resin composition of 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 of the present invention may contain a polymerization inhibitor. By containing a suitable amount of a polymerization inhibitor, the resolution after development is improved. The polymerization inhibitor is not particularly limited and known ones can be used. Examples thereof include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. . Commercially available polymerization inhibitors include “IRGANOX 1010”, “IRGANOX 1035”, “IRGANOX 1076”, “IRGANOX 1098”, “IRGANOX 1135”, “IRGANOX 1330”, “IRGANOX 1726”, “IRGANOX 1425”, “IRGANOX 1520”, “IRGANOX 245”, “IRGANOX 259”, “IRGANOX 3114”, “IRGANOX 565”, “IRGANOX 295” (above, manufactured by BASF) and the like.

  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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl Examples include 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, it is generally set to 50 wt% or more and 95 wt% or less of the entire negative photosensitive resin composition.

  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) ”,“ 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 (trade name) ”,“ BYK-345 (trade name) ”,“ BYK-307 (trade name) ”(manufactured by BYK Japan KK), polyalkylene, etc. Oxide-based surfactant, poly (meth) acte The like can be used rate based surfactant. 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 a film is formed by spin coating as will be described later, the solid content concentration is generally 5 wt% or more and 50 wt% or less.

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

  For example, after (B) a photopolymerization initiator, (D) a polyfunctional epoxy compound and other additives are added to an arbitrary solvent and dissolved by stirring, (A) a carboxyl group-containing acrylic resin and (C) many Add functional monomer and stir for another 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.

  Although there is no restriction | limiting in particular in the film thickness, the cured film obtained from the negative photosensitive resin composition of this invention has preferable 0.1-15 micrometers. 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 protective films for touch panels, various hard coat materials, flattening films for TFT, overcoats for color filters, antireflection films, passivation films, etc. It can be used for various protective films, optical filters, touch panel insulating films, TFT insulating films, color filter photo spacers, and the like. Among these, since it has high hardness, transparency, and heat resistance, 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 of 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 .

  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 Acrylic Resin Solution (A) A 500 ml flask was charged with 1 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). 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 30000, and the carboxylic acid equivalent was 560 g / mol.

Synthesis Example 2 Synthesis of Acrylic Resin Solution (B) 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate) were charged in a 500 ml flask. Thereafter, 26.5 g of methacrylic acid, 21.3 g of styrene, and 37.7 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were added and stirred for a while at room temperature, and the inside of the flask was bubbled. After sufficiently purging with nitrogen, the mixture was stirred with heating at 70 ° C. for 5 hours. Next, 14.6 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 ( 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 was 13000, and the carboxylic acid equivalent was 490 g / mol.

Synthesis Example 3 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. Thereafter, 32.3 g of methacrylic acid, 14.2 g of styrene, and 37.7 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged, stirred for a while at room temperature, and bubbled in the flask. After sufficiently purging with nitrogen, the mixture was stirred with heating at 70 ° C. for 5 hours. Next, 14.5 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 was 20000, and the carboxylic acid equivalent was 360 g / mol.

Synthesis Example 4 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, 26.4 g of methacrylic acid, 21.3 g of styrene, and 37.9 g of isobornyl methacrylate were charged, and the mixture was stirred for a while at room temperature. The inside of the flask was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 70 ° C. for 5 hours. . Next, 14.5 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 ( D) was obtained. 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 13000, and the carboxylic acid equivalent was 490 g / mol.

Synthesis Example 5 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, 29.4 g of methacrylic acid, 26.7 g of styrene, and 25.7 g of methyl methacrylate were charged, and the mixture was stirred for a while at room temperature. The inside of the flask was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 70 ° C. for 5 hours. Next, 18.2 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 ( E) was obtained. PGMEA was added to the obtained acrylic resin solution (E) so that the solid content concentration was 40 wt%. The weight average molecular weight of the acrylic resin was 20000, and the carboxylic acid equivalent was 470 g / mol.

  The evaluation methods in each example and comparative example are shown below. The compositions of Synthesis Examples 1 to 5 are summarized in Table 1.

  The evaluation methods in each example and comparative example are shown below.

(1) Transmittance measurement The produced negative photosensitive resin composition was spin coated ("1H-360S" (trade name) manufactured by Mikasa Co., Ltd.) on a 5 cm square Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.). ”) For 10 seconds at 500 rpm, spin for 4 seconds at 1000 rpm, and then 90 ° using a hot plate (“ SCW-636 (trade name) ”manufactured by Dainippon Screen Mfg. Co., Ltd.). Pre-baking was performed at 2 ° C. for 2 minutes to prepare 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) Hardness measurement Pencil conforming to “JIS K5600-5-4 (1999)” on a cured film having a thickness of 1.5 μm obtained by the method described in (1) above on a Tempax glass substrate. Hardness was measured.

(3) Moisture and heat resistance (3) -1 Base metal corrosion inhibition evaluation using PCT (pressure cooker test) On a glass having a molybdenum / aluminum / molybdenum multilayer film (MAM) as a base metal, After producing a cured film by the method, after performing a test of leaving in an oven (Espec Corp., “HAST CHAMBERE EHS-221MD (trade name)”) at a temperature of 121 ° C., a humidity of 100%, and an atmospheric pressure = 2 atm for 20 hours The ratio of the occupied area of the defects in which the MAM under the cured film was discolored by corrosion was visually evaluated. Seven or more were accepted.
10: The discolored area ratio of MAM under the cured film is 0%. No change in the appearance of the cured film itself.
9: The discolored area ratio of MAM under the cured film is 1% to 3%. No change in the appearance of the cured film itself.
8: The discolored area ratio of MAM under the cured film is 4% to 6%. No change in the appearance of the cured film itself.
7: The discolored area ratio of MAM under the cured film is 7% to 9%. No change in the appearance of the cured film itself.
6: The discolored area ratio of MAM under the cured film is 10% to 15%. No change in the appearance of the cured film itself.
5: Discolored area ratio of MAM under the cured film is 16% to 20%. No change in the appearance of the cured film itself.
4: The discolored area ratio of MAM under the cured film is 21% to 30%. No change in the appearance of the cured film itself.
3: The discolored area ratio of MAM under the cured film is 31% to 50%. No change in the appearance of the cured film itself.
2: The discolored area ratio of MAM under the cured film is 51% to 70%. No change in the appearance of the cured film itself.
1: The discoloration area ratio of MAM under the cured film is 71% to 100%. No change in the appearance of the cured film itself.
0: Discolored area ratio of MAM under the cured film is 100%, and discoloration, cracks, etc. occur in the cured film itself. (3) -2 Base metal corrosion inhibition evaluation using artificial sweat resistance test Equipped with MAM as the base metal A cured film was produced on the glass by the method described in (1) above, and then artificial sweat (NaCl = 1 g, lactic acid = 0.1 g, sodium hydrogenphosphate 12 hydrate = 0.25 g, histidine hydrochloride = 0) An aqueous solution in which 0.025 g is dissolved in 100 g of water) is dropped onto the substrate so as to have a diameter of 3 mm. ) ") After being tested for 24 days, the area of the MAM under the hardened film faded by corrosion on the concentric circle centering on the artificial sweat dripping site (excluding the artificial sweat dripping site) was evaluated. did The area was calculated after measuring the radius of the fading portion with a ruler. Further, in the case of spreading in an elliptical shape, the major axis and the minor axis were measured and calculated.
In the case of a circle: fading area = π × r ² −π × 1.5 ²
In the case of an ellipse: fading area = π × r _a × r _b −π × 1.5 ²
(R is .r _b is .π × 1.5 ² representing the radius of the circle .r _a representative of the artificial sweat dropping area representing the major axis of the ellipse representing the minor axis of the ellipse)
(4) Pattern workability (a) Sensitivity After rotating the negative photosensitive resin composition on a silicon wafer at 500 rpm for 10 seconds using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Corporation), 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 a prebaked film having a thickness of 2 μm Was made. 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.), shower development is performed for 90 seconds with a 0.4 wt% TMAH (tetramethylammonium hydroxide) aqueous solution, and then with water. Rinse 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.

(B) Resolution The minimum pattern size after development at the optimum exposure amount was measured.

(5) Evaluation of adhesiveness On a glass substrate (hereinafter referred to as “ITO substrate” or “MAM substrate”) whose surface is sputtered with ITO or MAM, a film thickness of 1.5 μm is formed in the same manner as described in (1) above. A cured film was formed, and the adhesion between ITO and the cured film was evaluated according to JIS “K5600-5-6 (established date = 1999/04/20)”.
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 determined to be 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%
Example 1
1.78 g of 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (“Irgacure OXE-01 (trade name)” manufactured by Ciba Specialty Chemicals) under a yellow light, 4-methoxyphenol 0.017 g, multifunctional epoxy compound “Techmore VG3101L (trade name)” (manufactured by Printec Co., Ltd., R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ^{6 in} formula (1) = Equivalent to H) 0.139 g of DAA (diacetone alcohol) 2.827 g and PGMEA 4.020 g were dissolved, and a silicone surfactant “BYK-333 (trade name)” (manufactured by Big Chemie Japan Co., Ltd.) ) 0.2000 g of PGMEA 1 wt% solution (corresponding to a concentration of 100 ppm) was added and stirred. Thereto was added 5.564 g of a 50% by weight PGMEA solution of dipentaerythritol hexaacrylate (“Kayarad (registered trademark)” DPHA (trade name), manufactured by Shin Nippon Kayaku) and 6.955 g of an acrylic resin solution (A). And stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition (A-1). About the obtained negative photosensitive resin composition (A-1), the transmittance | permeability, hardness, wet heat resistance, and pattern workability were evaluated by the said method.

Example 2
A negative photosensitive resin composition (A-2) was obtained in the same manner as in Example 1 except that the amount of “Techmore VG3101L (trade name)” was changed to 0.417 g. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-2).

Example 3
A negative photosensitive resin composition (A-3) was obtained in the same manner as in Example 2 except that the acrylic resin solution (B) 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 (A-3).

Example 4
A negative photosensitive resin composition (A-4) was obtained in the same manner as in Example 2 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 by using the obtained negative photosensitive resin composition (A-4).

Example 5
A negative photosensitive resin composition (A-5) was obtained in the same manner as in Example 2 except that the acrylic resin solution (D) 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 (A-5).

Example 6
A negative photosensitive resin composition (A-6) was obtained in the same manner as in Example 2 except that the acrylic resin solution (E) 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 (A-6).

Example 7
A negative photosensitive resin composition (A-7) was prepared in the same manner as in Example 2 except that 9,9-bis (4-glycidyloxyphenyl) fluorene was used instead of “Techmore VG3101L (trade name)”. Obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-7).

Example 8
A negative photosensitive resin composition (as in Example 2) except that 9,9-bis (4- (2-glycidyloxyethoxy) phenyl) fluorene was used instead of “Techmore VG3101L (trade name)”. A-8) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-8).

Example 9
A negative photosensitive resin composition (A) was prepared in the same manner as in Example 2 except that 9,9-bis (6-glycidyloxynaphthalen-2-yl) fluorene was used instead of “Techmore VG3101L (trade name)”. -9) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-9).

Example 10
A negative photosensitive resin composition (A-10) was obtained in the same manner as in Example 2 except that bis (4-glycidyloxyphenyl) diphenylmethane was used instead of “Techmore VG3101L (trade name)”. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-10).

Example 11
Under a yellow light, 0.259 g of “Irgacure OXE-01 (trade name)”, 0.016 g of 4-methoxyphenol and 0.388 g of “Techmore VG3101L (trade name)” were dissolved in 3.115 g of DAA and 4.212 g of PGMEA, A 0.2000 g PGMEA 1 wt% solution of “BYK-333 (trade name)” and 0.155 norbornane diisocyanate were added and stirred. Thereto, 5.180 g of a 50 wt% PGMEA solution of “DPHA (trade name)” and 6.475 g 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-11). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-11).

Example 12
Example 11 except that 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate (“Karenz MOI-BP (trade name)” manufactured by Showa Denko KK) was used instead of norbornane diisocyanate. In the same manner as above, a negative photosensitive resin composition (A-12) was obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-12).

Example 13
A negative photosensitive resin composition (A) was prepared in the same manner as in Example 11 except that 3-isocyanate triethoxysilane (“KBE-9007 (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of norbornane diisocyanate. -13) was obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (A-13).

Example 14
Except having used an acrylic resin solution (B) instead of an acrylic resin solution (A), it carried out similarly to Example 11 and obtained the negative photosensitive resin composition (A-14). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-14).

Example 15
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-16). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-15).

Example 16
Except having used an acrylic resin solution (B) instead of an acrylic resin solution (A), it carried out similarly to Example 13 and obtained the negative photosensitive resin composition (A-16). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (A-16).

Example 17
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 for 120 seconds with “N-300” manufactured by Co., Ltd., and a glass substrate having a patterned ITO (reference numeral 2 in FIGS. 1 and 2) having a film thickness of 150 nm was produced (FIG. 1). 1 corresponding to a).

(2) Production of transparent insulating film Using the negative photosensitive resin composition (A-1) on the obtained glass substrate, the transparent insulating film (reference numeral 3 in FIGS. 1 and 2) is used according to the procedure of the evaluation method described above. ) (Corresponding to b in FIG. 1).

(3) Production of MAM wiring On the obtained glass substrate, molybdenum and aluminum were used as targets, and H ₃ PO ₄ / HNO ₃ / CH ₃ COOH / H ₂ O = 65/3/5/27 (etching solution). (Mass ratio) MAM wiring (reference numeral 4 in FIGS. 1 and 2) was prepared in the same procedure as (1) except that the mixed solution was used (corresponding to c in FIG. 1).

(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 (corresponding to FIG. 2).

Comparative Example 1
Except not using "Techmore VG3101L (trade name)", the same procedure as in Example 1 was performed to obtain a negative photosensitive resin composition (H-1). Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (H-1).

Comparative Example 2
A negative photosensitive resin composition (H-2) was prepared in the same manner as in Example 2 except that 1,1,1-tris (4-glycidyloxyphenyl) ethane was used instead of “Techmore VG3101L (trade name)”. ) Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (H-2).

Comparative Example 3
Negative type photosensitive resin, except that “Epiclon 850S (trade name)” (DIC Corporation, bisphenol A type epoxy resin) is used instead of “Techmore VG3101L (trade name)”. A composition (H-3) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (H-3).

a: Top view after forming transparent electrode b: Top view after forming insulating film c: Top view after forming metal wiring 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 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 (6)

(A) carboxyl group-containing acrylic resin, (B) photopolymerization initiator, (C) polyfunctional monomer, (D) quaternary carbon having four or more aromatic rings and three or more bonds with aromatic rings. The negative photosensitive resin composition containing the polyfunctional epoxy compound which has , and (E) isocyanate compound . (E) an isocyanate compound, (e-1) negative-type photosensitive resin composition according to claim 1 Symbol mounting, characterized in that an isocyanate group-containing silane compound. (A) The negative photosensitive resin composition according to claim 1 or 2 , wherein the carboxyl group-containing acrylic resin is an acrylic resin obtained by copolymerizing styrene. The metal wiring protective film formed by hardening | curing the negative photosensitive resin composition in any one of Claims 1-3 . The metal wiring protective film according to claim 4 , wherein the metal wiring is a molybdenum-containing metal wiring. Panel member having a cured film of claim 1 or 2 negative photosensitive resin composition.

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