TW201142506A - Negative photosensitive resin composition, protective film and touch panel element using the same - Google Patents

Abstract

A negative photosensitive resin composition contains an alkali-soluble resin (A), a photopolymerization initiator (B), a polyfunctional monomer (C) and a zirconium compound (D). The carboxylic acid equivalent weight of the alkali-soluble resin (A) is 200 g/mol or more and is 1,400 g/mol or less. Provided is the negative photosensitive resin composition which is alkali developable, has excellent pattern workability, and can be cured by UV curing and thermal curing so as to obtain a hardened film having high hardness, high transparancy and excellent heat and humidity resistance.

Description

[Technical Field] The present invention relates to a negative photosensitive resin composition, a protective film using the same, and a touch panel member. [Prior Art] At present, the use of hard coating materials involves many aspects, such as surface hardness of containers, sheets, films, optical disks, thin displays, and the like which can be used for automobile parts, cosmetics, and the like. The properties required for the hard coat material include, in addition to hardness and scratch resistance, heat resistance, weather resistance, adhesion, and the like. Representative examples of the hard coat material include a radical polymerization type uv hardening type hard coat (for example, refer to the non-patent literature), which is composed of a polymerizable group-containing oligomer, a monomer, a photopolymerization initiator, and other additives. The oligomer and the monomer are subjected to radical polymerization by uv irradiation to crosslink to obtain a film having high hardness. The hard coat material has the advantages that the time required for hardening is short and the productivity is improved. The negative photosensitive material of the radical polymerization mechanism makes the manufacturing cost cheaper. However, there is a problem that the hardness and the scratch resistance are low compared with other hard coating materials due to the large number of organic components. The crack caused by the volume shrinkage of uv hardening. The capacitive touch panel that has received attention in recent years is one of the applications of hard coating materials. The capacitive touch panel has the following structure: A pattern made of ITO (Indium Tin Oxide) or a metal (silver, bismuth, or ruthenium). In order to protect the ITO and the metal, a film having high hardness, transparency, and moist heat resistance is required. It is difficult to balance these properties. 4 201142506 A hard coating material is required to solve this problem. Organic hard coating materials are known to have a uv hardening coating composition containing a polymerizable group-containing oligomer, single The body, photopolymerization initiator and other additives. The composition has pattern processing properties, and can obtain a cured film having hardness and transparency. (10) In terms of heat and humidity resistance, the same problem is known. Metal is added during the burning (> according to Patent Document 1). It is considered that the mechanism of the chelating agent promotes the cross-linking of Wei-burn and improves the heat-and-moisture resistance. Example of Ί石夕氧=聚下: By metal chelating agent It is used as a negative photosensitive material containing an organometallic compound, for example, with reference to the i-literal (polymerization) (i) energy source (ΐ:文:?) [Prior Art Document] [Patent Literature] Patent Unexamined Patent No. 1173, Patent No. 2008-203605 [Non-specialized Japanese Patent Laid-Open No. 2007-308688, hard coating, Daharasheng, etc., "The meeting centered on plastic substrates, 200s year coating and hardness The technical towel of the Technical Information Association on page 3, page 1 has the following problem: due to the organic 201142506, the hardness and scratch resistance are low compared with other hard coating materials, and The crack caused by the volume shrinkage of the uv hardening. In the technique of Patent Document 1, the main chain and the side chain of the resin are limited to the hydrophobic siloxane, and for example, a oxane having a carboxyl group in the side chain and ς The effect of the hydrophilic resin such as a resin containing a carboxyl group is not clear. In the technique of Patent Document 2, in order to suppress cross-linking of the cerium oxide in the pre-bake roasting, the content of the sterol group is small, and it is difficult to use an alkaline aqueous solution. In the technique of Patent Document 3, in order to form a metal film, calcination is performed, and no organic component remains. Therefore, the effect of the organometallic compound on the resin component is not clear. As described above, although a negative photosensitive material which has high hardness, high transparency, and high moisture and heat resistance and can be patterned by an alkaline developing solution is required, this technique has not been determined so far. SUMMARY OF THE INVENTION An object of the present invention is to provide a cured film of an alkali-developable negative photosensitive resin which is excellent in pattern processability and can be obtained by high-hardness, high transparency, and moist heat resistance by uv hardening and heat curing. Things. That is, the object of the present invention can be attained by a negative photosensitive resin composition containing an alkali solubility of (Α) carboxylic acid equivalent of 200 g/m〇l or more and MOOg/mol or less. Resin, (Β) photopolymerization initiator, (c) polyfunctional monomer, (D) zirconium compound. Further, the object of the present invention can be attained by a touch panel protective film which is obtained by hardening the above-mentioned negative photosensitive resin composition. 6 The purpose of 201142506 can be achieved by a metal wiring protective film which cures the negative photosensitive resin composition described above to 0. Moreover, the object of the present invention can be achieved by a touch panel. In the case of the member, the panel member includes the cured film of the above-described bismuth (four) photoresin composition, and the molybdenum-containing metal wiring is protected by the cured film. The negative photosensitive resin composition of the present invention is preferably a composition for forming a cured film. The negative photosensitive resin composition of the present invention is preferably a composition for forming a protective film. In the negative photosensitive resin composition of the present invention, it is preferred that (A) the repulsive acid 3: 200 g/mol or more and 1,400 g/mol or less of the soluble resin is an acrylic acid having an ethylenically unsaturated bond. Resin. In the negative photosensitive resin composition of the present invention, it is preferred that (A) a slow acid equivalent weight of 200 g/mol or more and 1,400 g/mol or less of the soluble resin is a polyoxyl group having an ethylenically unsaturated bond. alkyl. In the negative photosensitive resin composition of the present invention, it is preferred that the (D) junction compound is zirconia particles having an average particle diameter of 100 nm or less. In the negative photosensitive resin composition of the present invention, it is preferred that the (D) zirconium compound is any one or more of the compounds represented by the formula (1). [Chemical 1] 7 201142506

3 U1 represents hydrogen, aryl, aryl, county and its substituents, and r2 is a hydrogen, a aryl group, an alkenyl group, a silk group and a substituent thereof. More than you R, R and R3 can be the same or different. n represents an integer of 〇~4. [Effects of the Invention] The negative photosensitive resin composition of the present invention is excellent in pattern processability, and can be cured by UV curing and heat hardening, and is excellent in transparency, transparency, and moisture resistance. The above and other objects, features and advantages of the present invention will become more apparent and understood. <Embodiment> The negative photosensitive resin composition of the present invention contains (A) an alkali-soluble resin having a dicarboxylic acid equivalent of 200 g/m〇l or more and a moo g/m〇i or less, and (B) photopolymerization. Starting agent, (C) polyfunctional monomer, (D) zirconium compound. The negative photosensitive resin composition of the present invention is preferably a composition for forming a cured film. The cured film refers to a film obtained by removing all of the resin components by calcination or stripping treatment, and hardening by light and/or heat. The method of using the cured film is not particularly limited, and examples thereof include a protective film for a touch panel, a hard coat material, a flattening film for TFr, a protective layer for a color filter, a passivation film, an antireflection film, and a metal wiring. Bao 8 201142506 Various protective films such as protective film, various insulating films such as insulating films for touch panels, insulating films for TFTs, and interlayer insulating films, and optical filters, photosensitive spacers for color filters, microlenses, etc. . Among these methods of use, it is preferably used as a protective film from the viewpoint of high hardness, transparency, and heat and humidity resistance. The protective film is a cured film which is used for the purpose of protecting various underlying substrates. The method of using the protective film is not particularly limited, and the above may be mentioned as a specific example. The negative photosensitive resin composition of the present invention contains (A) a soluble resin having a retarding acid equivalent of 200 g/mol or more and 4 g/m〇i or less. The citric acid equivalent is a weight of a resin which is required to obtain a carboxyl group in an amount of 1 m〇, and the unit is g/mol. When the carboxylic acid equivalent of the alkali-soluble resin exceeds ι, 4 〇〇g/mol, the following problems occur: the solubility of the negative photosensitive resin composition is poor (developability), and a good pattern cannot be formed, and Even if it is developable, it is impossible to suppress the residue after development, or the type of the developer must be large, and the like. On the other hand, when the slow acid equivalent of the alkali-soluble resin is less than 200 g/m〇i, the film of the exposed portion cannot be suppressed from being reduced, and the resolution is inferior in addition to poor heat and humidity resistance. By setting the carboxylic acid equivalent to this range, a good pattern can be formed under various development conditions. Further, the alkali-soluble resin having a (A) carboxylic acid equivalent of 200 g/mol or more and 1,400 g/m〇1 or less used in the negative photosensitive resin composition of the present invention has an ethylenically unsaturated double bond group. Thereby, the crosslinking density can be increased 'and the hardness of the cured film can be improved. The preferred range of the carboxylic acid equivalent is 300 g/mol or more and 1200 g/mol or less, more preferably 4 〇〇 g/mol or more and 800 g/mol or less. 201142506 (A) The reductive acid equivalent is 200 g/mol or more and 1,400 g/mol or less. The solubility requirements are as follows: polyweishen, propyl miscellaneous, (iv) imine, polylysine, and polyamidamine. In order to increase the hardness of the cured film, it is preferred that the (A) carboxylic acid equivalent is 2 〇〇g/m 〇 1 or more and 14 〇〇 g/m 〇 1 or less; in the gluten resin, at least An ethylenically unsaturated double bond group is introduced into a part. From the viewpoint of easiness of introduction of the ethylenically unsaturated double bond group, (4) oxygen-fired, acrylic resin is more preferable among the polymers. Further, two or more kinds of these polymers may be contained. The soluble resin (A) having a carboxylic acid equivalent of 200 g/mol or more and 1,400 g/mol or less is preferably exemplified below, but is not limited thereto. For example, a compound obtained by hydrolyzing an organic sulfonium compound having a carboxyl group and/or a dicarboxylic anhydride group and condensing the hydrolyzate is preferably used. Further, in order to adjust the carboxylic acid equivalent, it is preferred to use other organic decane compounds at the same time. Among them, from the viewpoint of increasing the hardness of the obtained cured film, it is preferred to use an organic decane compound having an ethylenically unsaturated bond. The conditions of the hydrolysis reaction can be appropriately set. For example, it is preferably enthalpy to 180 liters in the solvent, and the acid catalyst and water are added to the organic sinter compound, and then reacted at room temperature or more and 11 〇〇c or less. ~18〇 minutes. By carrying out the hydrolysis reaction under such conditions, the reaction can be suppressed. The reaction temperature is more preferably 303⁄4 or more and i 〇 5 ° C or less. Preferably, the reaction is carried out in the presence of an acid catalyst. The acid catalyst is preferably an acidic aqueous solution containing citric acid, acetic acid or phosphoric acid. The preferred content of the acid catalyst is preferably from 1 part by weight to 5 parts by weight based on 100 parts by weight of all the organodecaneated 201142506 compound used in the hydrolysis reaction. By setting the amount of the acid catalyst to the above range, the hydrolysis reaction can be easily controlled to be carried out sufficiently and sufficiently. The conditions of the condensation reaction are preferably, for example, obtained by the hydrolysis reaction of the organodecane compound as described above, and then the reaction liquid is directly heated at 50 ° C or higher and below the boiling point of the solvent for 丨 1 to 1 hour. And make it react. Further, in order to increase the degree of polymerization of the polyoxyalkylene, it is also possible to reheat or add a base catalyst. Further, if it is hydrolyzed as necessary, it may be distilled under heating and/or reduced pressure to remove an appropriate amount of alcohol or the like, and then a suitable solvent may be added. It is desirable that the polyoxyalkylene having an ethylenically unsaturated bond of 200 g/mol or more and 1,4 〇〇g/m〇l or less has a carboxyl group and/or a dicarboxylic acid anhydride group. A compound obtained by hydrolyzing an organic decane compound and an organic decane compound having an ethylenically unsaturated bond to condense the hydrolyzate. Examples of the organodecane compound having a carboxyl group include 3-trisethoxydecylpropionic acid, 3-triethoxydecylpropionic acid, 3-dimethylmethoxydecylpropionic acid, and 3-didecyl. Ethoxy decyl propionic acid, 4 trimethoxy decyl butyl acid, 4 · triethoxy methoxy butyric acid, 4 dimethyl methoxy sulphuric acid, 4 - dimethyl ethoxy wei butyl acid , 5_ three? Oxyphylline ruthenium acid, 5-diethoxydecyl valeric acid, 5-dimethylmethoxyindolyl valeric acid, 5-methylethoxy sulphuric acid, and the like. Examples of the organodecane compound having a dihydric acid anhydride group include, for example, 3-trimethoxydecylpropyl succinic anhydride, 3·Bu シシシ シシシ シシシ シシシ 匕1^, continuation of anhydrous, 3 dimethyl methoxy Keweipropyl propyl glass shot 201142506 Anthraquinone anhydride, 3- mercaptoethoxy oxalate propyl sulphate j white acid Xuan, 3 _ tridecyloxy decyl propyl cyclohexane phthalic anhydride, 3 _ three Ethoxy decyl propylcyclohexanedicarboxylic acid needle, 3- mercapto methoxy oxalate propyl cyclohexane hexanoic acid liver, 3 - dimercapto ethoxy decyl propyl cyclohexane hexanoic anhydride , 3_tridecyloxydecyl propyl phthalic anhydride, 3_triethoxydecyl propyl phthalate, &quot; 3-dimercaptooxydecyl propyl phthalate Dicaptanic anhydride, 3-dimethylethoxy oxalate phthalic anhydride, and the like. Examples of the other organic decane compound include methyltrimethoxydecane, decyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, hexyltrimethoxydecane, and octadecyltrimethyl. Oxydecane, octadecyldiethoxy zeoxime, 3-aminopropyltriethoxylate, aminoethyl)-3-aminopropyltrimethoxydecane, 3-chloropropyl Trimethoxy oxime, 3-(N,N-glycidyl)aminopropyltrimethoxy oxime, 3-glycidoxypropyltrimethoxy decane, γ-aminopropyltrimethyl Oxydecane, γ-aminopropyltriethoxydecane, Νβ-(aminoethyl)-γ-aminopropyltrimethoxy decane, β-cyanoethyltriethoxy decane, shrinkage Glyceryloxymethyltrimethoxydecane, glycidoxycarbonyltriethoxydecane, α-glycidoxyethyltrimethoxysulfate, α-glycidoxyethyltriethoxylate Xishou, glyceryloxyethyltrimethoxy decane, β-glycidoxyethyl triethoxy sulphur, α-glycidoxypropyltrimethoxy sulphur, α-shrink Glyceroxypropyltriethoxy zeoxime, β-glycidoxypropyltrimethoxy decane, β-glycidoxypropyltriethoxy oxime, γ_glycidoxypropyltriazine Oxylate, γ-glycidoxypropyltriethoxydecane, α-glycidoxybutyltrimethoxy decane, α_shrinkage 12 201142506 Glyceroxybutyltriethoxydecane, β _ Glycidoxybutyl trimethoxy decane, β-glycidoxy butyl triethoxy decane, 7-glycidoxy butyl decyl oxysulphate, γ·glycidoxy butyl Triethoxy zebra, δ-glycidoxy butyl trimethoxy sulphur, g-glycidoxy butyl triethoxy decane, (3,4-epoxycyclohexyl)methyl trioxane Baseline, (3,4-epoxycyclohexyl)decyltriethoxydecane, 2_(3,4-epoxycyclohexyl)ethyldipropoxylate, 2-(3,4-epoxy Cyclohexyl)ethyltributyloxylinane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2·(3,4-epoxycyclohexyl)B Tris-oxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3 (3,4 epoxycyclohexyl)propyltriethoxydecane, 4-(3,4- Epoxycyclohexyl)butyltrimethoxydecane, 4-(3,4-epoxycyclohexyl)butyltriethoxydecane, dimethyldimethoxywei, dimethyldiethoxywei, γ•glycidoxypropylmethyldimethoxydecane,γ-aminopropylmercaptodimethoxydecane' 丫-aminopropylmethyldiethoxylate, Ν_(2_amine Base ethyl)_3_aminopropylmethyldimethoxydecane, glycidoxymethyldimethoxydecane, glycidoxycarbonyl fluorenyldiethoxy; ^,α•glycidyloxy Ethyl ethyl dimethoxy zebra, α·glycidoxyethylmethyldiethoxylate, β-glycidoxyethylmethyldimethoxy-wei, ρ•glycidol Oxyethylmercaptotriethoxy Wei, α•glycidoxypropylmethyldimethoxywei, a·glycidoxypropylmethyldiethoxyweiglycidoxypropyl? Dimethoxy Wei, β-glycidoxypropylmethyldiethoxy Wei, γ-glycidoxypropylmethyldimethoxysulfide, γ-glycidyloxymethyldiamide秘秘魏, γ缩缩 13 201142506 Oloxypropyl ethyl dimethoxy decane, γ-glycidoxypropyl ethyl diethoxy zexi, 3-cyclopropyl methyl dimethoxy stone Xiyuan, 3_gas propyl methyl diethoxy decane, cyclohexyl decyl dimethoxy decane, octadecyl decyl dimethoxy decane, tetradecyl decane, tetraethoxy decane, Trifluorodecyltrimethoxysulfanylsulfate, trifluoromethyltriethoxysulfate, trifluoropropyltrimethoxydecane, trifluoropropyltriethoxydecane, and the like. In addition, it can be obtained by using ethylene dimethoxy methoxy calcination, ethylene triethoxy dreaming, hydrazine, diterpenoids, bismuth, vinyl methyl diethoxy decane, Allyl trimethoxy decane, allyl triethoxy decane, allyl methyl dimethoxy decane, allyl methyl diethoxy decane, styryl trimethoxy decane, styryl Triethoxydecane, styrylmethyldimethoxydecane, styrylmethyldiethoxydecane, gamma-propenylpropyltrimethoxydecane, gamma-propenylpropyltriethoxylate Baseline, gamma methacryl propyl propyl trimethoxy decane, γ-mercapto propyl decyl propyl triethoxy decane, γ methacryl hydrazyl propyl methyl dimethoxy wei, γ Methyl propylene decyl propyl decyl diethoxy decane, γ-propylene decyl propyl methyl dimethoxy decane, 1 propylene I propyl propyl dimethyl diethoxy # burning, etc. Human ethylenically unsaturated double bond group. The carboxylic acid equivalent of the oxane can be calculated by 1H-NMR to calculate the acid value of the polyoxyalkylene. ^When Weigu has a case where B is unsaturated with a double bond group, it contains = 0^, and a special limit is preferred. The preferred double bond equivalent is 15 G g/mo1 or more. By setting the double bond equivalent to the above, hardness and crack resistance can be improved. The double bond equivalent can be calculated by measuring the angstrom value 201142506 zero * — , —p—lu. The weight average molecular weight (Mw) of the polyoxyalkylene is not particularly limited, and the ruthenium of Che Yijia is 1,000 or more and 100,000 in terms of a polystyrene conversion meter measured by gel permeation chromatography (GPC). the following. By setting Mw to the above range, good coating characteristics can be obtained, and the solubility in the developing liquid at the time of pattern formation is also improved. The &quot; acrylic resin is preferably an acrylic resin obtained by radically polymerizing (meth)acrylic acid or (meth)acrylic acid vinegar. The catalyst for radical polymerization is not particularly limited, and an azo compound such as azobisisobutyronitrile or an organic peroxide such as benzoquinone peroxide is usually used. The conditions of the radical polymerization can be appropriately set. For example, it is preferred to add (mercapto)acrylic acid, (mercapto) acrylate, and a radical polymerization catalyst to the solvent by defoaming or degassing under reduced pressure. After the gas is completely replaced in the vessel, the reaction is carried out at 6 Torr or more and 1 UT or less for 30 minutes to 300 minutes. Further, a chain transfer agent such as a thiol compound may be used as needed. (meth) acrylate can be used: (mercapto) decyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate , (fluorenyl) cyclohexyl acrylate, cyclohexenyl (mercapto) acrylate, 曱4·decyloxycyclohexyl (meth) acrylate, 2-(cyclopropyloxycarbonyl) (meth) acrylate Ester, (mercapto)acrylic acid _2_cyclopentyloxycarbonyl ethyl acetonate, (mercapto)acrylic acid _2_cyclohexyloxycarbonylethyl ester '(methyl)propanoic acid _2 _ hexenyloxy Carbonylethyl ester, 2-(4-methoxycyclohexyl)nonylcarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate Dilute tetracyclodecyl vinegar, (cyclo)acrylic acid dicyclopentanyl 15 201142506 ester, (mercapto) acrylic acid vinegar, (mercapto) acrylic acid methyl methacrylate, (meth) acrylate -1-methyl diamond just brewed. It may also be copolymerized with an aromatic vinyl compound such as styrene, p-methylstyrene, o-mercaptostyrene, m-methylstyrene or styrene-phenylene. The acid group having a carboxylic acid equivalent of 200 g/m〇l or more and 4〇〇g/m〇1 or less and having an ethylenically unsaturated bond is preferably, for example, a (meth)(tetra) acid and After the radical polymerization of (mercapto) acryl vinegar, an addition reaction with an epoxy compound having an ethylenically unsaturated double bond group is carried out. Further, the catalyst used in the addition reaction of the epoxy compound having a ethylenically unsaturated double bond group is not particularly limited. A known catalyst can be used, for example, dimethylaniline, 2, 4, 6 can be used. -Amino-based catalyst such as bis(dimethylaminomethyl)benzene, trimethylbenzylamine, tin-based catalyst such as tin 2-ethylhexanoate (8) or dibutyltin dodecanoate' 2-ethyl A titanium-based catalyst such as titanium (IV) hexanoate, a scaly catalyst such as triphenyl sulfonate, and a chromium-based catalyst such as chromium or chromium chloride. An epoxy compound having a ethylenically unsaturated double bond group, for example, can be (·(5)(tetra) acid glycidol vinegar, (mercapto)acrylic acid-α-ethylglycidyl ester, (meth)acrylic acid _α_ N-propyl glycidol g, (meth)acrylic acid _α• n-butyl glycidol vinegar, (methyl) propionate-3,4-epoxybutyl acrylate, (mercapto)acrylic acid _3,4· Epoxy vinegar, (mercapto) acrylic acid ethyl _6/7_epoxyheptyl ester, propyl propyl glycidol test, ^ dilute glycidyl _, o-vinyl ke sulphate _, vinyl Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, ... methyl-o-vinyl glycidyl glycidol test, aH between ethylene fresh silk glycerin bond, 2 base-p-ethylene fresh base shrinkage (4), 2, 3_Diglycidyloxy^Basic Ethylene, 2,4_Diglycidoxymethylstyrene, 2,5 Diglycid 201142506 ~ -~Γ—35^3'2'6_ Diglycidyl Oxymethylbenzene, 2,3,4-

Jm oxy-f silk, 3, 4, 5_ tricondensate dipropylene bis 2,4,6 diglycidoxymethyl styrene and the like. Acid resin has ethylenicity and double bond base ❹=❹ system, Wei Dang recorded money is (9) (four) or more

Hi Γ. The amount of Wei ## is the above, and can be calculated. Both hardness and resistance (four). The double bond equivalent can be determined by the enthalpy value and the weight average molecular weight (Mw) of the resin is not particularly limited. It is preferably converted into a polystyrene conversion solution by a 2 gram gel permeation chromatography (GPC). It is 2, more than 200 000. By setting Mw to the above range, good coating characteristics can be obtained, and the solubility in the developer at the time of pattern formation is also improved. In the negative photosensitive resin composition of the present invention, (A) the carboxylic acid equivalent is 200 g/m〇l or more, and the content of the alkali-soluble resin of 4 〇〇g/mol or less is not particularly limited. The film thickness or the intended use is arbitrarily selected. In general, the solid content of the negative photosensitive resin composition is 1% by weight or more and 60% by weight or less. The negative photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. (B) The photopolymerization initiator is preferably a photopolymerization initiator which can decompose and/or react due to light (including ultraviolet rays, electron beams) to generate a radical. Specific examples include 2-mercapto-[4-(indolylthio)phenyl]-2-N-morpholinylpropan-1-one and 2-didecylamino-2-(4-fluorenyl) Benzyl)-1-(4-morpholin-4- 17 201142506 phenyl-phenyl)-butan-1-one, 2-benzyl-2-didecylamino-1-(4-Ν-? Phenylphenyl)-butanone-1, 2,4,6-trimethylbenzimidylphenylphosphine oxide, bis(2,4,6-trimercaptophenyl)phenylphosphine Oxide, bis(2,6-dimethoxybenzylbenzyl)-(2,4,4-trimethylpentyl)-phosphine oxide, 1-phenyl-1,2-propanedione- 2-(o-ethoxycarbonyl)anthracene, 1,2-octanedione, 1-[4-(phenylthio)-2-(0-benzoquinone)], 1-phenyl-1, 2-butadiene 1-(o-nonyloxycarbonyl), 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)anthracene, ethyl ketone, 1-[9-ethyl -6-(2-mercaptobenzoyl)-9Η-σ卡嗤-3-yl]-, 1-(0-ethenyl group), 4,4-bis(didecylamino) Benzophenone, 4,4-bis(diethylamino)benzophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid ethylhexyl ester, p-diethyl Ethyl benzyl benzoate, diethoxy phenethyl ketone, 2-carbyl-2-methyl-1-phenylpropane·1 ketone, Di-decyl ketal, 丨_(4_isopropylphenyl)·2_hydroxy-2-methylpropane-fluorenone, 4-(2-hydroxyethoxy)phenyl-(2·yl) _2_ propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenyl fluorenone, orthoquinone , 4-phenyldiphenylhydrazine, 4,4-dibenzophenone, benzophenone, 4-benzofluorenyl-4,-mercapto-diphenyl sulfide, alkylation Benzophenone, 3,3,,4,4,-tetrakis(t-butylperoxycarbonyl)dibenzophenone, 4-benzofluorenyl-N,N-diindenyl-N-[2 -(l-Sideoxy-2-propenyloxy)ethyl] 曱 曱 ammonium bromide, (4-phenylhydrazinobenzyl)trimethylammonium hydride, 2 hydroxyj-(4- phenyl Nonylphenoxy)_N,N,N_trimethyl propylene vaporized ammonium monohydrate, 2-isopropylthioxanthone, 2,4-dithioxyl thioxanthone, 2,4 diethyl thiophene Tons of _, 2,4-dioxathioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-oxyl-9H-thrown_2_yloxy)_N,N,N _ tridecyl propyl propyl ammonium sulfate, 2, 2, ^ 201142506 ---~ Γ — (o-chlorophenyl)-4,5,4,,5,-tetraphenyl_1 2_Biimidazole, 1〇_butyl_2_gas acridine, 2-ethyl hydrazine, benzophenone, 9,1 〇 phenanthrenequinone, camphor quinone, decyl benzene acetate , η5·cyclopentane bake base ♦ iso-diphenyl iron hydrazine + ) _ six _ Jun S (1-), diphenyl sulfide derivative, double (... 'winter cyclopentadienyl) _ double (2 ,6-difluoro_3_(ex-pyrazol-1-yl)-phenyl)titanium, sulphonone, 2_mercaptothioxanthene, 2-oxothioxanthone, 4-stupylmethylsulfonyl 4-methylphenone, bis- ketone, ^, 2,3-diethoxyketanone, 2,2.dimethoxy-2-phenyl-2-phenyl-2-ketone, 2 - light keto-2-methylbenzene _, p-tert-butyl benzene acetophenone, fluorenyl methoxyethyl sulphate, fluorene 12 _ t-butyl oxime, 2-amino scream, β-chloropurine Brewing, anthrone, benzofluorenone, dibenzocycloheptanone, methylene hydrazine, 4-azidophenylstyryl ketone, 2 6_double-pair; base) ring, (4) pair Azidobenzylidene) bis = subs; sulfonium chloride, quinoline sulfonium, hydrazine phenyl thio. Photoreductive pigments such as acridone, benzothiazole disulfide, triphenylphosphine, tetra-evolved carbon, tribromo-p-phenyl, peroxidized blister, ruthenium blue, and the like, ascorbic acid, triethanolamine, etc. Combination of agents, etc. Two or more of these compounds may also be contained. θ In order to further increase the hardness of the cured film, an α-aminoalkylphenone compound, a mercaptophosphine oxide compound, an oxime ester compound, a benzophenone compound having an amine group, or an amine is preferable among the compounds. Base benzoquinone cool compound. Specific examples of the α-aminoalkylphenone compound include mercapto[4-(fluorenylthio)phenyl]-2-morphinylpropanone-oxime, 2-dimethylamino group. · 2-(4-indenyl) small (4-methylline _4·yl-phenyl) _ butyl ketone, ketone, 2 gram base • fluorenyl hydrazino-1 — (4 morpholine) Phenylphenyl)-butanone and the like. Specific examples of the mercaptophosphine oxide 201142506 compound: 2,4,6-trimethylphenylnonylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-benzene a phosphine oxide, bis(2,6-dimethoxyphenyl)-(2,4,4-tridecylpentyl)phosphine oxide, and the like. Specific examples of the compound can be exemplified by: i. phenyl·1&gt;2•propane-2-yl (o-ethoxy-carbyl) anthracene, 1,2-octanedione, phenylthio)-2-( 0-benzoquinone)], 1-phenyl•1,2-butanedione_2-(o-nonyloxycarbonyl)anthracene, 13-diphenylpropanetrione-2-(o-ethoxycarbonyl)肟, ethyl ketone, 1 [9 ethyl _6 (2 decyl phenyl fluorenyl)-9H-carbazol-3-yl] _, 1 _ (〇 醯 醯 醯 肟 。). Specific examples of the diphenylfluorenone compound having an amine group include 4,4-bis(didecylamino)benzophenone and 4,4·bis(monoethylamino)benzophenone. Wait. The benzoic acid vinegar having an amine group may be exemplified by p-didecylaminobenzoic acid ethyl ester, p-didecylaminobenzoic acid, 2-ethylhexanyl, p-diethyl Aminobenzoic acid, ethyl acetate, and the like. In the negative photosensitive resin composition of the present invention, (8) photopolymerization is started, and the content of the content is not limited, and is preferably G] wt% in the solid content of the quinoid photosensitive resin composition. Above 2G wt% or less. By setting the content of the (B) photopolymerization initiator to the above range, the curing can be sufficiently performed, and the residual polymerization initiator can be prevented from eluting or the like to ensure solvent resistance. The negative photosensitive resin composition of the present invention comprises (c) a polyfunctional single light irradiation, and the (6) polyfunctional monomer is polymerized by the above (8) photopolymerization initiator to form the negative (tetra) photoresin of the present invention. The exposed portion of the object becomes insoluble with respect to the alkaline aqueous solution, and a negative pattern can be formed. The term "multifunctional monomer" means having at least two or more B groups in the molecule, and the combination of the unsaturated double bonds is not particularly limited to S, and the preferred valer is easy to carry out radical polymerization with (meth) propyl group. The multi-functional single 201142506 body. Further, from the viewpoints of sensitivity and hardness, it is preferred that (c) the double bond of the polyfunctional monomer when 1 is 80 g/naoi or more and 400 g/mol or less. Examples of the (C) polyfunctional monomer include diethylene glycol diacrylate, diethylene glycol monopropionic acid S, tetraethylene glycol diacrylate vinegar, diethylene glycol dimercapto acrylate, and triethylene glycol. Alcohol dimercapto acrylate, tetraethylene glycol dimercapto acrylate, trihydroxy decyl propane di acrylate, trihydroxy decyl propane triacrylate, trishydroxy propyl propane dimethacrylate, trimethylol Propane trimethacrylate, 1,3-butanediol diacrylate, 13-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 〗 6, 6-hexanediol diacrylate, 1,9-nonanediol dimercapto acrylate, iota, 1 癸 癸 diol dimethacrylate Methyl-bicyclic tert-butyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tridecyl acrylate, pentaerythritol tetradecyl acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, Pentaerythritol non-acrylic acid ester, pentaerythritol decaacrylate, pentaerythritol eleven acrylate, pentaerythritol dodecyl acrylate, dipentaerythritol heptayl acrylate, tripentaerythritol octa methacrylate, tetrakis pentaerythritol nonyl acrylate, four Pentaerythritol decamethacrylate, pentaerythritol eleven methacrylate, pentaerythritol decyl acrylate, dihydroxy decyl tricyclodecane diacrylate, ethoxylated bisphenol A diacrylate , 9,9·bis[4_(2-propenyloxyethoxy)benzene, 9,9-bis[4_(2-methylpropenyloxyethoxy)phenyl]indole 9,91 [4-(2-Methylacryloxyethoxyethoxy)_3_tolyl] '(2_ propylene oxime ^ 21 201142506 propoxy)-3-fluorenyl phenyl], 9,9_ double ##·Acryl-based ethoxy)_3,5·dimethylphenyl]anthracene, 9,9-bis[4-(2·indolyl decyloxyethoxy)_3,5-dimethylbenzene Base] second class. Among them, pentaerythritol tetrapropylene vinegar, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, and the like are preferable from the viewpoint of improvement in sensitivity. Further, from the viewpoint of improvement in hydrophobicity, dihydroxyindenyl tricyclopyrene diacetin is preferred, di-methyl-tricyclic tert-butyl dimethyl acrylate, ethoxy group is preferred. Bisphenol A diacrylate, 9,9-bis[4_(2-propenyloxyethoxy)phenyl]anthracene, and the like. In the negative photosensitive resin composition of the present invention, (C) polyfunctionality is not contained in the content of the film, and may be selected from the negative photosensitive resin according to the principle of the use of the product. The solid umbrella of the object is 10 wt% or more and 6 wt% or less. # = The negative photosensitive resin composition of the invention contains (D) a ruthenium compound and contains (D) a dysfunctional compound, and the obtained cured film can be subjected to moist heat resistance. It is known that the resin of the county is derived from the hydrophilicity of Cheng, g = the hardened film can be made wet by containing (9) bismuth compound. It is known that a part of zirconium compound is known for polyfluorene. It has an effect of improving the heat and humidity resistance (see Patent Document 1). However, in the case of the recording, 'the money is red and only the hydrophobic group is hidden. As a result, the hydrophilic group such as the J group is rich, and it is not limited to the section. Oxygen burning, as '...' The alkali-soluble resin containing a carboxyl group in October can be found for the first time by the inclusion of the (D: 22 201142506 zirconium compound to improve the heat and humidity resistance of the cured film. Although it is not clear, it is considered that: (D) the zirconium compound forms a crosslinked structure by reacting a plurality of carboxyl groups of the base-soluble resin with (A) a carboxylic acid equivalent of 2 〇〇g/m 〇丨 or more to form a crosslinked structure. The film density is increased, and (4) the hydrophilicity derived from the silk is reduced, whereby the heat resistance of the obtained cured film is improved. (D) The zirconium compound is not particularly limited as long as it contains a ruthenium atom, for example, Preferably, the average particle diameter is below 100 nm. The cerium oxide particles or the compound represented by the formula (1). The average particle diameter of the oxidized erroneous particles is more than 40 knuckles. # By making the average particle diameter of the oxidized particles to be nm or less, the obtained cured film can be prevented from being cloudy. [Chemical 2]

23 201142506 Commercially available products can be used as the zirconia particles having an average particle diameter of 100 nm or less. Specific examples include "BAILAR Zr_C20 (trade name)" (average particle size is 20 nm, manufactured by Doki Chemical Co., Ltd.), NanoUse OZ-30M (trade name)" (average particle size: 7nm) (manufactured by Gifu Chemical Industry Co., Ltd.), "ZSL-10T (trade name)" (average particle size: 15 nm), "ZSL-l〇 A (trade name) (average particle diameter: 7 〇 nm) (above, manufactured by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.). In the formula (1), 'R1 may, for example, be an alkyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a phenyl group or a vinyl group, etc., from the viewpoint of stability of the compound, Preferred are n-propyl, n-butyl, phenyl. Examples of R2 and R3 include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, third T-group, phenyl, ethyl, methoxy, ethoxy, and Propyloxy, isopropoxy, n-butoxy, oxy, etc. Among them, a mercapto group, a second butyl group, a phenyl group, a decyloxy group, and an ethoxy group are preferable from the viewpoint of synthesizing glutamic acid and stabilizing the compound. Examples of the compound represented by the formula (1) include tetra-n-propoxy fluorene, tetra-n-butoxy-oxygen, tetra-second-oxygen, tetradox, tetraethylidene, and tetrakis (2, 2, 6, 6-Tetramethyl_3,5-heptanedionate), tetraethylammonium acetate, and the following;: ethyl acetate, tetramethyl malonate, tetrapropyl malonate: sulfhydryl acetone Bismuth, tetrakis(diphenylnonane) oxime, mono-n-butoxyacetamidine acetonide (acetonitrile acetate), mono-n-butoxyacetic acid ethyl acetate double (acetamidine) Slaughter m soap n-butoxytriacetonitrile oxime, mono-n-butoxydiethyl hydrazide zirconium, di-n-butoxy bis(acetic acid ethyl acetate) zirconium, 24 201142506 -· ---x- -- Di-n-butoxy bis(acetamidineacetone), di-n-butoxy bis(ethylmalonate), one-n-butoxy double (stupidyl), and di-n-butoxy Bis (diphenylmethane) zirconium and the like. Among them, tetra-n-propoxy fluorene, tetra-n-butoxy ruthenium, tetraphenoxy zirconium, tetraethyl fluorene oxime, etc. are preferred from the viewpoints of solubility in various solvents and/or stability of the compound. Tetrakis(2,2,6,6-tetradecyl_3,5-heptanedionyl)anthracene, methyl tetramalonate, zirconium tetramalonate, zirconium tetraacetate, zirconium, di-n-butyl Butoxy bis(acetonitrile ethyl acetate) oxime and mono-n-butoxyacetamidine acetonide (acetic acid ethyl acetate) were wrong. In the negative photosensitive resin composition of the present invention, the content of the (D) dysfunctional compound is not particularly limited, and in the case of oxidized hammer particles having an average particle diameter of 1 〇〇 nm or less, it is preferably negative. The solid content of the photosensitive resin composition is 1 wt% or more and 6 wt% or less, and in the case of the (D) wrong compound other than the above, it is preferably in the solid matter of the negative photosensitive resin composition. 0.1 wt% or more and 10 wt% or less. By setting the content of the (D) ruthenium compound to the above range, transparency and heat and humidity resistance can be achieved at a high level. The negative photosensitive resin composition of the present invention may contain polymerization inhibition = ° by containing a polymerization inhibitor, and the storage stability of the resin composition can be improved', and the resolution after development can be improved. The content of the polymerization inhibitor is preferably 1 wt% or less on the 〇 〇丨 wt 固 in the solid content of the negative photosensitive resin composition. Specific examples of the polymerization inhibitor include phenol, catechol, m-diphenol, p-diphenol, 4-tert-butyl catechol, 2,6-di(t-butyl)·-para Convenient, phenothiazine, 4-methoxyphenol and the like. The negative photosensitive resin composition of the present invention may also contain an ultraviolet absorbing agent 25 201142506. By containing an ultraviolet absorber, the light resistance of the obtained cured film can be improved. The resolution after development is improved in applications where pattern processing is required. The ultraviolet absorber is not particularly limited, and a known ultraviolet absorber can be used. From the viewpoints of transparency and non-coloring property, a benzotriazole compound, a benzophenone compound, or a triazine compound can be preferably used. Examples of the ultraviolet absorber of the benzotrisal compound include 2-(2H benzotriazol-2-yl)phenol and 2-(2H-benzotriazol-2-yl)-4,6-tripentyl. Phenol, 2-(2H benzotriazole-; 2-yl)_4_(i,i,3,3-tetramethylbutyl)phenol, 2(2Η-benzotriazol-2-yl)-6-ten Dialkyl-4-methylphenol, 2-(2,-hydroxy-5'-mercaptopropenyloxyethylphenyl) 2 oxime, benzotriazole, and the like. Examples of the ultraviolet absorber of the benzophenone compound include 2-hydroxy-4-inoxodibenzophenone. The ultraviolet absorber of the triazine-based compound may, for example, be 2,6,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol or the like. The negative photosensitive resin composition of the present invention may contain a solvent. It is preferred to use a compound having an alcoholic radical or a cyclic compound having a carbonyl group in view of the fact that the components are uniformly dissolved and the transparency of the obtained coating film is improved. Two or more of these compounds can also be used. Further, it is more preferable that the boiling point at atmospheric pressure is 11 (rc or more and 25 〇〇 c or less. By setting the boiling point to ll 〇 ° C or more, it is possible to dry appropriately at the time of coating the film.) On the other hand, when the boiling point is 25 ° C or less, the amount of residual solvent in the film can be suppressed to a small extent, and the film shrinkage at the time of thermosetting can be further reduced, thereby obtaining a better flatness. Specific examples of the compound having an alcoholic hydroxyl group and having a boiling point at atmospheric pressure of U (y> c or more and 25 〇〇 c or less include acetol, 3 hydroxy _ 3 fluorenyl _2 _ 26 201142506 _, 4-, By benzyl-3-mercapto ibupropanone, 5-pyl-p-pentyl-, 4-trans--4-ylmercapto-2-pentanone (diacetone alcohol), lactic acid, lactic acid, butyl vinegar , propylene glycol monoterpene ether, propylene glycol monoethyl ether, dodecyl alcohol mono-n-propyl bond, propylene glycol mono-n-butyl &amp; |, propylene glycol mono-tert-butyl ether, triterpene oxybutanol, 3 · decyl -3 曱 oxygen Small butanol, etc. Among these compounds, di- and fluorene are preferred from the viewpoint of storage stability, and it is particularly preferable from the viewpoint of step coverage. A propylene glycol mono-tert-butyl ether is used. Specific examples of the cyclic compound having a carbonyl group and having a boiling point of at least 25 〇t or less at atmospheric pressure include 丫-butyrolactone, 丫-valerolactone, δ·, ester, Propylene carbonate, hydrazine-methylpyrrolidinium, cyclohexanone, cycloheptanone, etc. Among these compounds, γ-butyrolactone oxime is particularly preferably used, and the negative photosensitive resin composition of the present invention is also The solvent other than the above may be contained, and examples thereof include ethers such as ethylene glycol dioxime ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethyl ether; butanone, acetamidine acetone, and mercaptopropyl ketone. a mercaptobutyl ketone, a decyl isobutyl ketone, a diisobutyl ketone, a cyclic ruthenium steel, a 2, heptanone, etc.; an acid amine such as a dimercapto (tetra)amine or a dimethyletheneamine; , propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoterpene ether acetate, acetic acid _3_methoxybutyl ester, acetic acid-3-mercapto-3- The content of the solvent is not particularly limited, and may be used in an arbitrary amount according to the coating method, etc., for example, by spin coating. In the case of forming a film, the content of the granule is usually 5 Å or more and 95% by weight or less of the entire negative photosensitive resin composition. The negative photosensitive resin composition of the present invention may further contain a promoting resin group 27 201142506 A curing agent which hardens or hardens the material. A hardening agent can be used in combination with a known hardening agent, and specific examples thereof include a nitrogen-containing organic resin hardener, various metal alkoxides, and various metal chelate compounds: isocyanide-compound And a polymer thereof, a trimeric amine derivative, a methylated urea derivative, etc., and may also contain two kinds of such compounds, such as self-hardening stability, and coating processability obtained, etc. It is considered that 'metal chelate compound amine derivative, methylolated urea charm can be preferably used. In the case where the polyoxyalkylene oxide is used in the negative photosensitive resin composition of the present invention, it can also be hardened by a heat generating agent or the like. catalyst. The thermal acid generator can be a known thermal acid generator, and examples thereof include various aromatic compounds such as an aromatic diazonium salt, a phosphonium salt, a diarylsulfonium salt, a triaryl sulphate, and a trisyl group (tetra). a horizontal acid ester, a halogen compound, and the like. In order to improve the fluidity at the time of coating, the negative photosensitive resin composition of the present invention may contain various interface activities such as various fluorine-based interface activities and poly-wei surfactants (4). The interface correction (4) is not particularly limited. For example, "Megafac (registered trademark), "F142D (product name)", "Π72 (product name)", "F173 (product name)", "F183 (trade name)" can be used. ), "F445 (product name)", "F47 () (product name)", "F475 (product name)", "F477 (product name)" (above) manufactured by Otsuka Ink Chemical Industry Co., Ltd. "Fluorine surfactants such as "NBX-15 (product name)" and "FTX_218 (product name)" (made by Neos Co., Ltd.), "Βγκ 333 (product name)", "ΒΥΚ-301 (product name)" , γβυκ_331 (product name), 28 201142506 "ΒΥΚ-345 (product name)", "ΒΥΚ-307 (product name)", "ΒΥΚ-352 (product name)" (BYK-CHEMIE JAPAN KK) A ruthenium-based surfactant, a polyoxyalkylene-based surfactant, a poly(fluorenyl) acrylate-based surfactant, and the like. Two or more of these compounds can also be used. The negative photosensitive resin composition of the present invention may optionally contain an additive such as a dissolution inhibitor, a stabilizer, or an antifoaming agent. The solid content concentration of the negative photosensitive resin composition of the present invention is not particularly limited. Any solvent or sol may be used depending on the coating method or the like. For example, when a film is formed by spin coating as will be described later, the solid content is usually 5 wt% or more and 50 wt% or less. A representative production method of the negative photosensitive resin composition of the present invention will be described below. For example, (B) a photopolymerization initiator, (D) a ruthenium compound, and other additives are added to any solvent, stirred and dissolved, and then (A) a slow acid equivalent of 200 g/mol or more and 1,400 g is added. Further, the base-soluble resin of /mol or less and (C) the polyfunctional monomer are further stirred for 2 to 3 hours. The negative photosensitive resin composition was obtained by the obtained solution. A method of forming a cured film using the negative photosensitive resin composition of the present invention will be described by way of example. The present invention is coated with a 'negative type of light-weight resin composition by a known method such as micro gravure printing, spin coating, dip coating, curtain coating, coating, spraying, slit coating, and the like. On the base substrate, the device is prebaked by a heating plate, a supply box, or the like. The prebaking is carried out in the range of 5 Å and 2 Torr for 3 G seconds to 3 Torr minutes, and the film thickness after prebaking is 29 201142506, preferably 〇·1 μηη or more and 15 μηη or less. After pre-baking, 'using a stepper, a specular projection reticle to align the exposure machine (ΜΡΑ), a parallel light ray aligning machine (hereinafter referred to as PLA), etc. Dielectric ~ 4,000 J / m2 (wavelength 365 nm exposure cover. The source of exposure is not limited, you can use i-ray, g-ray, 11-ray UV or KrF (wavelength 248 nm) laser, ArF (wavelength is 193.) Laser or the like. Thereafter, the film may be subjected to post-exposure baking, that is, heating in a heating device such as a hot plate or an oven at a temperature of 150 Å or more and 45 (the range below rc is heated for about 1 hour). The negative photosensitive resin composition of the present invention preferably has a sensitivity of 100 j/m 2 or more and 〇〇〇j/m 2 or less under exposure by PLA. The pattern is exposed by PLA. The sensitivity can be obtained, for example, by the following method: spin-coating the composition at a random number of revolutions on a Shi Xi wafer, using a hot plate at 12 Torr, and pre-baking for 2 minutes. A film with a film thickness of 2 μm was produced. PLA (Manufactured by Canon Inc., PLA-501F ( (product name) ") "Using an ultra-high pressure mercury lamp to expose the produced crucible by a gray scale mask for sensitivity measurement, and then using an automatic developing device (AD-2000 (trade name) manufactured by TAKIZAWA CO., LTD.) </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; The exposure amount of the line and the gap pattern is obtained as the sensitivity. After the patterning exposure, the exposed portion is dissolved by development, and the pattern of 201142506--'-r-negative pattern is obtained. The development method is developed by a method. W straw is an electrophotographic developer such as stealing, _, liquid coating, etc.; = 2 0; clock. The developer can use a known acid salt, a dish acid containing a metal hydroxide, carbon ethanol, single B; face Inorganic test of salt, salt, etc. -2-diethylamine test, etc., four-stage money = equal amines, 'tetramethyl-nitrogen oxide record, better aqueous solution of gallbladder, etc. After development, the r囹 meat bin The water is rinsed, and then the wire can be baked at a temperature below 5 ° C and below 150 ° C. Thereafter , in the ucrc above 28 (r rc below the range of ^ and other thermal hardening, to obtain a cured film. η from the t-type negative photosensitive resin composition obtained by the cured film is better ^ is the atomic content For reading of wt% or more and 75 wt% or less, carbon atom content of 25 趟 or more and 8 〇 wt% or less, and Shih's atomic content of 〇$ or more and O wt/o or less. By making it into the above range, it is well balanced. The degree of resolution of the transmittance, the hardness, and the resistance to the dyeing n is preferably 2 or less. The film thickness of the cured film is not particularly limited, and is preferably 〇1 μm or more and 15 μm or less. Further, it is preferable that the film thickness 丨 5 μηη has a hardness of 4 η or more and a transmittance of 90% or more. In addition, the transmittance refers to the transmittance at a wavelength of 4 〇〇 nm. The hardness or transmittance can be adjusted by selecting the exposure amount and the heat hardening temperature. The cured film obtained by curing the negative photosensitive resin composition of the present invention can be used for various protections such as a protective film for a touch panel, various hard coating materials, a planarizing film for a TFT, a protective layer for a color filter, and an antireflection film. Film, optical light guide, insulating film for touch sensor, insulating film for TFT, and color extinguishing 201142506. In these cases, "there is a high hardness and a consideration of m", which is suitable for use as a protective film for a touch panel. The touch surface i or the like, the optical type, the electromagnetic type, and the static capacitance = too 2 valley type touch panel require a particularly high hardness, and thus the cured film of the present invention can be suitably used. The hardened f obtained by curing the negative photosensitive resin composition of the invention has high heat and humidity resistance, so that the light (four) metal wiring protective film can be used for lifting on the metal wiring to prevent the corrosion of the metal. And ^« is deteriorated (conductivity is lowered, etc.). The metal to be protected is not particularly limited, and examples thereof include copper, silver m, titanium, iota, IZ〇 (indium zinc oxide), AZO (added with the oxidation of the name), and Zn〇2. In particular, it can be suitably used in a touch panel member to be contained. Here, the term "touch surface" means a glass film substrate including an electrode and an insulating film and/or a protective film, and can be used as a member of a sensor substrate for a touch panel. The method of manufacturing the touch panel member is not particularly limited, and for example, the method described below can be cited. Forming a transparent electrode film on a glass substrate at an arbitrary film thickness, patterning the photoresist material by photolithography, performing chemical etching of the transparent electrode using an etching solution, and performing a protective layer peeling step using a stripping solution A glass substrate (Fig. - a) for patterning a transparent electrode forming part of the X-axis electrode and the γ-axis electrode was produced. A metal oxide such as IT〇, IZ0, AZ〇, Zn〇2, or tin-recording acid or a thin film of a metal such as gold, silver, copper or aluminum is formed on the transparent electrode. These transparent conductive electrodes can be formed by a physical method such as vacuum evaporation, sputtering, ion plating, ion beam evaporation, or a chemical vapor deposition method, which has been carried out since the previous method 32 201142506. Then, a cured film obtained from the negative photosensitive resin composition of the present invention is formed as a transparent insulating film at a portion intersecting the electrode formed later (Fig. 1-b). Thereafter, an electrode thin film is formed with an arbitrary film thickness, and a wiring connected to the IC drive and a Y-axis electrode conductive wiring (Fig. 1_c) are formed by a step of photoresist pattern processing, etching, and photoresist stripping. As the electrode here, in addition to the transparent electrode material, indium, bismuth/molybdenum/molybdenum laminated film (MAM), key-sharp alloy, chromium, titanium, titanium/inscription/titanium laminated film (TAT), Aluminum and so on. Finally, a transparent protective film is formed by using a cured film obtained from the negative photosensitive resin composition of the present invention at a portion other than the portion where the 1C is driven to be connected to the end portion of the substrate (the upper left side and the lower right portion of the drawing). Control panel components. Fig. 2 is a cross-sectional view showing a fabrication example of the touch panel member. [Examples] Hereinafter, the present invention will be described using this example, but the aspect of the invention is not limited to the examples. (Synthesis Example 1: Synthesis of Polyoxane Solution (i)) A 500 mL three-necked flask was charged with methyltrimethoxyoxane 47 67 g (0.35 mol) and phenyltrimethyldecyldecane 39 66 g ( 〇2〇1), 3-trimethoxy sulfonylpropyl succinic acid 26.23 g (0.10 mol), γ-acryloyl propyl tridecyloxy decane 82.04 g (〇·35 mol), diacetone Alcohol (hereinafter referred to as DAA) 185.08 g, immersed in an oil bath of 4 〇〇c while stirring. Adding 0.39 g of phosphoric acid to 55.8 g of water by a dropping funnel in 10 minutes (relative to the monomer charged) In the case of 〇 2 wt%) aqueous phosphoric acid. After stirring at 40 ° C for 1 hour, the oil bath temperature was set to 7 (rc and stirred 1 33 201142506). The oil bath was heated to U5 ° C in 3G minutes. After the temperature rise = time, within the solution The temperature reaches the trace C, and then the temperature is _~110. 〇. The total amount of steam is distilled out in the reaction. · It is the work of (4) and water. The DAA dissolved in the obtained poly-salt = the degree of polymerization becomes * The wt% square green plus daa is used to obtain the poly-stone solution (1). In addition, the polymer obtained by Gpc _ weight average molecular weight (MW) is 8, _ (polystyrene conversion). The acid-equivalent equivalent was 620 g/m〇l. (Synthesis Example 2: Synthesis of polyoxane solution (ii)) A three-necked flask was charged with methyltrimethoxy-Wei 54 48 g__(m〇1), benzene. Tris-methoxy oxalate 39.66 g (〇.20 m〇1), 3-dimethoxyweipropylpropyl benzoate 13 12 g ( 〇〇5 _), brewed, propyl tridecyloxy Wei 82.04 g ( 〇·35 mGl), DAA 174 -, = oil slanted to the surface of the 4G °C slant-face county - surface by drop (four) bucket with 1 〇 is known to be added in water 54·9 g towel dissolved with phosphoric acid Q still g (0.2 wt% relative to the monomer charged) aqueous phosphoric acid. Secondly, Heating under the conditions of the synthesis example i: and steaming out the total methanol and water of the n-product. In the case of the DAA solution, the material is subjected to a 4% wt% a surface plus a DAA. (4) Oxygen-sintering solution (nj. In addition, the weight average molecular weight (Mw) of the polymer obtained by GPC_ was found to be 6, _ (polystyrene), and the acid equivalent was 1,190 g/mol. Synthesis Example 3: Synthesis of Polyoxane Solution (Extracted) A 500 mL three-necked flask was charged with methyltrimethoxyoxane 27 &amp; 34 201142506 g (0.20 mol), phenyltrimethoxydecane 39.66 g ( 0.20 mol), 3-dimethoxy group, propyl ketone acid 65.58 g (0.25 mol), γ-propyl propyl propyl tridecyloxy decane 82.04 g (0.35 mol), DAA 198.02 g, dip The crucate was dissolved in 58.5 g of water by a dropping funnel while stirring in an oil bath of 40 ° C, 416 g (0, 2 wt% relative to the monomer charged) The aqueous phosphoric acid solution was heated and stirred under the same conditions as in Synthesis Example i, and a total of 13 〇g of a sterol and water as a by-product was distilled off. The DAA of the obtained polyoxyalkylene oxide was obtained. In the solution, DAA was added to obtain a polyaluminoxane solution (iii) so that the polymer concentration became 40% by weight. Further, the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, and as a result, it was 7. 〇〇 (poly stupid ethylene conversion). Moreover, the carboxylic acid equivalent was 280 g/mol. (Synthesis Example 4: Synthesis of poly-stone-oxygen-burning solution (iv)) In a 500-mL three-necked flask, methyltrimethoxy-shixiyuan was charged with $8 (〇.2〇111〇1), and phenyl three.曱 石 石 39 39 66 § 〇 〇 〇 〇 66 66 66 66 66 66 66 66 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 M〇1), DAA 182 4 ° ° C in the oil bath - face win - face by the dropping funnel with iq = add 54.0g of water dissolved in Wei 〇 395 g (relative to 褒 and 〇 〇. 2 wt%) of a mixed aqueous solution. Next, in the same way as the synthetic m: the addition of dirty 'steaming' to take a total of 12 〇 g as a by-product =:, water. DAA was added in such a manner that the obtained DAA solution of the polyoxo-oxygenated gas was 40 wt%, and the concentration was concentrated (iv). In addition, Sa by GPC, and the Japanese 丨 又 又 & amp amp amp amp amp amp amp amp 石 石 石 另外 另外 另外 另外 另外 另外 另外 另外 另外 2011 2011 2011 2011 2011 2011 2011 2011 Further, the molecular weight (Mw) of the defect was 8, and the acid equivalent of 〇〇〇 (polystyrene) was 640 g/mol. (Synthesis Example 5. Synthesis of t-oxygen-burning solution (v)) A 500 mL three-necked flask was charged with methyltrimethoxy-wei 681 g (0.50 m〇l), and phenyltri-feta 15 g (〇% 〇(4),&gt; fluorenyl-3·methoxybutanol (hereinafter referred to as MMB) 143 37 g, reed by the bath surface while stirring with a dropping funnel for 10 minutes: added to water 54.0 g is dissolved in 167 g of phosphoric acid aqueous solution (0.1 wt% with respect to the monomer charged), and then heated and decomposed in the same manner as in the synthesis example, and 12 G g is added as a by-product. Methanol and water were added to the obtained MMB solution of polyweiwei, and MMB was added so that the polymer concentration became 40 wt% to obtain a polyoxyl&amp; solution (V). Further, the obtained polymer was measured by GPC. The weight average molecular weight (Mw) was 8,000 (in terms of polystyrene), and the carboxy group: equivalent weight was 0 g/mol. The synthesis example 5 is the aspect described in the patent document! (Synthesis Example: Acrylic resin) Synthesis of Solution (a)) ~7 In a 50〇1^ flask, 2,2,-azobis(isobutyronitrile)3L, propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) was added. g. Thereafter, incorporation of 2,0 g of methyl acrylate, 315 g of benzyl methacrylate, tricyclohexyl methacrylate [5.2.1. 〇 2'6] 癸 I I vinegar 32 8 g After fully dissipating at room temperature, the flask was thoroughly purged with nitrogen by bubbling, and then heated at 7 〇t for 5 hours. Secondly, methyl (tetra) acid glycidyl ester was added to the obtained towel. 12.7 g, dimercaptobenzylamine ig, p-methoxyphenol oxime PGMEA 100 g, heated under armpit for 4 hours to obtain C 36 201142506 olefinic acid resin solution (a). The solid concentration was 40 wt. The method of 〇/〇 is applied to the obtained propylene-lipid solution (4) towel to add npGMEA. The average molecular weight of the acrylic resin is 18 qing, and the acid equivalent weight is 56 () g/m 〇 (Synthetic Example 7. Acrylic resin solution (b) (Synthesis)) In a 500 ml flask, 2,2,-dioxane (isobutyl) PGMEA (propylene glycol oxime ether acetate) 5 〇g was charged. Thereafter, 16.8 g of citric acid and methyl group were charged. Acrylic acid, 34 4 g, methacrylic acid tris [5.2 丄 0 ' ] 癸 each base from the purpose of 36 · 9 g 'full interference at room temperature = bubble after the flask is fully replaced with nitrogen, at 7 Under the armpit, carry out 5 small heat mixing. Secondly, add methyl (10) acid glycosaminoglycol, diester 11.9g, dimercaptoylamine lg, p-methoxybenzene 〇 2^? / 100 g, heating was carried out for 4 hours at TC (4) to obtain a fat solution (b). PGMEA was added to the sassafras acid resin solution (b) in such a manner that the solid content became 4% by weight. The acrylic resin had a uniform molecular weight of 13,000 'carboxylic acid equivalent of 89 〇g/mol.曰里平 (Synthesis Example 8: Synthesis of Acrylic Resin Solution (c)) A 500 ml flask was charged with 2,2,-azobis(isobutyl hydrazine PGMEA 50 g. Thereafter, thioglycol 33 9 g was charged. Month g, benzyl ester 34.4 g, trimethyl methacrylate [5.2.1.02,6] decane 8 ^, enoic acid g, stirred well at room temperature, after the flask was fully 36·9 by foaming, Heat and stir for 5 hours at 7 (TC). Secondly, add glycidyl methacrylate 14·〇g, dimethoate 1 ^g, p-methoxyphenol 0.2 g, PGMEA. 100 g, heating and stirring at 9 〇 &amp; arylamine for 1 hour to obtain an acrylic resin solution (c). Add 4 to the obtained acrylic resin solution (4) from the solid concentration 37 201142506 to 40 wt%. PGMEA. The weight average molecular weight of the acrylic tree is 24, _, and the decanoic acid equivalent is 340 g/mol. (Synthesis Example 9. Synthesis of Acrylic Resin Solution (d)) In a 5 〇〇 ml flask, 2 is charged. 2,-azobis(isobutyronitrile) 3 g, P(10)EA 50 g. Thereafter, 8 24 g of methacrylic acid, 35.58 of benzyl mercapto acrylate, tricyclomethacrylate [52 1〇2,6]decane-8-yl ester 455 g' was stirred well at room temperature, and the flask was thoroughly purged with nitrogen by foaming, and then mixed at 7 ° C for 5 hours. To the obtained solution, thioglycolic acid glycidol vinegar g, dimethyl benzylamine 1 g to decyloxy group 0.2 g, PGMEA 100 g, and heating and stirring at 9 ° C for 4 hours were added. The acrylic resin solution (d) was obtained, and PGMEA was added to the obtained acrylic resin solution (d) 7 in such a manner that the solid content became 40 wt%. The weight average molecular weight of the acrylic resin was 9, hydrazine, and the carboxylic acid equivalent was 4,600. g/mol. (Synthesis Example 10: Synthesis of Acrylic Resin Solution (e)) In a flask of 5 〇 0 ml, 2 g of 2,2,-azobis(isobutyronitrile) and 50 g of PGMEA were charged. 69 5 g of methacrylic acid and 7.9 g of a nail were added, and 9.9 was thoroughly stirred at room temperature, and the flask was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 7 ° C for 5 hours. To the solution, 12.8 g of glycidyl methacrylate, ig of dimethyl hydrazide, 0.2 g of p-methoxyphenol, 100 g of PGMEA, and 9 (TC) were added. The heating and stirring were carried out for 4 hours to obtain an acrylic resin solution (e). PGMEA was added to the obtained acrylic resin solution (e) in such a manner that the solid content concentration 38 201142506 was 40 wt%. The weight average molecular weight of the acrylic resin was 40,000. The carboxylic acid equivalent was 140 g/mol. The compositions of Synthesis Examples 1 to 9 are collectively shown in Table 1. 39 201142506 七^06卜 £ [Id monomer composition (mol%) phenyl trimethoxy decane (20) phenyl trimethoxy decane (20) phenyl tridecyloxy cumane (20) phenyl trimethoxy Decane (20) phenyltrimethoxydecane (50) tricyclo[5.0.1.02,6]decane-8-yl ester (25) methacrylic acid tricyclic [5.2.1.02,6]癸炫- 8-Base Ester (30) Tricyclo [5.0.1.02,6]decane-8-yl methacrylate (20) Tricyclo[5.1.0.02,6]oxacin-8-yl ester (41 Trimethyl cyanoacrylate [5.2.1.02,6]decane-8-yl ester (5) methyltrimethoxy oxacyclohexane (35) methyltrimethoxy oxetane (40) methyltrimethoxylate Cyclohexane (20) methyltrimethoxy decane (25) methyltrimethoxy oxalate (50) benzyl methacrylate (30) benzyl methacrylate (35) benzyl methacrylate (20) 曱Benzyl acrylate (40) benzyl methacrylate (5: γ-acryloyl propyl trimethoxy oxalate (35) γ-propylene propyl propyl trimethoxy oxalate (35) γ-acryl hydrazine Propyltrimethoxysulfane (35) γ-acrylamidopropyltrimethoxy oxalate (35) armored Φ1 塄Jc if Β- 塄f C B- 塄td 塄ίί ¢- 3-trimethoxy oxalate propyl succinic acid (10) 3-trimethoxy hydroxyalkyl succinic acid (5) 3-trimethoxy decane Propyl succinic acid (25) 4-trimethoxy oxacyclobutanoic acid (20) methacrylic acid (30) methacrylic acid (20) methacrylic acid (45) methacrylic acid (4) methacrylic acid (80 Polyoxymethane solution (i) Polyoxane solution (5) Polyoxane solution (iii) Polyoxane solution (iv) Polyoxane solution (V) Acrylic resin solution (a) Acrylic resin solution (8) Acrylic acid Resin solution (C) Acrylic resin solution (4) Propionate resin solution (e) Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 201142506 The evaluation methods in the examples and the comparative examples are as follows. (1) The transmittance was measured by using a rotary coater ("1H-360S (trade name)" manufactured by Mikasa Corporation) at 500 rpm for 1 sec. , 〇〇〇 rpm rotation for 4 seconds to spin the prepared negative photosensitive resin composition to 5 cm After using the hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Mfg. Co., Ltd.), the square of the Tempax glass substrate (made by Asahi Yuki / Iri, manufactured by Tosoh Co., Ltd.) Prebaking at 90 ° C for 2 minutes to form a film having a film thickness of 2 μm. Using a parallel light ray aligning exposure machine (hereinafter referred to as PLA) (manufactured by Canon Inc., rPLA_5〇1F (trade name))) 'Using an ultra-high pressure mercury lamp as a light source to expose the film produced' using an oven (ESPECCORP The manufactured "IHPS-222" was cured in air at 230 C for 1 hour to prepare a cured film having a film thickness of 15 μm. For the obtained cured film, a transmittance of 400 nm was measured using an ultraviolet-visible spectrophotometer "UV-260 (trade name)" (manufactured by Shimadzu Corporation). Also' use Dainipp〇n Mfg

The "Lambda ACE STM-602 (trade name)" manufactured by Co., Ltd. was measured at a refractive index of 1.55. The film thickness described below is also the same. (2) Measurement of hardness The hardness of the ship was measured on the basis of JIS K 5600-5-4 (1999) based on the cured film having a film thickness of 15 Å obtained by the method described in the above (1). (3) The heat and humidity are on the glass with the tunicate film, and after the cured film is produced by the method 201142506 described in the above (1), the oven is placed at an air temperature of 85 ° C and a humidity of 85% (ESPEC Co., Ltd., "EX- 111 (After the test in which the product name was placed for 3 hours, the degree of discoloration of molybdenum was evaluated. Further, the glass substrate of the molybdenum sputter only film was tested at the same time, and the degree of discoloration before and after the test was determined as follows. 5: Before and after the test, no discoloration of molybdenum under the cured film was found. 4: Before and after the test, the molybdenum under the hardened film was about 10% discolored compared with the molybdenum without the cured film. 3 : Before and after the test 'The molybdenum under the hardened film is about 20% discolored compared with the molybdenum which is not covered with the cured film. 2: Before and after the test, the molybdenum under the hardened film is 40% compared with the uncovered hardened molybdenum. Left and right discoloration 1 : Before and after the test, the molybdenum under the hardened film has a discoloration of about 60% or more compared with the molybdenum which is not covered with the cured film. (4) Pattern processing property (4-1) Sensitivity using a rotary coating Cloth machine (1H-360 by Mikasa Corporation) S (trade name)") was rotated at 500 rpm for 1 second, and then rotated at 1, rpm for 4 seconds to spin-coat the negative photosensitive resin composition A on the Shihwa wafer, and then use a hot plate ( "SCW-636 (trade name)" manufactured by Dainippon Screen Mfg. Co., Ltd. was prebaked at 90 ° C for 2 minutes to prepare a prebaked film having a film thickness of 2 μm. Using PLA, an ultrahigh pressure mercury lamp For the light source, the obtained pre-baked film was exposed with a gap of 100 μm through a gray scale mask for sensitivity measurement. Thereafter, an automatic developing device 42 201142506 ("AD-2000 (trade name)", TAKIZAWA was used. (manufactured by c〇LTD), sprayed with a 4 wt% (or 2.38 wt%) aqueous solution of tetramethylammonium (hereinafter referred to as TMAH) for 90 seconds, followed by rinsing for 3 seconds in water. After development, a line of 30 μm is formed with a width of 1 to 1 and a light amount of the gap 11 (hereinafter referred to as an optimum exposure amount) is used as the sensitivity. The exposure amount is measured by an I illuminance meter. Resolution determines the minimum pattern size after development of the best exposure shirt. (4-3) Residue after development by the above (4-1) The method described in the method is performed on the Shiyue wafer, and the degree of dissolution of the unexposed portion is determined as follows: 0 and 5 are visually observed without residual solution. There is no residue in the fine pattern below the % division. The two eyes see: f 'exciting residue, under the microscope observation, above the 5〇μιη, but above the 50_= The value of ==resolved residue was observed under microscope observation, and there was a residue in the pattern of 50 qing or more. Under the visual view, 'at the end of the substrate (thickness (example υ, first 4, there is dissolved residue in the whole. Under the yellow light, make 1,2-Xin-Hang, ^ succinylthio)-2-(0-benzene曱醯躬〇] ("Irgacure OXE-Ol r Yong „ A, 、, two. °Name)” Ciba Specialty Chemicals Co., Ltd. 43 201142506 Manufactured by the company 0.277 g Dissolved in DAA 2.846 g, PGMEA 2.317 g, add two positive Butoxy bis(ethyl acetonitrile acetate) hydrazine (7 〇 wt% butanol &gt; gluten) ("ORGATIX ZC-580 (trade name)", Matsumoto Fine

Chemical Co丄td_manufactured) 0.227 g, "BYK-333 (trade name)" (ByK_chemie JApAN manufactured by Fork) PGMEA 1 wt% solution 0.2000 g (corresponding to a concentration of 1〇) Mouthwash? 111), 4-tert-butyl catechol 1) (}] £ 八 1 1% solution of 1671 g, stirring, adding dipentaerythritol hexaacrylate ("''KAYARAD (registered (trademark),, DpHA (trade name), manufactured by Shinjuku Chemical Co., Ltd.) PGMEA 50 wt% solution 5.538 g, poly-stone oxygen-burning solution (1) 6.9 ^ g, stirring. Secondly, 〇45 μιη The filter was subjected to 遽' to obtain a negative-type new-tree test (8). With respect to the obtained negative photosensitive composition (S)), transmittance, hardness, moist heat resistance, and pattern processability were evaluated by the above method. (Example 2), = = Ju Shi Xi oxygen burning solution (Η) instead of poly day oxygen burning solution (1), in addition to this

Example 1 was carried out in the same manner, and a negative photosensitive resin composition was obtained and evaluated in the same manner as in the negative photosensitive property obtained in Example 1. B

In the case where the developing solution was used, 2.38 wt% TMAH (Example 3), the Si dilactane solution (10) was used instead of the polyoxyalkylene solution (1), and the negative photosensitive composition was obtained in addition to the sample. The negative photosensitive resin composition (S-3) was evaluated in the same manner as in Example 1 of 201142506 ^ ^ ^ ^ a. (Example 4) A negative photosensitive resin composition (S-4) was obtained in the same manner as in Example 1 except that the polyoxane solution (iv) was used instead of the polyoxyalkylene solution (i). The negative photosensitive resin composition (s_4) obtained was used for evaluation in the same manner as in Example 1. (Example 5) Add 2-methyl-[4-(decylthio)phenyl]-2-N-morpholinylpropan-1-one under "yellow lamp" ("Irgacure 9〇7 (trade name)" Manufactured by Ciba Specialty Chemicals Co., Ltd., 0,503 g, 4,4-bis(diethylamino)benzophenone ("EAB-F (trade name)" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.026 g, DAA 3.030 g, PGMEA 2.515 g, "ZC-580 (trade name)" 0.227 g, BYK-333 (1 wt% PGMEA solution) 矽.2000g as a polyfluorene-based surfactant (equivalent to a concentration of l〇〇) Puncture was carried out at a concentration of 1.588 g of 4-butylbutyl catechol (1 wt% PGMEA solution). The mixture was mixed with "DPHA" (50 wt% PGMEA solution) 5.294 g and polysulfate oxygen solution (i) 6.617 g. Next, filtration was carried out with a filter of 0.45 μm to obtain a negative photosensitive resin composition (S-5). The negative photosensitive resin composition (S_5) thus obtained was used in the same manner as in Example 1. 7 (Example 6) Using ethyl ketone, 1-[9-ethyl-6_(2-methylphenylhydrazinyl)·9Η “卡唾_3-基]-,Η〇-乙醯基) ( In the same manner as in Example 1 of 45 201142506, the negative photosensitive resin composition (s_6) was obtained in the same manner as in the example of 45 201142506 except for the Irgacure ΟΧΕ-02 (trade name), which was manufactured by Ciba Specialty Chemicals Co., Ltd. The negative photosensitive resin composition (S-6) thus obtained was used for evaluation in the same manner as in Example 1. (Example 7) The same procedure as in Example 1 was carried out except that tripentaerythritol octaacrylate ("V# 802 (trade name)", manufactured by Osaka Organic Chemical Co., Ltd.) was used instead of "DPHA (trade name)". A negative photosensitive resin composition (S-7) was obtained. The negative photosensitive resin composition (S-7)' obtained was evaluated in the same manner as in Example 1. (Example 8) Using "V#802 (trade name)" (50% PGMEA solution) 3.323 g and 9,9~bis[4_(2_acryloxyethoxy)phenyl]g ("BPEFA (Commodity) In the same manner as in Example 1, except that "DPHA (trade name)" was used instead of "DPHA (trade name)", a negative photosensitive resin composition (s_8) was obtained. The negative photosensitive resin composition (S-8) was evaluated in the same manner as in Example 1. (Example 9) Under the yellow lamp, "〇XE-01 (trade name)" 〇.277 g, DAA 2_846 g was added. , PGMEA2.016 g, "NanoUse OZ-30M (trade name)" (sterol solution 'solids = 30.9 wt%) 0.538 g, BYK-333 (1 wt% PGMEA solution) as a polyoxo surfactant 0. 2 〇 00 g (corresponding to a concentration of 100 ppm) and 4-tributyl catechol 〇 wt% PGMEA solution) 1.661 g were stirred. A scramble was carried out by adding rDPHA (product 46 201142506 name) (50% PGMEA solution) 5.538 g and polyoxyalkylene solution (i) 6.923 g. Next, filtration was carried out with a filter of 0.45 μηη to obtain a negative photosensitive resin composition (S-9). The negative photosensitive resin composition (S-9) thus obtained was evaluated in the same manner as in Example 1. (Example 10) Under the yellow light, add "ΟΧΕ-01 (trade name)" 0.239 g, DAA 3.410 g, PGMEA0.846 g, "NanoUse OZ-30M (trade name)" (sterol solution, solids = 30.9 Wt〇/0) 3.098 g, BYK-333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 100 ppm), 4-tert-butyl catechol (1) The wt〇/0 PGMEA solution was stirred at 1.436 g. Stirring was carried out by adding "DPHA (trade name)" (5 % PGMEA solution) 4.787 g and polyoxyalkylene solution (i) 5.984 g. Next, filtration was carried out with a filter of 〇·45 μm to obtain a negative photosensitive resin composition (S-i〇). The negative photosensitive resin composition (S_10) thus obtained was used for evaluation in the same manner as in Example 。. (Example 11) Use "BAILAR Zr-C2〇 (trade name)" (methanol solution, solids = 20wt%) 〇.831g instead of "NanoUse〇Z-30M (trade name)" 0/38 g, in addition to Example 9 was carried out in the same manner to obtain a negative photosensitive resin composition (S-11). The negative photosensitive resin composition (S-11) thus obtained was used for evaluation in the same manner as in Example 1. (Example 12) Under the swatch light, add "OXE-01 (trade name)" 〇.277 g, DAA 1846 g, PGMEA 2·388 g, tetraacetyl acetonide zirconium ("Nacem 201142506

Zirconium (trade name), manufactured by Sakamoto Chemical Co., Ltd.) 0166g, BYK-333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 1〇〇ppm) as a polyoxonated surfactant, 4- The third butyl group was mixed with 1.661 g of 1 wt% PGMEA solution. Add "DPHA (trade name)" (50 wt% PGMEA solution) 5.538 g, polyoxymethane solution (i) 6.923 g and stir. Next, the negative photosensitive resin composition (S-12) was obtained by using a 0.45 μηη filter. The negative photosensitive resin composition (S-12) thus obtained was used in the same manner as in Example 1. (Example 13) A negative photosensitive resin composition (S-13) was obtained in the same manner as in Example 12 except that the amount of the Nacem Zirconium was changed to 0.017 g. The negative photosensitive resin composition (s_13) thus obtained was used for evaluation in the same manner as in Example 1. (Example 14) A negative photosensitive resin composition ^S_14) was obtained in the same manner as in Example 12 except that the amount of the Nacem Zirconium was changed to 0.323 g. The negative photosensitive resin composition (s_14)' obtained was evaluated in the same manner as in Example 1. (Example 15) A negative photosensitive resin composition (s_13;) was obtained in the same manner as in Example ^ except that a tetrapropoxy group was used instead of Nacem Zirconium. The negative photosensitive resin composition (S-13) thus obtained was used for evaluation in the same manner as in Example 1. 48 201142506 (Example 16) A negative photosensitive resin composition (S·14) was obtained in the same manner as in Example 1 except that the Nacem Zirconium was used instead of the Nacem Zirconium. The negative photosensitive resin composition (S-14) thus obtained was used for evaluation in the same manner as in Example 1. (Example 17) A negative photosensitive property was obtained in the same manner as in Example 12 except that tetrakis(2,2,6,6-tetramethyl-3,5-heptanedone)zirconium was used instead of Nacem Zirco^a'. Resin composition (s_15). The negative photosensitive resin composition (S-15)' obtained was evaluated in the same manner as in Example 。. (Example 18) A negative photosensitive resin obtained by using a negative-sensitive sensible resin composition (S-16) was obtained in the same manner as in Example 12 except that the bismuth propionate was used instead of Nacem Zirconium. The composition (s_i6) was evaluated in the same manner as in Example 1. (Example 19) A negative photosensitive resin composition obtained by using a negative-type sensible resin composition (S 17) was obtained in the same manner as in Example 12 except that four enamel acetonide were used instead of Nacem zirconium (ϋ7). Fish example 1 was evaluated in the same manner. 〃 (Example 20) using single n-butoxyethyl II acetone bis(acetonitrile acetate) instead

Nacem Zirconium, risk, ι·ΐ·,,, and also from, Α “ “ “ “ 与 与 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 蒋 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 49 201142506 Lip group: 2 8) 'Evaluation in the same manner as in Example 1. Using dichlorobis(η5-cyclopentane)

Zirconium, in addition to the example soil. The NaCem photo-resin composition (4) was subjected to 'obtaining a negative-type sensory substance (4)), and the composition of the example-type photosensitive resin (Example 22) was carried out in the same manner as in Example 12 except that hydrogen gas (η5_penta-I^4Zl_um) was used. Obtained: =; === type sensation first _ composition (example 23) using again (monofluoro 曱 夂 夂 一 一 一 一 Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Photosensitive resin composition (S-21). The obtained lipid composition (S-2D was evaluated in the same manner as in Example i. (4) Nine (Example 24) The stomach was treated with an acrylic resin solution U) instead of Ju Shi Xi Wei Solution (1)

- Adding the same amount of PGMEA instead of DAA, and performing the same with the sample, obtaining a negative photosensitive resin composition (A 〇 J; negative photosensitive resin group money (A·1)' and an example; (Example 25) Using an acrylic resin solution (b) instead of a polyfluorene gas solution (^) 50 201142506 I.-f Further adding the same amount of PGMEA instead of DAA, except for the same as in Example 2 The resin composition (A-2) was used, and the obtained negative photosensitive resin composition (A-2) was used for evaluation in the same manner as in Example 1. The developer was used in an aqueous solution of 2.38 wt% TMAH. (Example 26) A negative photosensitive resin composition (A-3) was obtained in the same manner as in Example 3 except that the same amount of PGMEA was used instead of DAA in place of the polyoxylate resin solution (c). Using the obtained negative photosensitive resin composition (A-3), it was evaluated in the same manner as in Example 1. D (Example 27) An acrylic resin solution (a) was used instead of the polyoxyalkylene solution (丨), and further added. The same amount of PGMEA replaces DAA, except for example 5 The negative photosensitive resin composition (A_4) was obtained. The obtained negative photosensitive resin composition (A-4) was used in the same manner as in Example 二. (Example 28) Using an acrylic resin solution (a) A negative photosensitive resin composition (A-5) was obtained in the same manner as in Example 6 except that the same amount of PGMEA was used instead of the DAA, and the resulting negative photosensitive resin was used. (A·5), evaluation was carried out in the same manner as in the example! (Example 29) Using a propylene glycol resin solution (a) instead of the polysulfide solution (1), proceeding to 51 201142506, the same amount of PGMEA was added instead of DAA. In the same manner as in Example 7, except that the negative photosensitive resin composition (A-6) was obtained, the same as Example 1 was used to carry out the flat 4 only 0 ~ (Example 30) ~ An acrylic resin solution (a) was used instead of the polyoxyalkylene solution (丨), and the same amount of PGMEA was added in place of DAA in the same manner as in the above, except that Example 8 was carried out to obtain a negative photosensitive resin composition. (A_7)., using the ^ = negative photosensitive resin composition (A-7), evaluated in the same manner as in Example i (Example 31) Using an acrylic resin solution (a) instead of the polyoxyalkylene solution (i), adding the same amount of PGMEA instead of DAA, and other examples In the same manner, a negative photosensitive resin composition (A_8) was obtained, and the obtained negative photosensitive resin composition (A-8) was used in the same manner as in Example 。. (Example 32) Using acrylic acid A negative photosensitive resin composition (A-9) was obtained in the same manner as in Example 1 except that the resin solution (a) was replaced by the same amount of PGMEA in place of the DAA. The negative photosensitive resin composition (A-9) thus obtained was evaluated in the same manner as in Example 1. (Example 33) An acrylic resin solution (a) was used instead of the polyoxygen oxide solution (i), and 52 201142506 was added in the same manner as in the case of the same amount of PGMEA in the same manner as in Example u to obtain a negative photosensitive resin. Composition (A-ίο). The evaluation was carried out in the same manner as in Example 1 except that the negative photosensitive resin composition (A-10) was used. (Example 34) An acrylic resin solution (a) was used instead of the polyoxyalkylene solution 〇), and the same amount of PGMEA was added instead of hydrazine, and the same procedure as in Example 12 was carried out to obtain a negative photosensitive resin composition. (A-11). The negative photosensitive resin composition (A-11) obtained was used for evaluation in the same manner as in Example 1. 7 (Example 35) A negative photosensitive resin composition (A-) was obtained in the same manner as in Example 13 except that the same amount of PGMEA was used instead of the DAA in the acrylic resin solution (a). 12). The negative photosensitive resin composition (A-12) was used for evaluation in the same manner as in Example 1. (Example 36) A negative photosensitive resin composition was obtained in the same manner as in Example 14 except that the acrylic resin solution (a) was used instead of the polyoxyalkylene solution (丨), and the same amount of PGMEA was added instead of DAA. . The negative photosensitive resin composition (A-13) of the rod was used for evaluation in the same manner as in Example 1. (Example 37) Using an acrylic resin solution (a) instead of a polyoxygen oxy-saturated solution (丨), proceeding 53 201142506: Steps were added to the same amount of PGMEA instead of DAA, and otherwise performed in the same manner as in Example i5, to obtain a negative photosensitive property. Resin composition (A-14). Using the negative photosensitive resin composition (A-14) to be used, in the same manner as in Example 1 (Example 38), an acrylic resin solution (a) was used instead of the polyoxyalkylene solution (i), and the same amount was added. In the same manner as in the example, PGMEA was used instead of the DAA to obtain a negative photosensitive resin composition (A-15). The negative photosensitive resin composition (A-15) thus obtained was evaluated in the same manner as in Example i. (Example 39) A negative photosensitive property was obtained in the same manner as in Example 17 except that the acrylic resin solution (a) was used instead of the polyoxyalkylene solution (i), and the same amount of PGMEA was added instead of DAA. Resin composition (A_16). The negative photosensitive resin composition (A-16) obtained was used for evaluation in the same manner as in Example 1. A 7 (Example 40) An acrylic resin solution (a) was used instead of the polyoxyalkylene solution, and the same amount of PGMEA was added in place of DAA in the same manner as in Example 18, to obtain a negative photosensitive resin composition. (A-17). The negative photosensitive resin composition (A-17) obtained was used for evaluation in the same manner as in the example. (Example 41) Using acrylic resin solution (a) instead of polyoxyalkylene solution (i), enter 54 201142506 - Step to add the same amount of PGMEA instead of DAA, except for this w_ the same secret, 隹 / show this from the outside and the Example 19, a negative photosensitive resin composition (A-18) of the negative electrode type photosensitive resin composition (4) 8 was obtained, and it was evaluated with Example i. °""Example (Example 42) Using an acrylic resin solution (a) instead of the polyoxygen oxy-saturated solution (丨), :: Add the same amount of PGMEA instead of DAA, and otherwise perform the same as the actual = to obtain a negative-type photosensitive Resin composition (a_19,). The obtained negative photosensitive resin composition (Α·19) was evaluated for fish use. 〃 J Η 地 (Example 43) Using the acrylic resin solution (a) instead of the polyoxygen oxy-combustion solution (i), the same amount of PGMEA was added instead of DAA, and otherwise the same as in Example j, the negative sensitization was obtained. Resin composition (A_2〇). The negative photosensitive resin composition (A-20) obtained was used for evaluation in the same manner as in Example i. (Example 44) A negative photosensitive resin composition was obtained in the same manner as in Example 22 except that the acrylic resin solution (a) was used instead of the polyoxygen oxide solution (i), and the same amount of PGMEA was added instead of DAA. (A_21). The negative photosensitive resin composition (A-20) obtained was used for evaluation in the same manner as in Example i. (Example 45) An acrylic resin solution (a) was used instead of the polysulfide solution (丨), and 55 201142506 was added in the same manner as in Example 23 except that the same amount of PGMEA was added in one step instead of the DAA. Resin composition (A-22). The negative photosensitive resin composition (A-20) obtained was used for evaluation in the same manner as in Example 1. (Example 46) A touch panel member was fabricated in the following order. (1) ITO was produced by using a sputtering apparatus HSR-521A (manufactured by Shimadzu Corporation, Ltd.), and sputtering was performed at a power of i.4 kW and a vacuum of 12.5 minutes. A ruthenium film having a film thickness of 150 nm and a surface resistance of 15 Ω/□ was formed on the substrate, and a je type photoresist ("OFPR-800" manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied at 8 (rc) A 20-minute pre-baked film was obtained to obtain a photoresist film having a thickness of 1.1 μm. Using PLA, the resulting film was subjected to pattern exposure with an ultra-high pressure mercury lamp through a remote cover, and an automatic developing device was used for L 2·38 Wt%. The hydrazine aqueous solution was subjected to spray development for 90 seconds, followed by rinsing for 30 seconds, and thereafter, by the immersion in the mixed solution of 仞α/ΗΝ〇3/Η2() = ::5 (weight ratio) In the case of a leap second, the peeling liquid of 5〇C ("N-300" manufactured by Nagase Chemical Co., Ltd.) was treated for 120 seconds, thereby removing the photoresist to have a film thickness of 200 angstroms. The glass edge plate of the transparent electrode which has been patterned and embossed 0 (2) The transparent insulating film is fabricated on the obtained glass substrate, so that Negative photosensitive resin composition 56 201142506 (Al), a transparent insulating film was produced in the order of the above evaluation method. (3) A molybdenum/aluminum/molybdenum laminated film (MAM) wiring was produced on the obtained glass substrate, and used. Molybdenum and aluminum were used as targets, and a mixed solution of H3P04/HN03/CH3C00H/H20 = 65/3/5/27 (weight ratio) was used as an etching solution, and mam wiring was produced in the same order as (1). 4) The transparent protective film was formed on the obtained glass substrate, and a transparent protective film was produced in the order of the evaluation method described above using the negative photosensitive resin composition (A-1). The conduction test of the connection portion was carried out using a tester. (Contrast Example 1) A resin was obtained in the same manner as in Example 1 except that the polyacrylic acid resin solution (d) was used instead of the polychlorinated oxygen-burning solution (〇, the same amount of PGMEA was further added instead of DAA). The composition (Η-D. Here, the acid equivalent of the acrylic resin solution (d) was 4,600 g/mol. The obtained resin composition) was evaluated in the same manner as in Example 1. Further, the unexposed portion was dissolved. At 2.38 wt% TMAH water In the solution, pattern processing could not be performed, and other evaluations were carried out by development. (Comparative Example 2) An acrylic resin solution (e) was used instead of the polyoxyalkylene solution (〇, injection; addition of PGIME in the same place instead of DAA) The same procedure as in Example 1 was carried out to obtain a resin composition (H 2 ). Here, the decanoic acid equivalent of the acrylic resin dissolved in e) was 140 g/m〇i. The obtained resin composition 57 201142506 (H-2) ' Evaluation was performed in the same manner as in Example 1. (Comparative Example 3) Under the smear lamp, 'PGMEA 4 74 〇g, "ZC 58 〇 (trade name)" 0.249 g, and bYK 333 (1 wt% PGMEA+ solution) 0.2 矽 as a polyoxo-based surfactant were added. 〇〇g (corresponding to a degree of 100 ppm) and 1.342 g of 4-tert-butyl catechol (1 wt% PGMEA solution) were stirred. The DPHA (trade name) (5 〇 wt% pGMEA solution) 5 8 〇 6 g and the acrylic resin solution (a ) 7.258 g were added and stirred. Next, filtration was carried out with a filter of 〇 45 μm to obtain a resin composition (Η_3). The resin composition (Η-3) does not contain a photopolymerization initiator. The obtained resin composition (Η-3) was used for evaluation in the same manner as in the example. Further, the exposed portions and the unexposed portions all had solubility in a wt.4 wt% TMAH aqueous solution, and it was impossible to carry out pattern processing, and other evaluations were carried out without performing development. (Comparative Example 4) Under the yellow light, 'Additional force σ "〇XE-01 (trade name)" 〇277 g, PGMEA 3.778 g, and "ZC-580 (trade name)" 0.237 g, as a polyfluorene-based interface activity Stirring BYK-333 (1 wt% PGMEA solution) 0.2000 g (equivalent to 100 ppm for Hanting) and 1.36 g of 4-tert-butyl phthalate (1 wt〇/〇pGMEA $) . The acrylic resin solution (a) i3 846 g was added and stirred. Next, filtration was carried out with a filter of 0.45 μm to obtain a resin composition (Η-4). The polyfunctional monomer was not contained in the resin composition (Η-4). The obtained resin composition (Η_4) was used for evaluation in the same manner as in Example i. (Comparative Example 5) 58 201142506

Under the yellow light, add 0.285 g of "〇χΕ_01 (trade name)" and 4.990 g of pGMEA as a polyfluorene-based surfactant bYK_333 (1 wt% PGMEA solution) 0.2000 g (corresponding to a concentration of 1 〇〇 ppm). 4_Telebutyl catechol (1 wt% pGMEA solution) 17 〇 9 g was stirred. Stirring was carried out by adding "DPHA (trade name)" (5 〇 wt% pGMEA solution) to 5 g and 7.20 g of the acrylic resin solution (a). Next, filtration was carried out in a filtered state of 〇45 μΓη to obtain a resin composition (Η_5). The ruthenium compound was not contained in the resin composition (Η_5). The obtained resin composition (?-5) was used for evaluation in the same manner as in Example 1. (Comparative Example 6)

Under the yellow light, add "〇χΕ_01 (trade name)" 〇 285 g, pGMEA 2·262 g, DAA 2.846 g, BYK-333 (1 wt% PGMEA solution) as a polyoxygenated surfactant 〇2〇 〇〇g (corresponding to a concentration of 100 ppm) and 4-tert-butyl catechol (丨wt% pGMEA solution) 1.709 g were stirred. 5.96 g of rDpHA (trade name) (5 〇 PGMEA solution) and 712 〇g of a polyoxyalkylene solution (丨) were added and stirred. Next, filtration was carried out with a filter of 0.45 μm to obtain a resin composition (Η-6). The ruthenium compound was not contained in the resin composition (Η_6). The obtained resin composition (?_6) was used and evaluated in the same manner as in the example. (Comparative Example 7) A negative photosensitive resin composition (H-7) was obtained in the same manner as in Example 1 except that the polyoxane solution (v) was used instead of the polyoxyalkylene solution (丨). The negative photosensitive resin composition (H-7) thus obtained was used for evaluation in the same manner as in Example 1 of 2011. In addition, the unexposed portion was not dissolved in the 0.4 wt% TMAH aqueous solution. 201142506

Jui 卜e [CN&lt;] Residue after pattern processing development»〇寸 in in νη in inch resolution [μιη] 〇〇in 00 VO to CN ν〇o Ο 〇oo oo oo oo 00 oo oo Sensitivity (mJ/cm2 ) § s 〇Ο gsssss δ § s sparse in yn inch inch W-ϊ cn ^Τ) yn hardness « XX l〇X VO inch ^Τ) XXX »T) ffi XX ID ^1 »义透' 1 S_✓ K -J· ¥峰日. Hungarian a – 96.2% 1 96.2% 96.5% 95.8% 94.4% 93.1% 96.3% 96.1% 95.0% 95.0% 95.0% 96.2% 97.2% | 94.2% I | 95.9% 1 | 95.5% 1 96.1% 95.9% 95.3% Η,(3)("(D)锉 compound\R,/^ α cs CN CN &lt;N (N (N 1 1 1 ooo inch ο oo cn B- ¢- S- 1 1 1 1 &amp;- ¢- 1 1 ** methoxyphenyl 2 ethoxy l ethoxy 1 ethoxy 1 ethoxy 1 ethoxy I ethoxy I ethoxy I | ethoxy | 1 1 1 rugged - ¢ - 1 1 tert-butylmethoxy B-2 n-butyl l-n-butyl l-n-butyl 1-n-butyl I 1 n-butyl | 1 n-butyl 1 1 n-butyl I | n-butyl 1 1 1 1 1 1 1 n-propyl stupid 1 1 1 (D) 之 compound type ZC-580 | ZC-580 ZC-580 ZC-580 ZC-580 ZC-580 ZC-580 ZC-580 NaaoUse OZ-30M NanoUse OZ- 30M BAILARZr-C20 Nacem Zirconium Nacem Zirconium Nacem Zirconium Tetrapropoxy phenoxytetradecyl cn? ^ ( 1 Ό » (Ν ^ ri ¥ tetramalonic acid vinegar vinegar wrong four-fold thymol acetone zirconium (A) soluble Resin carboxylic acid equivalent [g/mol] 〇(N 1190 1 ο ο CN ο &lt;N ο CN o CN o cs irj ο CNj «τϊ o CN V) o CM ^Ti o CN o (N ο (S § § § (A) Alkali Soluble Resin Type Polyoxane Solution (i) | Polyoxane Solution (ii) Polyoxane Solution (iii) Polyoxane Oxygen Solution (iv) Polyoxane Solution ( i) Polyoxane solution (i) Polyoxane solution (i) Polyoxane solution (i) Polyoxane solution (i) Polyoxane solution (i) Polyoxane solution (i) Polyoxane solution (i) 1 polyoxyalkylene melt (i) polyoxymethane solution (i) polyoxyalkylene solution (i) polyoxyalkylene solution (i) polyoxyalkylene solution (i) Polyoxane solution (i) Polyoxane solution (i) - 4 1 cs c/b cn X/ll ζλ v〇OQ rp ΚΛ 00 K/l Ό\ ζΛ S-10 t/1 S-12 CO Ob S-14 S-16 S-17 00 S-19 Example 1 I 丨 Example 2 1 丨 Example 3 1 1 Instance 4 I 1 Instance 5 I 1 Instance 6 丨 1 Instance 7j | Example 81 1 Instance 9 1 | 〇 | Ur example ii I | Example 12 | i instance A3j | instance 14j | example 15 | | example 16 | example 17 1 instance 18 | 1 example 19 | 19 201142506

Jas6 卜 ε οο 00 § S m X yr» ffi 95.6% 95.1% 1 1 ? group 1 1 1 ethoxy I δ-1 n-butyl 1 , tO 3: o dioxo bis (η5-cyclopentadienyl) Zirconium (II) 520 520 Polyoxane solution (i) Polyoxane solution (i) S-20 S-21 Example 20 Example 21 ΰ 201142506

Ja(N06 ε ε pattern processing development residual Wi inch l〇»/*&gt; »Τ) in inch resolution [μπι] 00 m XTi rH v〇〇〇〇00 00 00 〇〇00 oo sensitivity (mJ/ Cm2) S 〇(N 〇og SS § s § δ Moisture resistance _ tr> iT) inch yr> CO to u-ϊ ίο hardness ffi X ^Τ) κ X a ffi v〇K Κ ffi ffi in ffi KX κ «ο ^ Ο 哿 i i 96.5% | 96.2% I 1 96.3% 1 94.7% 91.5% 96.5% 96.0% 94.7% 94.7% 94.7% 96.5% 97.2% 94.2% 96.4% 96.2% 95.5% 96.1% (9) Misty Yang a &lt;N CN CN cs &lt;N CN 1 1 1 ο (N &lt;N inch inch ο cn pi Pi B- ¢- 1 material 1 B-shift 1 1 1 1 Β Β - δ- s- 1 1 Η , , 1 difficult to oxy 2 ethoxy ethoxy ethoxy ethoxy ethoxy I ethoxy I ethoxy 1 1 1 Β - ¢ - 1 1 卜,, (5) methoxy 5 n- butyl 1 n-Butyl 1 n-butyl 1 n-butyl | 丨-n-butyl | I n-butyl I 1 n-butyl 1 1 1 1 1 1 1 n-propylphenyl 1 I (D) Deuterated content type ZC -580 ZC-580 ZC-580 ZC-580 ZC-580 ZC-580 ZC-580 ! NanoUse OZ-30M NanoUse OZ-30M BAILAR Zr-C20 N Acem Zirconium Nacem Zirconium S .2 _S 〇N iz tetrapropoxy octaphenoxy oxime Έ ^ (1 v〇y &lt;N ^ Cl Λ 0 ^ tetramethyl malonate zirconium 1 (A) Alkali-soluble resin carboxylic acid equivalent [g/mol] 〇ν〇〇Os 00 〇〇v〇ο ν〇ov〇o VO 〇V〇〇VO vr&gt; ο ν〇tn ο v〇ov〇in 〇Ο ν〇〇 V〇§ δ (A) Type of alkali-soluble resin Acrylic resin solution (a) Acrylic resin solution (y Acrylic resin solution (C) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Propionic acid Resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin Solution (a) Acrylic resin solution (a) Acrylic resin solution (a) 1 - Η &lt; (N &lt; cn &lt; inch &lt; VJ &lt;&lt;&lt;: 00 &lt;: ON &lt; 1 A- 10 I A-ll A-12 A-13 A-14 A-15 A-16 A-17 Example 24| |Example 25| |Example 26 |Example 27|1Example 28| |Example 29| 丨Example 30| 丨Example 31|1 Instance 32| |Example 33| |Example 34| |Example 35| |Example 36| |Example 37| |Example 38| |Example 40| 201142506

Jursl06 卜e inch&lt;] Remaining in pattern processing development in κη in 1 ΙΓ ί Resolution [μπι] 00 00 00 00 00 00 00 1 1 1 1 00 00 1 Sensitivity (mJ/cm2) § § § δ 〇1 &gt; 300 1 &gt;300 § § 1 Moisture and heat resistance in CO cn (N inch V) ^ Η Hardness XXK in V) ffi ΙΛ X ffi cn &lt;6B XX V-) Transmittance of hardened film (λ = 400 nm, film Thickness 1.5 μπι) I 95.4% I 95,6% 95.1% 95.2% 94.4% 96.4% 96.0% 95.8% 96.4% 96.5% 1 97.5% 1 97.5% J (1) (D) False compound a Π C o 1 1 1 &lt;Ν fS &lt;N CN 1 1 CN 2 Stupid L^l 1 1 1 Mercaptomethyl 1 1 2 5硪IIA] 1 1 1 Ethoxy 5 硪 ethoxy 5 硪 1 1 ethoxy 5 1 n-butyl 1 1 1 n-butyl n-butyl n-butyl n-butyl 1 1 n-butyl (D) hydrazine compound type tetraphenyl hydrazine zirconium st lR> S is 4 &lt; 0 digastric double ( Η5-cyclopentadienyl) zirconium argon bis(η5-cyclopentadienyl) 韶矣^ Ψ δ- ^ «δέ &gt;s^ u| B ZC-580 ZC-580 ZC-580 ZC-580 1 1 ZC-580 (A) Alkali-soluble resin carboxylic acid equivalent [g/mol] 1 560 560 560 560 560 4600 ο 560 560 1 560 1 1 520 1 〇 (A) type of alkali-soluble resin acrylic resin solution (a) acrylic resin solution (a) acrylic resin solution (a) acrylic resin solution (a) acrylic resin solution (a) acrylic resin solution (d) Acrylic resin solution (e) Acrylic resin solution (a) Acrylic resin solution (a) Acrylic resin solution (a) Polyoxane solution (i) Polyoxane solution (V) Composition | A-18 I A -19 A-20 A-21 A-22 »·Η a H-2 H-3 H-4 H-7 | Example 41 I Example 42 Example 43 Example 44 Example 45 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 1 Comparative Example 5] |Comparative Example 6|Comparative Example 7 Inch 9 201142506 [Industrial Applicability] The cured film obtained by curing the negative photosensitive resin composition of the present invention can be suitably used for a touch panel. In addition to various hard coating films such as a protective film, it can also be suitably used for an insulating film for a touch panel, a planarizing film for a TFT of a liquid crystal or an organic EL display, a metal wiring protective film, an insulating film, an antireflection film, and an antireflection film. , optical filters, protective layers for color filters, pillars, etc. Although the present invention has been disclosed in the above preferred embodiments, the present invention is not intended to limit the invention, and it is intended that the invention may be modified and practiced without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. [Simple diagram of the diagram] Figure! It is an outline of each step in the manufacture of the touch panel member. Fig. 0 is a schematic cross-sectional view showing the touch panel member. [Description of main component symbols] 1 : Glass substrate 2 · Transparent electrode 3 : Transparent insulating film 4 : Wiring electrode 5 : Transparent protective film 65

Claims (1)

201142506 VII. Patent application scope: 1. A negative photosensitive resin composition containing (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol or more and 1,400 g/mol or less, (B) photopolymerization Starting agent, (C) polyfunctional monomer, (D) zirconium compound. 2. The negative photosensitive resin composition as described in claim 1, wherein the negative photosensitive resin composition is a cured film forming composition. 3. The negative photosensitive resin composition according to the first or second aspect of the invention, wherein the negative photosensitive resin composition is a protective film forming composition. The negative photosensitive resin composition of any one of the above-mentioned (A) carboxylic acid equivalents of 200 g/m〇1 or more and 1,400 g/m〇. The following alkali-soluble resin is a propylene glycol resin having an ethylenically unsaturated bond. The negative photosensitive resin composition of any one of the above-mentioned (A) carboxylic acid equivalent is 2 〇〇g/m〇i or more and 1,400 g. The alkali-soluble resin of /m〇l or less is a polyglycol having an ethylenically unsaturated bond. The negative photosensitive resin composition according to any one of the preceding claims, wherein the (D) # compound is a cerium oxide particle having an average particle diameter of 100 run or less. The photosensitive lion composition of any one of Claims 1 to 5, wherein the (9) contact compound is a general formula (any compound of the compound represented). More than, 66 201142506 [Chemical 1] 3 YRl represents hydrogen, alkyl, aryl, alkenyl and their substituents, R2 and 'non-nitrogen, alkyl, aryl, alkenyl, alkoxy and their substituents; multiple R, R and R3 The same can be different; n means an integer of 〇~4). ^ A touch panel protective film which is obtained by hardening a ruthenium dimming composition as described in the items of items i to 7 of the patent application. A metal wiring protective film which is obtained by hardening a negative photosensitive photosensitive resin composition according to any one of the above claims. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> Wiring. 67