JP5504689B2 - Negative photosensitive resin composition and touch panel material using the same - Google Patents

Description

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

  Currently, hard coat materials are used for various purposes, and are used for improving the surface hardness of, for example, containers for automobile parts, cosmetics, sheets, films, optical disks, thin displays, and the like. Properties required for the hard coat material include heat resistance, weather resistance, adhesiveness and the like in addition to hardness and scratch resistance. A representative example of the hard coat material is a radical polymerization type UV curable hard coat (see, for example, Non-Patent Document 1), and the constitution thereof is a polymerizable group-containing oligomer, monomer, photopolymerization initiator, and other additives. It is. The oligomer and the monomer are radically polymerized by UV irradiation to crosslink and obtain a high hardness film. This hard coat material has the advantage that the time required for curing is short and the productivity is improved, and a negative photosensitive material by a general radical polymerization mechanism can be used, and the production cost is low.

Touch panels are one of the main uses of hard coat materials. The current mainstream resistive film type touch panel cannot be processed at high temperature because the sensor is mounted on the film. For this reason, the above-mentioned UV curable hard coat that does not require thermal curing or can obtain a cured film by low-temperature curing has been favorably used (for example, see Patent Document 1). On the other hand, the capacitive touch panel that has been attracting attention in recent years forms an ITO (Indium Tin Oxide) film on glass that can be processed at a high temperature, and thus can form a transparent ITO film that has been sufficiently crystallized. . However, since there is no layer having a function of mitigating external impacts such as a resistive touch panel, higher hardness is required for the surface protective film. Furthermore, in order to perform processing for circuit connection, higher adhesion is required in heat treatment and chemical treatment in addition to photosensitivity. On the other hand, as a capacitive touch panel, for example, one having a protective film formed of high-hardness inorganic SiO ₂ , SiNx, transparent resin or the like using glass with ITO film as a substrate is disclosed. (For example, refer to Patent Document 2). However, the inorganic hard coat is formed by forming SiO ₂ or SiNx by CVD (Chemical Vapor Deposition) or by performing high-temperature treatment near 300 ° C. for a long time after coating SOG (Spin On Glass). Consumption increases. Furthermore, since the inorganic hard coat does not have photosensitivity, it is necessary to separately perform a protective film processing for circuit connection, which increases the number of processes, resulting in an increase in manufacturing cost.

  On the other hand, as an organic hard coat material, a UV curable coating composition containing a polymerizable group-containing oligomer, monomer, photopolymerization initiator and other additives is known. Such a composition has pattern processability and can provide a cured film having high hardness and transparency. However, since there are many organic components, there is a problem that sufficient adhesion to the substrate surface or element surface made of metal or inorganic substance cannot be obtained after heat treatment or chemical treatment, compared to inorganic hard coat. It was. As a method for improving the adhesion after heat treatment or chemical treatment, a method of adding a silane coupling agent having a heat-resistant skeleton has been proposed. For example, a composition containing an inorganic material, a resin binder, and a silane coupling agent having an isocyanurate skeleton (see, for example, Patent Document 3), a polysiloxane obtained by reacting an imide group-containing silane compound and an organosilane compound, and a quinonediazide compound And a photosensitive siloxane composition containing a solvent and a solvent (see, for example, Patent Document 4) and a photosensitive siloxane composition containing a polysiloxane, a quinonediazide compound, a solvent, and an imidosilane compound (for example, see Patent Document 5). Yes. In addition, as a low-temperature curable resin composition, an alkali-soluble copolymer, a polymerizable compound having an ethylenically unsaturated bond, a photo radical generator, a compound having two or more oxetanyl groups in a molecule, and an acid generator A resin composition containing a radiation-sensitive resin composition (for example, see Patent Document 6), a carboxyl group-containing polysiloxane, a solvent, a compound having a double bond and / or a triple bond, and a photopolymerization initiator (for example, , See Patent Document 7). Although these compositions improve the adhesion with Si atoms-containing glass or silicon nitride substrates, the substrates without Si atoms such as ITO and molybdenum have insufficient adhesion after heat treatment and chemical treatment. There was a problem.

JP 2001-330707 A JP 2007-279819 A (0024 paragraph) JP-A-11-185643 (Claim 1) JP 2008-185672 A (Claim 1) JP 2009-015285 A (Claim 1) JP 2009-3366 A (Claim 1) JP 2008-208342 A (Claims 1 and 2)

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

  An object of the present invention is to provide a negative photosensitive resin composition that provides a cured film having excellent adhesion to a substrate surface or an element surface composed of a metal or an inorganic material after heat treatment or chemical treatment. .

The present invention relates to (A) a polymer having a carboxyl group and / or a phenolic hydroxyl group and an ethylenically unsaturated double bond group,
(B) a photo radical polymerization initiator,
(C) a compound having a (meth) acryloyl group and not containing a silicon atom and an isocyanurate structure,
(D) An isocyanurate compound represented by the following general formula (1) and (E) an imidosilane compound and / or an oxetane compound represented by any one of the following general formulas (3) to (5) A negative photosensitive resin composition.

In the general formula (1), R ^{1 to} R ³ may be the same or different and each represents an ethylenically unsaturated double bond-containing group or a group represented by the following general formula (2).

In the general formula (2), each R ⁴ may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or an alkyl having 2 to 6 carbon atoms. A carbonyloxy group or a substituted product thereof is represented. n represents an integer of 1 to 5.

In the general formula (3), each of R ⁵ and R ⁶ may be the same or different each represents an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, 2 carbon atoms Represents an alkylcarbonyloxy group of ˜6 or a substituted product thereof. R ⁷ and R ⁸ represent a divalent organic group having 1 to 10 carbon atoms. R ⁹ represents a tetravalent organic group having 2 to 30 carbon atoms that does not contain a silicon atom. In the general formula (4), R ¹⁰ does not contain silicon atoms and ethylenically unsaturated double bond, a divalent organic group having 2 to 20 carbon atoms. R ¹¹ represents a divalent organic group having 1 to 10 carbon atoms. Each R ¹² may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituent thereof. Represents. In the general formula (5), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms that does not contain a silicon atom. R ¹⁴ represents a trivalent organic group having 2 to 20 carbon atoms. Each R ¹⁵ may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituent thereof. Represents.

  According to the negative photosensitive resin composition of the present invention, it is possible to obtain a cured film having excellent adhesion to a substrate surface or an element surface made of a metal or an inorganic material after heat treatment or chemical treatment.

The negative photosensitive resin composition of the present invention is
(A) a polymer having a carboxyl group and / or a phenolic hydroxyl group and an ethylenically unsaturated double bond group,
(B) a photo radical polymerization initiator,
(C) a compound having a (meth) acryloyl group and not containing a silicon atom and an isocyanurate structure,
(D) containing an isocyanurate compound represented by the general formula (1) and (E) an imidosilane compound and / or an oxetane compound represented by any one of the general formulas (3) to (5). And

  The negative photosensitive resin composition of the present invention can be applied to ITO or molybdenum having no Si atom by combining (D) a specific isocyanurate compound and (E) a specific imidosilane compound and / or oxetane compound. It has a specific effect of dramatically improving the adhesion after heat treatment and chemical treatment. When either component (D) or component (E) is used alone, the adhesion with a substrate having Si atoms is improved, but the adhesion with a substrate having no Si atoms is insufficient. is there.

  Hereinafter, each component of the negative photosensitive resin composition of the present invention will be described.

  The negative photosensitive resin composition of the present invention contains (A) a polymer having a carboxyl group and / or a phenolic hydroxyl group and an ethylenically unsaturated double bond group. By having a carboxyl group and / or a phenolic hydroxyl group, the negative photosensitive resin composition is excellent in alkali solubility (developability), and a good pattern can be formed while suppressing the residue after development. Moreover, since it has an ethylenically unsaturated double bond group, it has a (C) (meth) acryloyl group, which will be described later, and causes a radical polymerization reaction with a compound that does not contain a silicon atom and an isocyanurate structure. The crosslink density of the obtained cured film can be improved, and the hardness and scratch resistance of the cured film can be dramatically improved.

  (A) As a polymer having a carboxyl group and / or a phenolic hydroxyl group and an ethylenically unsaturated double bond group, an acrylic resin, polysiloxane, vinyl ether resin, polyhydroxystyrene, novolac resin, polyimide having these groups, Examples thereof include polyamide. A polymer having a carboxyl group and / or a phenolic hydroxyl group may be formed and then an ethylenically unsaturated double bond group may be introduced, or an ethylenically unsaturated double bond group may be introduced simultaneously with the polymer formation. It may be a thing. Among these polymers, acrylic resin, polysiloxane, vinyl ether resin, and polyhydroxystyrene are preferable because of the ease of introduction of the ethylenically unsaturated double bond group. Moreover, you may contain 2 or more types of these polymers.

  Although a preferable example is given below as a polymer of (A), it is not limited to this.

  As an acrylic resin having a carboxyl group and / or a phenolic hydroxyl group, (a) a radical polymerizable compound having a carboxyl group and / or a phenolic hydroxyl group, if necessary, using another radical polymerizable compound and a radical polymerization initiator After radical polymerization by a known method, for example, a method obtained by addition reaction of (d) an epoxy compound having an ethylenically unsaturated double bond group by the method described in JP-A No. 05-170517. It is done. Examples of the other radical polymerizable compound include (b) a radical polymerizable compound having a phenyl group and (c) a radical polymerizable compound having an alicyclic hydrocarbon group. By having a phenyl group, the heat resistance of the cured film is improved, and by having an alicyclic hydrocarbon group, the transparency of the cured film is improved. For this reason, it is preferable that the acrylic resin having a carboxyl group and / or a phenolic hydroxyl group further has a phenyl group and an alicyclic hydrocarbon group.

  Examples of the radical polymerizable compound (a) include an unsaturated carboxylic acid having an ethylenically unsaturated double bond, a phenolic hydroxyl group, or an ethylenically unsaturated group having a group that decomposes with an acid or alkali to generate a phenolic hydroxyl group. A double bond compound etc. are mentioned. Two or more of these may be used.

  Examples of the unsaturated carboxylic acid having an ethylenically unsaturated double bond include (meth) acrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, fumaric acid, crotonic acid, 1,4-cyclohexenedicarboxylic acid, o -, M-, p-vinylbenzoic acid, (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropionic acid, 2- (meth) acryloyloxypropionic acid, 4- (meth) acryloyloxybutanoic acid, 4- (Meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 2- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxyphthalic acid, 3- (meth) acryloyloxyphthalic acid, 4- (Meth) acryloyloxyisophthalic acid, 5- (meth) acryloyloxyisophthalic acid Mention may be made of the acid and the like. “(Meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, “(meth) acryloyl” is a generic term for acryloyl and methacryloyl, and so on.

  Examples of the ethylenically unsaturated double bond compound having a phenolic hydroxyl group or a group that decomposes with an acid or an alkali to form a phenolic hydroxyl group include, for example, o-, m-, p-hydroxystyrene, o-, m-, p. -T-butoxystyrene, isopropenylphenol, o-, m-, p-acetoxystyrene and the like can be mentioned.

  Of these, (meth) acrylic acid, p-hydroxystyrene, and isopropenylphenol are preferable from the viewpoints of solubility in an alkaline developer and adhesion to a base substrate during development.

  Examples of the radically polymerizable compound (b) having a phenyl group include styrene, α-, o-, m-, p-methylstyrene, benzyl (meth) acrylate, and the like. Of these, styrene and α-methylstyrene are preferred from the viewpoint of the heat resistance of the cured film and the solubility in an alkali developer. Two or more of these may be used.

  Examples of the radical polymerizable compound (c) having an alicyclic hydrocarbon group include cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, (Meth) acrylic acid 4-methoxycyclohexyl, (meth) acrylic acid 2-cyclopropyloxycarbonylethyl, (meth) acrylic acid 2-cyclopentyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexyloxycarbonylethyl, (meth) 2-cyclohexenyloxycarbonylethyl acrylate, 2- (4-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclode (meth) acrylate Nyl, tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, 1-methyladamantyl (meth) acrylate, etc. it can. Of these, cyclopropyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclo (meth) acrylate Decanyl and adamantyl (meth) acrylate are preferred. From the viewpoint of water absorption of the cured film and adhesion to the base substrate during development, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and tetracyclodecanyl (meth) acrylate are more preferable. Two or more of these may be used.

  Furthermore, other radically polymerizable compounds can be copolymerized with the above (a). For example, butadiene, 2,3-dimethylbutadiene, N, N-dimethylacrylamide, N, N-dipropylacrylamide, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl acetate, (meth) Examples include methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and t-butyl (meth) acrylate. From the viewpoint of adjusting the molecular weight, butadiene, methyl (meth) acrylate, and ethyl (meth) acrylate are preferred. Two or more of these may be used.

  Examples of the epoxy compound having (d) an ethylenically unsaturated double bond group include glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-n-propylglycidyl (meth) acrylate, ( Α-n-butylglycidyl methacrylate), 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate Allyl glycidyl ether, vinyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl Ether, α-methyl-p-vinylbenze Glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-tri Glycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyloxy And methyl styrene. From the viewpoint of pattern workability and improved hardness of the cured film, glycidyl (meth) acrylate, p-vinylbenzyl glycidyl ether, and vinyl glycidyl ether are preferred. Two or more of these may be used.

  In the acrylic resin having a carboxyl group and / or a phenolic hydroxyl group, the ratio of the compounds (a) to (d) and other radical polymerizable compounds used for the polymerization is preferably (a ) Is 10 to 45 mol%, (b) is 10 to 40 mol%, (c) is 10 to 40 mol%, (d) is 10 to 35 mol%, and other radical polymerizable compounds are less than 10 mol%. is there. If (a) is 10 mol% or more, the solubility with respect to alkali developability will improve, and if it is 45 mol% or less, the adhesiveness with the base substrate at the time of development will improve. If (b) is 10 mol% or more, heat resistance will improve, and if it is 40 mol% or less, the solubility with respect to alkali developability will improve. If (c) is 10 mol% or more, the hygroscopicity can be reduced, and if it is 40 mol% or less, the adhesion to the base substrate during development is improved. If (d) is 10 mol% or more, the hardness is further improved, and if it is 35 mol% or less, the adhesion to the base substrate during development is improved.

  The molecular weight of the acrylic resin having a carboxyl group and / or a phenolic hydroxyl group is preferably a weight average molecular weight of 5,000 or more in terms of polystyrene measured by gel permeation chromatography (GPC). , Developability and heat resistance are improved. On the other hand, 50,000 or less is preferable, 40,000 or less is more preferable, 36000 or less is more preferable, and the pattern shape, sensitivity, and developability are good.

  The acid value of the acrylic resin having a carboxyl group and / or a phenolic hydroxyl group is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, from the viewpoint of sensitivity. On the other hand, from the viewpoint of the remaining film rate, 150 mgKOH / g or less is preferable, and 130 mgKOH / g or less is more preferable.

  Examples of the solvent used in producing the acrylic resin having a carboxyl group and / or a phenolic hydroxyl group include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; cyclic ethers such as tetrahydrofuran and dioxane; Aromatic hydrocarbons such as benzene, toluene and xylene; aprotic polar solvents such as dimethylformamide (DMF) and N-methylpyrrolidone (NMP); acetates such as ethyl acetate and butyl acetate; diethylene glycol dimethyl ether and propylene glycol Glycol ethers such as monomethyl ether; glycol ether esters such as propylene glycol monomethyl ether acetate; cellosolve esters such as methyl cellosolve acetate And the like. The amount of these reaction solvents used is preferably 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

  Examples of the polymerization initiator used for producing the acrylic resin having a carboxyl group and / or a phenolic hydroxyl group include 2,2′-azobisisobutyronitrile and 2,2′-azobis- (2,4 -Dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds, benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1- Examples thereof include organic peroxides such as bis- (t-butylperoxy) cyclohexane, hydrogen peroxide, and the like. When a peroxide is used as an initiator, it may be combined with a reducing agent as a redox initiator.

  Among the polymers of (A) used in the negative photosensitive resin composition of the present invention, polysiloxane having a carboxyl group and an ethylenically unsaturated double bond group is used as (e) a carboxyl group and / or dicarboxylic acid anhydride. A known method such as a method described in JP-A-2006-178436, an organosilane compound having a physical group, (f) an organosilane compound having an ethylenically unsaturated double bond group, and if necessary, other organosilane compounds And polysiloxane obtained by condensing the hydrolyzate. Examples of other organosilane compounds include organosilane compounds having fluorine, organosilane compounds having a phenyl group, and organosilane compounds having an alicyclic hydrocarbon group. By containing fluorine, the scratch resistance of the cured film is improved. Moreover, the heat resistance of a cured film improves by having a phenyl group, and the transparency of a cured film improves by having an alicyclic hydrocarbon group. In the present invention, the polysiloxane having a carboxyl group and an ethylenically unsaturated double bond group preferably has a phenyl group and an alicyclic hydrocarbon group.

  Of the organosilane compounds having a carboxyl group and / or dicarboxylic anhydride group (e), examples of the organosilane compound having a carboxyl group include a urethane group-containing organosilane compound represented by the following general formula (6): And urea group-containing organosilane compounds represented by the following general formula (7). Two or more of these may be used.

In the general formula ^{(6) ~ (7),} R 16 and ^{R 18} represents a divalent organic group having 1 to 20 carbon atoms. R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹⁹ may be the same or different, and represents an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituent thereof. Represent.

Specific examples of R ^{16 in} the general formulas (6) to (7) include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a phenylene group, —CH ₂ —C ₆ H ₄ —CH ₂ —. , Hydrocarbon groups such as —CH ₂ —C ₆ H ₄ — and the like. Among these, a hydrocarbon group having an aromatic ring is preferable from the viewpoint of heat resistance.

R ¹⁷ in the general formula (7) is preferably hydrogen or a methyl group from the viewpoint of reactivity.

Specific examples of R ^{18 in} the general formulas (6) to (7) include hydrocarbon groups such as a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-pentylene group, an oxymethylene group, Examples thereof include an oxyethylene group, an oxy n-propylene group, an oxy n-butylene group, and an oxy n-pentylene group. Among these, methylene group, ethylene group, n-propylene group, n-butylene group, oxymethylene group, oxyethylene group, oxy n-propylene group, and oxy n-butylene group are preferable from the viewpoint of easy synthesis.

Among R ^{19 in} the general formulas (6) to (7), specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the viewpoint of ease of synthesis, a methyl group or an ethyl group is preferable. Specific examples of the alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. From the viewpoint of ease of synthesis, a methoxy group or an ethoxy group is preferable. Specific examples of the alkylcarbonyloxy group include an acetoxy group. In addition, examples of the substituent of the substituent include a methoxy group and an ethoxy group, and specific examples of the substituent include a 1-methoxypropyl group and a methoxyethoxy group.

  The urethane group-containing organosilane compound represented by the general formula (6) includes a hydroxycarboxylic acid compound represented by the following general formula (8) and an organosilane having an isocyanate group represented by the following general formula (10). It can be obtained from a compound by a known urethanization reaction. The urea group-containing organosilane compound represented by the general formula (7) has an aminocarboxylic acid compound represented by the following general formula (9) and an isocyanate group represented by the following general formula (10). It can be obtained from an organosilane compound by a known urea reaction.

In the general formula ^{(8) ~ (10),} R 16 and ^{R 18} represents a divalent organic group having 1 to 20 carbon atoms. R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹⁹ may be the same or different and represents an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or a substituted product thereof. The preferable specific example of each group is the same as the example in General formula (6)-(7).

  Other examples of the organosilane compound having a carboxyl group include compounds represented by the following general formula (11).

In the general formula (11), R ²⁰ represents an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituted product thereof. Represents. p represents an integer of 1 to 3, and q represents an integer of 2 to 20. When p is 2 or more, each R ²⁰ may be the same or different.

  Among the organosilane compounds having a carboxyl group and / or a dicarboxylic anhydride group, examples of the organosilane compound having a dicarboxylic anhydride group include any of the following general formulas (12) to (14). The organosilane compound represented by these is mentioned. Two or more of these may be used.

In the general formulas (12) to (14), each R ²¹ may be the same or different, and an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or 2 carbon atoms. Represents an alkylcarbonyloxy group of ˜6 or a substituted product thereof. R ^{22 to} R ^{24 each} have a single bond, a chain or cyclic aliphatic hydrocarbon group, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group, or a substituent thereof, or any of these. Represents a divalent group. h and l represent an integer of 0 to 3.

Specific examples of R ^{22 to} R ²⁴ include —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —O—, —C ₃ H ₆ OCH ₂ CH (OH) CH ₂ O. ₂ C—, —CO—, —CO ₂ —, —CONH—, organic groups shown below and the like can be mentioned.

  Specific examples of the organosilane compound represented by the general formula (12) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic acid. An anhydride etc. are mentioned. Specific examples of the organosilane compound represented by the general formula (13) include 3-trimethoxysilylsilylpropylcyclohexyl dicarboxylic acid anhydride. Specific examples of the organosilane compound represented by the general formula (14) include 3-trimethoxysilylsilylpropylphthalic anhydride.

  Specific examples of the organosilane compound (f) having an ethylenically unsaturated double bond group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, γ -Glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styryltriacetoxysilane, γ- (meth) acryloylpropyltrimethoxysilane, γ- (meta ) Acryloylpropyltriethoxysilane, γ- (meth) acryloylpropylmethyldimethoxysilane, γ- (meth) acryloylpropylmethyldiethoxysilane, and the like. Two or more of these may be used. Of these, γ- (meth) acryloylpropyltrimethoxysilane and γ- (meth) acryloylpropyltriethoxysilane are preferred from the viewpoint of further improving the hardness of the cured film and the sensitivity during pattern processing.

  Preferable examples of the fluorine-containing organosilane compound include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and tridecafluorooctyltriethoxysilane. Two or more of these may be used.

  Specific examples of the organosilane compound having a phenyl group include phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltri (methoxyethoxy) silane. Two or more of these may be used.

  Specific examples of the organosilane compound having an alicyclic hydrocarbon group include (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4). -Epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 2- (3,4-epoxycyclohexyl), 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3 4-epoxycyclohexyl) butyltrime Kishishiran, 4- (3,4-epoxycyclohexyl) butyl triethoxy silane, and the like. Two or more of these may be used.

  Examples of other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, and methyltri (methoxyethoxy) silane.

  Organosilane in which polysiloxane having carboxyl group and ethylenically unsaturated double bond group includes organosilane compound having carboxyl group and / or dicarboxylic anhydride group and organosilane compound having ethylenically unsaturated double bond group When the compound is obtained by hydrolyzing the compound in the presence of metal compound particles described later and condensing the hydrolyzate, the hardness, scratch resistance, and crack resistance of the cured film are further improved. By polymerizing polysiloxane in the presence of metal compound particles, chemical bonds (covalent bonds) with metal compound particles occur in at least part of the polysiloxane, and the metal compound particles are uniformly dispersed and the coating solution is stored. This is considered to improve stability and homogeneity of the cured film. Moreover, the refractive index of the cured film obtained can be adjusted with the kind of metal compound particle.

  Examples of metal compound particles include silicon compound particles, aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, barium compound particles, and the like, and an appropriate one can be selected depending on the application. For example, in order to obtain a cured film having a high refractive index, titanium compound particles such as titanium oxide particles and zirconium compound particles such as zirconium oxide particles are preferably used. In order to obtain a cured film having a low refractive index, it is preferable to contain hollow silica particles and the like.

Examples of commercially available metal compound particles include tin oxide-titanium oxide composite particles “OPTRAIK” (registered trademark) TR-502, “OPTRAIK” TR-504, and silicon oxide-titanium oxide composite particles “OPT”. “Lake” TR-503, “Optlake” TR-513, “Optlake” TR-520, “Optlake” TR-527, “Optlake” TR-528, “Optlake” TR-529, titanium oxide particles "Optlake" TR-505 (above, trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd.), zirconium oxide particles (manufactured by High Purity Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particles (JGC Catalysts & Chemicals Industries ( Co., Ltd.), tin oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), silica particles IPA-ST, MIBK-ST, IPA-ST-L, IPA-S -ZL, PGM-ST (above, trade name, manufactured by Nissan Chemical Industries, Ltd.), "Oscal (registered trademark)" 101, "Oscal" 105, "Oscal" 106, "Cataloid (registered trademark)" -S ( As described above, trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), "Quartron (registered trademark)" PL-2L-PGME, "Quartron" PL-2L-BL, "Quartron" PL-2L-DAA, "Quartron" PL- 2L, GP-2L (above, trade name, manufactured by Fuso Chemical Industry Co., Ltd.), (SiO ₂ ) SG-SO100 (trade name, manufactured by Kyoritsu Material Co., Ltd.), “Leolo Seal (registered trademark)” (trade name, (Manufactured by Tokuyama Corporation), “Optlake” TR-113, which is a hollow silica particle.

  The number average particle diameter of the metal compound particles is preferably 1 nm to 200 nm. In order to obtain a cured film having a high transmittance, the number average particle diameter is more preferably 1 nm to 70 nm. Here, the number average particle diameter of the metal compound particles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a transmission electron microscope, or a scanning electron microscope.

  There is no restriction | limiting in particular in content of a metal compound particle, Although it can be set as a suitable quantity according to a use, It is common to set it as about 1-70 weight% in solid content of a negative photosensitive resin composition.

  The polysiloxane having a carboxyl group and an ethylenically unsaturated double bond group is obtained by hydrolyzing an organosilane compound in the presence of metal compound particles as necessary, and then the hydrolyzate in the presence of a solvent or without solvent. Can be obtained by a condensation reaction. Various conditions for the hydrolysis reaction, such as acid concentration, reaction temperature, reaction time, etc. can be appropriately set in consideration of the reaction scale, reaction vessel size, shape, etc., for example, in solvent, organosilane compound After adding an acid catalyst and water over 1 to 180 minutes, the reaction is preferably carried out at room temperature to 110 ° C. for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 30 to 105 ° C.

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

  After obtaining the silanol compound by the hydrolysis reaction of the organosilane compound, it is preferable to carry out the condensation reaction by heating the reaction solution as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours. In order to increase the degree of polymerization of the polysiloxane, reheating or a base catalyst may be added.

  The solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent. Preferred examples of the solvent include diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono t-butyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, etc. Is mentioned.

  When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the reaction. In addition, after hydrolysis according to the purpose, an appropriate amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

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

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

  The content of the carboxyl group in the polysiloxane having a carboxyl group and an ethylenically unsaturated double bond group is preferably 0.1 mol or more with respect to 1 mol of Si atoms, and can improve the crack resistance of the cured film. it can. More preferably, it is 0.2 mol or more, More preferably, it is 0.3 mol or more. Moreover, 0.8 mol or less is preferable and the hardness of a cured film can be improved more. More preferably, it is 0.6 mol or less.

The content of the carboxyl group in the polysiloxane is, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of the polysiloxane, and the ratio of the peak area of Si to which the carboxyl group is bonded to the peak area of Si to which the carboxyl group is not bonded. Can be obtained from Moreover, when Si and a carboxyl group are not directly bonded, the carboxyl group content of the whole polysiloxane is calculated from the integration ratio of the peak derived from the carboxyl group and other peaks excluding silanol from ¹ H-nuclear magnetic resonance spectrum. The content of the carboxyl group that is indirectly bonded is calculated together with the result of the ²⁹ Si-nuclear magnetic resonance spectrum.

  The content of the ethylenically unsaturated double bond group in the polysiloxane having a carboxyl group and an ethylenically unsaturated double bond group is preferably 0.01 mol or more, preferably 0.1 mol or more with respect to 1 mol of the Si atom. Is more preferable. Moreover, 0.6 mol or less is preferable and 0.4 mol or less is more preferable. If it is the said range, the cured film which can make hardness and crack resistance compatible at a higher level will be obtained.

The content of the ethylenically unsaturated double bond group in the polysiloxane can be determined by, for example, performing thermogravimetric analysis (TGA) of the obtained polymer up to 900 ° C. in the atmosphere and confirming that the ash content is SiO ₂ by infrared absorption. After confirmation by analysis, the number of moles of Si atoms per gram of polysiloxane can be calculated from the weight reduction rate, and then the iodine value can be measured.

  The weight average molecular weight (Mw) of the polysiloxane having a carboxyl group and an ethylenically unsaturated double bond group used in the negative photosensitive resin composition of the present invention is not particularly limited, but in terms of polystyrene measured by GPC, Preferably it is 1,000 or more, More preferably, it is 2,000 or more. Moreover, Preferably it is 100,000 or less, More preferably, it is 50,000 or less. By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good.

  In the negative photosensitive resin composition of the present invention, the content of the polymer (A) is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application. 0.1 to 60% by weight in the solid content is common. 10% by weight or more in the solid content is more preferable.

  The negative photosensitive resin composition of the present invention contains (B) a radical photopolymerization initiator. (B) The photo-radical polymerization initiator may be anything as long as it decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals, but the cured film has a higher hardness. For this purpose, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having an amino group or benzoic acid ester compounds having an amino group are preferred. Two or more of these may be contained.

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

  (B) The content of the photo radical polymerization initiator is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more in the solid content of the negative photosensitive resin composition. Moreover, 20 weight% or less is preferable and 10 weight% or less is more preferable. By setting it as the said range, radical hardening can fully be advanced and elution of the residual radical polymerization initiator etc. can be prevented and solvent resistance can be ensured.

  The negative photosensitive resin composition of this invention contains the compound which has a (C) (meth) acryloyl group and does not contain a silicon atom and an isocyanurate structure. By having a (meth) acryloyl group, a radical polymerization reaction occurs with the ethylenically unsaturated double bond in the polymer (A) described above, so the crosslink density of the resulting cured film is improved and the hardness of the cured film is increased. And the scratch resistance can be dramatically improved. Moreover, since it can harden | cure with little light irradiation amount, the sensitivity of a negative photosensitive resin composition can be improved.

  (C) As specific examples of the compound having a (meth) acryloyl group and not containing a silicon atom and an isocyanurate structure, monofunctional specific examples include (meth) acrylic acid, methyl (meth) acrylate, (meth ) Butyl acrylate, hydroxyethyl (meth) acrylate, dimethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, acryloyl morphophore, 1-hydroxyethyl α-chloroacrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxyethyl α-chloroacrylate, 1-hydroxypropyl (meth) acrylate, 1-hydroxypropyl α-chloroacrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl α-chloroacrylate, (meth ) Acrylic acid 3-hydroxy Propyl, 3-hydroxypropyl α-chloroacrylate, 1-hydroxy-1-methylethyl (meth) acrylate, 1-hydroxy-1-methylethyl α-chloroacrylate, 2-hydroxy-1-methyl (meth) acrylate Ethyl, 2-hydroxy-1-methylethyl α-chloroacrylate, 1-hydroxybutyl (meth) acrylate, 1-hydroxybutyl α-chloroacrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxybutyl α- Chloroacrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxybutyl α-chloroacrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl α-chloroacrylate, 1-hydroxy- (meth) acrylate 1-methylpropyl, 1-hydride Xyl-1-methylpropyl α-chloroacrylate, 2-hydroxy-1-methylpropyl (meth) acrylate, 2-hydroxy-1-methylpropyl α-chloroacrylate, 1-hydroxy-2-methyl (meth) acrylate Propyl, 1-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydroxy-2-methylpropyl (meth) acrylate, 2-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydroxy (meth) acrylate -1,1-dimethylethyl, 2-hydroxy-1,1-dimethylethyl α-chloroacrylate, 1,2-dihydroxypropyl (meth) acrylate, 1,2-dihydroxypropyl α-chloroacrylate, (meth) acrylic Acid 2,3-dihydroxypropyl, 2,3-dihydro Cypropyl α-chloroacrylate, 2,3-dihydroxybutyl (meth) acrylate, 2,3-dihydroxybutyl α-chloroacrylate, p-hydroxystyrene, p-isopropenylphenol, phenethyl methacrylate, phenethyl acrylate, phenethyl α-chloro Acrylate, N-methylol (meth) acrylamide, α-chloroacrylic acid, crotonic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonanoic acid, 9-decanoic acid, 10 -Undecylenic acid, brassic acid, ricinoleic acid, 2- (methacryloyloxy) ethyl isocyanate, 2- (acryloyloxy) ethyl isocyanate, 2- (α-chloroacryloyloxy) ethyl isocyanate, isobornyl acrylate, tetrahydride It may be mentioned furfuryl acrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalic acid.

  As specific examples of polyfunctionality, 2,2- [9H-fluorene-9,9-diylbis (1,4-phenylene) bisoxy] diethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, glycerin di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapenta Erythritol deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate, pentape Taerythritol dodeca (meth) acrylate, dipentaerythritol hexaacrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, Examples include pentapentaerythritol undeca (meth) acrylate and pentapentaerythritol dodeca (meth) acrylate.

  As the compound (C), those having 6 or more (meth) acryloyl groups in one molecule are preferable from the viewpoint of improving hardness. Specifically, tripentaerythritol poly (meth) acrylate, tetrapentaerythritol poly (meth) acrylate, and pentapentaerythritol poly (meth) acrylate are preferable.

  The content of the compound (C) is preferably 5% by weight or more, more preferably 20% by weight or more in the solid content of the negative photosensitive resin composition. Moreover, 80 weight% or less is preferable and 70 weight% or less is more preferable.

  The negative photosensitive resin composition of the present invention contains (D) an isocyanurate compound represented by the following general formula (1). Two or more of these may be contained. Since the isocyanurate skeleton site interacts efficiently with the Si atom, the polymer of (A), and the compound of (C), after the heat treatment with the glass substrate or the silicon nitride substrate, which is a substrate having Si atoms, and chemical treatment Later adhesion is improved. On the other hand, with the component (D) alone, the effect of improving the adhesiveness is not observed with respect to molybdenum or ITO substrate having no Si atom. Further, by containing the compound (D), in addition to the heat resistance derived from the isocyanurate skeleton, an appropriate chain length and number of polymerizable groups are contained in one molecule, so that a cured film having high hardness is obtained. be able to.

In the general formula (1), R ^{1 to} R ³ may be the same or different and each represents an ethylenically unsaturated double bond-containing group or a group represented by the following general formula (2).

In the general formula (2), each R ⁴ may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or an alkyl having 2 to 6 carbon atoms. A carbonyloxy group or a substituted product thereof is represented. A methyl group, ethyl group, methoxy group, ethoxy group or acetoxy group is preferred. n represents an integer of 1 to 5.

Preferable examples of R ^{1 to} R ³ in the general formula (1) include an allyl group, a (meth) acryloylethyl group, — [(CH ₂ ) ₂ OCO— (CH ₂ ) ₅ —OCO—CH═CH ₂ ]. Group, the group represented by the general formula (2), and the like. Among these, from the viewpoints of hardness, heat resistance, adhesiveness after heat treatment and chemical treatment with a glass substrate or silicon nitride substrate, allyl group, (meth) acryloylethyl group, represented by the above general formula (2) The group is particularly preferred. In particular, the group represented by the general formula (2) has a silane site and selectively interacts with Si atoms, so that after heat treatment with a glass substrate or silicon nitride substrate, which is a substrate having Si atoms, and chemicals Since the adhesiveness after a process improves, it is preferable. In addition, the component (D) having the group represented by the general formula (2) is used in combination with the component (E) described later, so that the molybdenum or ITO substrate having no Si atom is also heat-treated. In addition, it is preferable in order to further improve the adhesion after chemical treatment.

  The content of the compound (D) is the solid content of the negative photosensitive resin composition from the viewpoint of adhesion after heat treatment and chemical treatment with a glass substrate or silicon nitride substrate which is a substrate having Si atoms. 0.1 weight% or more is preferable and 0.5 weight% or more is more preferable. On the other hand, from the viewpoint of pattern processability, it is preferably 20% by weight or less, and more preferably 15% by weight or less.

  The negative photosensitive resin composition of the present invention contains (E) an imidosilane compound and / or an oxetane compound represented by any one of the following general formulas (3) to (5). Two or more of these may be contained. In the case of the imide silane compound represented by any one of the general formulas (3) to (5), the imide skeleton site interacts efficiently with the Si atom, the polymer (A) and the compound (C), and the silane site Since this selectively interacts with those containing Si atoms, adhesion after heat treatment and chemical treatment with a glass substrate which is a substrate containing Si atoms or a silicon nitride substrate is improved. In the case of an oxetane compound, the oxetanyl group is ring-opened at the time of curing, and interacts efficiently with the Si atom, the polymer of (A) and the compound of (C), and a glass substrate, which is a substrate having Si atoms, is nitrided Adhesiveness after heat treatment and chemical treatment with the silicon substrate is improved. On the other hand, in any case, only the component (E) does not show an effect of improving adhesion to molybdenum or ITO substrate having no Si atom.

In the general formula (3), each of R ⁵ and R ⁶ may be the same or different each represents an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, 2 carbon atoms Represents an alkylcarbonyloxy group of ˜6 or a substituted product thereof. R ⁷ and R ⁸ represent a divalent organic group having 1 to 10 carbon atoms. R ⁹ represents a tetravalent organic group having 2 to 30 carbon atoms that does not contain a silicon atom.

In the general formula (4), R ¹⁰ does not contain silicon atoms and ethylenically unsaturated double bond, a divalent organic group having 2 to 20 carbon atoms. R ¹¹ represents a divalent organic group having 1 to 10 carbon atoms. Each R ¹² may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituent thereof. Represents.

In the general formula (5), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms that does not contain a silicon atom. R ¹⁴ represents a trivalent organic group having 2 to 20 carbon atoms. Each R ¹⁵ may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituent thereof. Represents.

In R ⁵ , R ⁶ , R ¹² , and R ¹⁵ in the general formulas (3) to (5), the alkyl group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like. Can be mentioned. Of these, a methyl group and an ethyl group are preferable. Specific examples of the alkoxyl group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group and the like. Of these, a methoxy group and an ethoxy group are preferable. Examples of the alkylcarbonyloxy group having 2 to 6 carbon atoms include an acetoxy group. Moreover, 1-methoxypropyl group etc. are mentioned as these substitution products.

In ^{R 7, R 8, R 11} in the general formula (3) to (4), specific examples of the divalent organic group having 1 to 10 carbon atoms, a methylene group, an ethylene group, n- propylene radical, n -Butylene group, n-pentylene group, oxymethylene group, oxyethylene group, oxy n-propylene group, oxy n-butylene group, oxy n-pentylene group, etc. are mentioned. Of these, a methylene group, an ethylene group, an n-propylene group, and an n-butylene group are preferable.

R ^{9 in the} general formula (3) represents a structural component of an acid dianhydride, preferably contains an aromatic ring or an aliphatic ring, and preferably has 5 to 30 carbon atoms. Examples of acid dianhydrides include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ) Ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride, bis (3,4-dicar Boxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxy) Phenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2 , 3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride , Aromatic tetracarboxylic dianhydrides such as 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, hydrogenated pyromellitic dianhydride, butanetetracarboxylic Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, “Licacid®” TDA-100 (trade name) , Manufactured by Shin Nippon Rika Co., Ltd.), "Licacid" BT-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), "EPICLON (registered trademark)" B-4400 (trade name, Dainippon Ink & Chemicals, Inc.) )) And an aliphatic tetracarboxylic dianhydride having the following structure.

When R ⁹ is an aromatic group such as a tolyl group or a naphthyl group, the cured film obtained from the negative photosensitive resin composition contains a compound having a structure similar to that of the aromatic imide oligomer as a coloring source. Transparency may be reduced. Moreover, when said aromatic group is contained, compatibility with the polymer of (A) component will fall and the light transmittance of a film | membrane may fall. Therefore, when R ⁹ is an aromatic group, it is preferable to reduce the content. On the other hand, when R ⁹ is an aliphatic organic group, it is preferable because it has a high light transmittance. Preferred specific examples of the compound represented by the general formula (3) are shown below.

R ^{10 in the} general formula (4) and R ^{14 in the} general formula (5) represent a structural component of the acid anhydride of the acid anhydride-containing silane, and preferably contain an aromatic ring or an aliphatic ring. The number of carbon atoms is preferably 4-20. Examples of acid anhydrides include maleic anhydride, phthalic anhydride, methyl phthalic anhydride, succinic anhydride, glutaric anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, cis-4-cyclohexene- 1,2-dicarboxylic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, 1,8-naphthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2 , 3-dicarboxylic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), “Licacid” HNA, “Licacid” HNA-100 (above, trade name, new Nippon Rika Co., Ltd.). Among these, phthalic anhydride, succinic anhydride, glutaric anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 1,8-naphthalic anhydride, 5-norbornene-2,3-dicarboxylic acid An anhydride and methyl phthalic anhydride are preferred. Among them, succinic anhydride, glutaric anhydride, and 5-norbornene-2,3-dicarboxylic anhydride are heat-resistant and transparent, after heat treatment with a glass substrate or silicon nitride substrate which is a substrate having Si atoms, and chemical treatment It is particularly preferable from the viewpoint of the later adhesiveness.

R ^{13 in the} general formula (5) represents a hydrogen atom or an organic group having 1 to 20 carbon atoms that does not contain a silicon atom. Specific examples of the organic group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, cyclohexyl group, 2-hydroxyethyl group, phenyl group, methoxyphenyl group, and methoxy group. Ethoxy group, n-propoxy group, isopropoxy group and the like, and methoxy group and ethoxy group are preferable. Moreover, 1-methoxypropyl group etc. are mentioned as these substitution products. In particular, adhesion after heat treatment and chemical treatment with a glass substrate or silicon nitride substrate in which a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, a 2-hydroxyethyl group, or a phenyl group is a substrate having Si atoms. In order to improve the property, it is preferable. In addition, when R ^{13 in the} general formula (5) is a hydrogen atom, a methyl group, a t-butyl group, or a 2-hydroxyethyl group, it does not have a Si atom when used in combination with the component (D) described above. It is also preferable for molybdenum and ITO substrates in order to further improve the adhesion after heat treatment and chemical treatment.

The imidosilane compound represented by the general formula (3) or (4) can be easily obtained from, for example, the following isocyanate silane compound and acid dianhydride by a known direct imidization method.
^{OCN-R 7 -Si- (R 5} ) 3
^{OCN-R 8 -Si- (R 6} ) 3
^{OCN-R 11 -Si- (R 12} ) 3
The definition of R < ⁵ > -R < ⁸ >, R < ¹¹ > -R < ¹² > is the same as the definition in General formula (3)-(4).

  The imidosilane compound represented by the general formula (4) or (5) can be easily obtained from, for example, an amine compound and an acid anhydride-containing compound by a known imidization method via an amic acid. From the viewpoint of reducing coloring due to by-products, the synthesis method of the imide silane compound represented by the general formula (4) is similar to the imide silane compound represented by the general formula (3) and the isocyanate silane compound and the acid anhydride. A direct imidization method comprising a product is preferred.

  The amine compound and acid anhydride-containing compound used for the imidosilane compound represented by the general formula (4) are shown below.

Definition of R ¹⁰ to R ¹² are as defined in the general formula (4).

  The amine compound and acid anhydride-containing compound used for the imidosilane compound represented by the general formula (5) are shown below.

The definition of R < ¹³ > -R < ¹⁵ > is the same as the definition in General formula (5).

  Among the imidosilane compounds represented by any one of these general formulas (3) to (5), the one represented by the general formula (5) is a heat treatment with a glass substrate or a silicon nitride substrate which is a substrate having Si atoms. More preferable from the viewpoint of adhesion after and after chemical treatment. This is because the nitrogen atom of the imide group faces the direction in which the silane moiety and C = O of the imide group are bonded, so the silane moiety interacts with the one containing Si atoms, and the imide moiety is ( In addition to interacting efficiently with the polymer of A) and the compound of (C), it is thought to selectively interact with those containing Si atoms.

  Moreover, what is represented by the general formula (3) or the general formula (5) is used in combination with the component (D) described above, so that the molybdenum or ITO substrate having no Si atom is also heat-treated. In addition, it is preferable in order to further improve the adhesion after chemical treatment. In the case of what is represented by the general formula (3), since there are two imide groups in one molecule, it interacts strongly with the substrate having no Si atom in combination with the component (D). It is estimated that. In the case of the compound represented by the general formula (5), it is presumed that, in combination with the component (D), the direction of the imide group is suitable for strong interaction with a substrate having no Si atom. Among these, those represented by the general formula (5) are particularly preferable for molybdenum and ITO substrates having no Si atom because the adhesion after heat treatment and after chemical treatment is further improved.

  Since the imidosilane compound represented by any one of these general formulas (3) to (5) has high reactivity at low temperatures, a cured film is produced by low-temperature heat treatment at, for example, 130 to 170 ° C. due to restrictions on the base substrate. In particular, it can be preferably used. Moreover, it can be preferably used also in the case of forming a cured film by high-temperature treatment at 180 to 280 ° C.

  The oxetane compound is not particularly limited as long as it is a compound having an oxetanyl group, but a compound having a silicon atom is preferable. The effect of selectively interacting with silicon atoms containing Si atoms is added, dramatically improving the adhesion after heat treatment and chemical treatment with glass substrates, silicon nitride substrates, and silicon nitride substrates. To do. In addition, the oxetane compound having a silicon atom can be used in combination with the component (D) described above to further improve the adhesion after heat treatment and chemical treatment to molybdenum and ITO substrate having no Si atom. This is preferable.

  Specific examples of oxetane compounds having no silicon atom include “Aron Oxetane (registered trademark)” OXT-101 (oxetane alcohol), “Aron Oxetane” OXT-221 (di [1-ethyl (3-oxetanyl)] methyl Ether), “Aron oxetane” OXT-121 (main component 1,4-bis [[(3-ethyl-3-oxetanyl) methoxy] methyl] benzene) (above, manufactured by Toa Gosei Co., Ltd.), “Ethanacol (registered) Trademark) "OXBP (Bis [(3-ethyl-3-oxetanyl) methyl] biphenyl-4,4'-dicarboxylate)," Ethanacol "OXTP (Bis [(3-ethyl-3-oxetanyl) methyl] terephthalate) (Above, manufactured by Ube Industries, Ltd.).

  Examples of the oxetane compound having a silicon atom include a compound represented by the following general formula (17) or a compound represented by the following general formula (18) which is a condensate thereof.

Si (R ²⁵ ) _x (OR ²⁶ ) _4-x (17)
In the general formula (17), R ²⁵ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R ²⁶ may be the same or different and is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, or the following general group. The oxetanyl group containing organic group represented by Formula (19) is represented. However, at least one of R ²⁶ is an oxetanyl group-containing organic group represented by the following general formula (19). x represents an integer of 0 to 3.

In the general formula (18), R ^{27 to} R ²⁸ may be the same or different, and are a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Represents. R ^{29 to} R ³² may be the same or different and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 2 to 5 carbon atoms. The alkylcarbonyl group or the oxetanyl group-containing organic group represented by the general formula (19) is represented. However, at least one of R ^{29 to} R ³² is an oxetanyl group-containing organic group represented by the general formula (19). t and u represent the range of 0-10.

In the general formula (19), R ^{33 to} R ³⁷ represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. s represents the integer of 1-6.

  The oxetane compound represented by the general formula (18) can be synthesized using, for example, the following two methods. The first method is a method obtained from the oxetanyl group-containing alkoxysilane represented by the general formula (17) by a known hydrolysis condensation reaction. In the second method, a compound represented by the following general formula (20) is heat-condensed by a known method without hydrolysis, and a hydroxyl group-containing oxetane compound represented by the following general formula (21) and a known ether This is a method obtained by an exchange reaction.

Si (R ³⁸ ) _y (OR ³⁹ ) _4-y (20)
In the general formula (20), R ³⁸ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R ³⁹ may be the same or different and represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms. y represents an integer of 0-2.

In the general formula (21), R ^{33 to} R ³⁷ represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. s represents the integer of 1-6.

  Specific examples of the compound represented by the general formula (17) include (oxetane-3-yl) methyltrimethoxysilane, (oxetane-3-yl) methyltriethoxysilane, and (oxetane-3-yl) methyltri Acetoxysilane, [(oxetane-3-yl) methyl] methyldimethoxysilane, [(oxetane-3-yl) methyl] methyldiethoxysilane, [(oxetane-3-yl) methyl] methyldiacetoxysilane, [(oxetane -3-yl) methyl] ethyldimethoxysilane, [(oxetane-3-yl) methyl] ethyldiethoxysilane, [(oxetane-3-yl) methyl] ethyldiacetoxysilane, [(oxetane-3-yl) methyl ] Phenyldimethoxysilane, [(oxetane-3-yl) methyl] phenyldietoxy Silane, [(oxetane-3-yl) methyl] phenyldiacetoxysilane, di [(oxetane-3-yl) methyl] dimethoxysilane, di [(oxetane-3-yl) methyl] diethoxysilane, di [(oxetane -3-yl) methyl] diacetoxysilane, di [(oxetane-3-yl) methyl] methylmethoxysilane, di [(oxetane-3-yl) methyl] methylethoxysilane, di [(oxetane-3-yl) Methyl] methylacetoxysilane, di [(oxetane-3-yl) methyl] ethylmethoxysilane, di [(oxetane-3-yl) methyl] ethylethoxysilane, di [(oxetane-3-yl) methyl] ethylacetoxysilane , Di [(oxetane-3-yl) methyl] phenylmethoxysilane, di [(oxetane- -Yl) methyl] phenylethoxysilane, di [(oxetane-3-yl) methyl] phenylacetoxysilane, tri [(oxetane-3-yl) methyl] methoxysilane, tri [(oxetane-3-yl) methyl] ethoxy Silane, tri [(oxetane-3-yl) methyl] acetoxysilane, and the like can be given. Among these, those having a methoxy group are more preferable from the viewpoint of hydrolyzability.

  Specific examples of the compound represented by the general formula (20) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, and ethyltrimethoxysilane. , Ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, Diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, tet Acetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, cyclohexyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diethyldiacetoxysilane, diphenyldiacetoxysilane, methylphenyl And diacetoxysilane. Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, which have less steric hindrance due to ether exchange reactivity. More preferred is ethoxysilane.

  Oxetane compound having 4 or more oxetanyl groups in one molecule from the viewpoint of adhesion to a glass substrate or silicon nitride substrate, which is a substrate having Si atoms, and adhesion to molybdenum or ITO substrate not having Si atoms Is more preferable, and the oxetane compound represented by the general formula (18) is particularly preferable.

Commercially available oxetane compounds include TESOX, TMSOX represented by the general formula (17) (above, trade name, manufactured by Toa Gosei Co., Ltd.), and “Aron oxetane” OXT represented by the general formula (18). -191 (R ^{29 to} R ³² are (3-ethyl-3-oxetanyl) methyl group, t = 0, u = average 5), OX-SQ, OX-SQ-H (above, trade name, Toa Gosei Co., Ltd.) ))).

  Since these oxetane compounds have low reactivity at low temperatures as compared with imidosilane compounds, they can be preferably used when a cured film is formed by high-temperature treatment at 180 to 280 ° C., for example.

  (E) The total content of the imidosilane compound and the oxetane compound represented by any one of the general formulas (3) to (5) is the viewpoint of adhesion after heat treatment with a glass substrate or silicon nitride substrate and after chemical treatment. Therefore, 0.2% by weight or more in the solid content of the negative photosensitive resin composition is preferable, and 0.5% by weight or more is more preferable. On the other hand, from the viewpoint of pattern processability, it is preferably 20% by weight or less, and more preferably 15% by weight or less.

  In the present invention, the combined use of the compound (D) and the compound (E) exhibits adhesion after heat treatment and chemical treatment even for molybdenum and ITO, which are materials not containing Si atoms. To do. The preferable content of the compound (D) and the compound (E) for expressing the adhesiveness is 5% to 20% by weight in total in the solid content of the negative photosensitive resin composition, And it is preferable that the ratio of the compound of (D) with respect to the total content in the compound of (D) and the compound of (E) is 20 to 80 weight%. If the total content is 5% by weight or more, the adhesion to molybdenum or ITO is further improved, and if it is 20% by weight or less, the pattern workability is good. Moreover, if the ratio of the compound of (D) with respect to the total content in the compound of (D) and the compound of (E) is 20 weight% or more, adhesiveness with molybdenum or ITO will improve more and it will be 80 weight%. If it is below, pattern workability will become favorable.

  The negative photosensitive resin composition of the present invention preferably contains (F) a polysiloxane having an ethylenically unsaturated double bond group and not containing a carboxyl group and a phenolic hydroxyl group. By containing such polysiloxane, the scratch resistance of the cured film obtained from the negative photosensitive resin composition is improved. Two or more of these may be contained. The polysiloxane of (F) can be obtained by hydrolyzing (f) an organosilane compound having an ethylenically unsaturated double bond group together with another organosilane compound, if necessary, and condensing the hydrolyzate. it can. Hydrolysis reaction conditions, solvents used, and the like are the same as those described for the polymer (A).

  Examples of the organosilane compound (f) having an ethylenically unsaturated double bond group used for the polysiloxane (F) include those exemplified for the polymer (A). Of these, γ- (meth) acryloylpropyltrimethoxysilane and γ- (meth) acryloylpropyltriethoxysilane are preferred from the viewpoint of further improving the scratch resistance of the cured film and the sensitivity during pattern processing.

  Moreover, as another organosilane compound used for the polysiloxane of (F), what was illustrated with the polymer of (A) is mentioned. From the viewpoint of improving slipperiness and scratch resistance, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltri Methoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, and diethyldimethoxysilane are preferred. In particular, from the viewpoint of easy availability and improved slipperiness due to water repellency, trifluoropropyltrimethoxysilane, tridecafluorooctyltriethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane Diethyldimethoxysilane is more preferable.

  The content of the ethylenically unsaturated double bond group in the polysiloxane (F) is preferably 0.01 mol or more, more preferably 0.1 mol or more with respect to 1 mol of Si atoms. Moreover, 0.6 mol or less is preferable and 0.4 mol or less is more preferable. If it is the said range, photosensitivity and abrasion resistance of a cured film can be made compatible at a higher level. The content of the ethylenically unsaturated double bond group in the polysiloxane can be calculated by the method described for the polymer (A).

  The weight average molecular weight (Mw) of the polysiloxane (F) is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, in terms of polystyrene measured by GPC. Moreover, Preferably it is 100,000 or less, More preferably, it is 50,000 or less. By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good.

  In the negative photosensitive resin composition of the present invention, the content of the polysiloxane (F) is preferably 0.03% by weight or more, preferably 0.05% by weight or more in the solid content from the viewpoint of improving slipperiness and hardness. Is more preferable. On the other hand, from the viewpoint of compatibility and transparency in the composition, it is preferably 5% by weight or less, more preferably 3% by weight or less.

  The negative photosensitive resin composition of the present invention may contain a thermal acid generator. Crosslinking is accelerated by the thermal acid generator, and the hardness of the cured film can be improved. Specific examples of the thermal acid generator preferably used include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI -110L, SI-145L, SI-150L, SI-160L, SI-180L (above, trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, their methanesulfonate, trifluoromethanesulfonate, Camphorsulfonate, p-tolu Nsuruhon acid salts. Preferably 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyl Oxyphenylmethylsulfonium, these methanesulfonates, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate. Two or more of these may be contained.

  The content of the thermal acid generator is preferably 0.01% by weight or more in the solid content of the negative photosensitive resin composition, and the hardness of the cured film is improved. On the other hand, it is preferably 10% by weight or less, more preferably 0.5% by weight or less, from the viewpoints of sensitivity, crack resistance and transparency.

  The negative photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability of the composition is improved, and the resolution after development is improved in applications requiring pattern processing. Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, 4-methoxyphenol and the like.

  The content of the polymerization inhibitor is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more in the solid content of the negative photosensitive resin composition. On the other hand, from the viewpoint of keeping the hardness of the cured film high, it is preferably 5% by weight or less, and more preferably 1% by weight or less.

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

  Examples of ultraviolet absorbers for benzotriazole compounds include 2- (2Hbenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-t-pentylphenol, 2- (2H Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2 And '-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole. Examples of the ultraviolet absorber of the benzophenone compound include 2-hydroxy-4-methoxybenzophenone. Examples of the ultraviolet absorber of the triazine compound include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  The negative photosensitive resin composition of the present invention may contain a solvent. A compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferably used in that each component can be dissolved uniformly and the transparency of the resulting coating film can be improved. Two or more of these may be contained. Moreover, the compound whose boiling point under atmospheric pressure is 110-250 degreeC is more preferable. By setting the boiling point to 110 ° C. or higher, drying proceeds moderately at the time of coating, and a good coating without uneven coating can be obtained. On the other hand, when the boiling point is 250 ° C. or lower, the amount of residual solvent in the film can be reduced, and film shrinkage during thermosetting can be further reduced, so that better flatness can be obtained.

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

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

  Moreover, the negative photosensitive resin composition of this invention may contain various solvents, such as acetates, ketones, ethers other than the above.

  There is no restriction | limiting in particular in content of a solvent, According to the coating method etc., arbitrary amounts can be used. For example, when film formation is performed by spin coating, the amount of solvent is generally 50 to 95% by weight of the entire negative photosensitive resin composition.

  The negative photosensitive resin composition of the present invention may contain other organosilane compounds as long as the effects of the present invention are not impaired. By containing other organosilane compounds, crosslinking during heat treatment can be promoted and the hardness of the cured film can be improved. Specific examples of other organosilane compounds that can be preferably used include vinyltrimethoxysilane, vinyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, methylpolysilicate 53A (manufactured by Colcoat Co., Ltd.), M silicate 51, and silicate 40. Silicate 45 (trade name, manufactured by Tama Chemical Industry Co., Ltd.), γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. Two or more of these may be contained. Among these, γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, which have a large catalytic activity with a base, are particularly preferable.

  The content of the organosilane compound is preferably 0.1% by weight or more in the solid content of the negative photosensitive resin composition, and the hardness of the cured film is improved. On the other hand, from the viewpoint of sensitivity, crack resistance, and transparency, 5.0% by weight or less is preferable, and 3.0% by weight or less is more preferable.

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

  The negative photosensitive resin composition of the present invention may contain various surfactants such as a fluorine-based surfactant and a silicone-based surfactant in order to improve the flowability during coating. There is no restriction | limiting in particular in the kind of surfactant, For example, a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant, a poly (meth) acrylate type surfactant etc. can be used. Two or more of these may be used.

  Commercially available fluorosurfactants include “Megafuck (registered trademark)” F142D, “Megafuck” F172, “Megafuck” F173, “Megafuck” F183, “Megafuck” F445, and “Megafuck” F470. "Megafuck" F475, "Megafuck" F477 (above, trade name, manufactured by Dainippon Ink & Chemicals, Inc.), NBX-15, FTX-218 (above, trade name, manufactured by Neos Corporation) are preferable. Used. As commercially available products of silicone surfactants, BYK-333, BYK-301, BYK-331, BYK-345, and BYK-307 (above, trade names, manufactured by BYK Japan Co., Ltd.) are preferably used.

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

  The typical manufacturing method of the negative photosensitive resin composition of this invention is demonstrated. For example, the polymer (A) synthesized by the above-mentioned method after (B) a photopolymerization initiator, the compound (C), and, if necessary, other additives are added to an arbitrary solvent and dissolved by stirring. The isocyanurate compound of (D), the imidosilane compound and / or oxetane compound of (E) are added, and the mixture is further stirred at room temperature for 20 minutes to 3 hours. The obtained solution is filtered to obtain a negative photosensitive resin composition.

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

The negative photosensitive resin composition of the present invention is applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, Pre-bake with a heating device such as an oven. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm. After pre-baking, using an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA), light of about 10 to 4000 J / m ² (wavelength 365 nm exposure equivalent) is passed through the desired mask. Irradiate with or without intervention. The exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used. Thereafter, the film is heated in a range of 150 to 450 ° C. for 20 minutes to 1 hour with a heating device such as a hot plate or oven.

For applications requiring pattern processing through a mask, the negative photosensitive resin composition of the present invention preferably has a sensitivity of 100 to 4000 J / m ² when exposed to PLA. In this process, post-exposure baking may be performed as necessary after exposure.

  The sensitivity in the patterning exposure by the PLA is determined by the following method, for example. The composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater, and prebaked at 120 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 2 μm. The prepared film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). ) And paddle development with a 0.4 wt% aqueous tetramethylammonium hydroxide solution for an arbitrary period of time, followed by a 30 second rinse with water. In the formed pattern, an exposure amount for resolving a 30 μm line-and-space pattern with a one-to-one width is obtained as sensitivity.

  After patterning exposure, the exposed portion is dissolved by development, and a negative pattern can be obtained. As a developing method, it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.

  Thereafter, this film is heat-treated in a range of 120 to 280 ° C. for about 1 hour with a heating device such as a hot plate or oven to obtain a cured film. The resolution is preferably 20 μm or less. Although there is no restriction | limiting in particular in the film thickness of a cured film, It is preferable to set it as 0.1-15 micrometers.

  The cured film of the present invention preferably has a hardness of 5H or more and a transmittance of 95% or more when the film thickness is 1.5 μm. The transmittance refers to the transmittance at a wavelength of 400 nm. The hardness and transmittance can be adjusted by selecting the exposure amount and the thermosetting temperature.

  The cured film obtained by curing the negative photosensitive resin composition of the present invention is used as a touch panel protective film, a touch panel insulating film, various hard coat materials, an antireflection film, and an optical filter. Moreover, since it has negative photosensitivity, it is suitably used for TFT flattening films, insulating films, antireflection films, color filter overcoats, column materials, etc. for liquid crystal and organic EL displays. Among these, in particular, it can be suitably used as a touch panel protective film or a touch panel insulating film that requires adhesion after heat treatment and chemical treatment with a substrate having no Si atom, such as ITO or molybdenum. Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type. Since especially high hardness is calculated | required by an electrostatic capacitance type touch panel, the cured film of this invention can be used suitably.

  The present invention will be described below with reference to examples thereof, but the embodiment of the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of Acrylic Resin Solution (A-1) A 500 mL flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50.0 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 30.0 g (0.349 mol) of methacrylic acid, 22.48 g (0.216 mol) of styrene, and 35.0 g (0 of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate) 149 mol), and stirred for a while at room temperature. After the atmosphere in the flask was replaced with nitrogen, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 15.00 g (0.106 mol) of glycidyl methacrylate, 1.00 g of dimethylbenzylamine, 0.200 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and heated at 90 ° C. for 4 hours. Stirring to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solid content concentration was 40% by weight to obtain an acrylic resin solution (A-1). The weight average molecular weight of the acrylic resin was 16000, and the acid value was 118 mgKOH / g.

Synthesis Example 2 Synthesis of Acrylic Resin Solution (A-2) A 500 mL flask was charged with 3.00 g of 2,2′-azobis (isobutyronitrile) and 50.0 g of PGMEA. Then, 15.0 g (0.174 mol) of methacrylic acid, 22.48 g (0.216 mol) of styrene and 33.21 g (0.149 mol) of isobornyl methacrylate were charged and stirred for a while at room temperature. After the replacement, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 15.0 g (0.106 mol) of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.200 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. An acrylic resin solution was obtained. PGMEA was added to the obtained acrylic resin solution so that the solid concentration was 40% by weight to obtain an acrylic resin solution (A-2). The weight average molecular weight of the acrylic resin was 12000, and the acid value was 104 mgKOH / g.

Synthesis Example 3 Synthesis of Acrylic Resin Solution (A-3) A 500 mL flask was charged with 3.00 g of 2,2′-azobis (isobutyronitrile) and 50.0 g of PGMEA. Thereafter, 15.0 g (0.174 mol) of methacrylic acid, 22.48 g (0.216 mol) of styrene and 25.13 g (0.149 mol) of cyclohexyl methacrylate were charged, and the mixture was stirred for a while at room temperature, and the atmosphere in the flask was replaced with nitrogen. Thereafter, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 30.0 g (0.211 mol) of glycidyl methacrylate, 1.00 g of dimethylbenzylamine, 0.200 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and heated at 90 ° C. for 4 hours. Stirring to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solid concentration was 40% by weight to obtain an acrylic resin solution (A-3). The weight average molecular weight of the acrylic resin was 13500, and the acid value was 100 mgKOH / g.

Synthesis Example 4 Synthesis of Acrylic Resin Solution (A-4) A 500 mL flask was charged with 3.00 g of 2,2′-azobis (isobutyronitrile) and 50.0 g of PGMEA. Thereafter, 15.0 g (0.174 mol) of methacrylic acid, 11.24 g (0.108 mol) of styrene, and 66.42 g (0.299 mol) of isobornyl methacrylate were charged and stirred for a while at room temperature. After the replacement, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 40.14 g (0.211 mol) of p-vinylbenzylglycidyl ether, 1.00 g of dimethylbenzylamine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution at 90 ° C. The mixture was heated and stirred for 4 hours to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solid content concentration was 40% by weight to obtain an acrylic resin solution (A-4). The weight average molecular weight of the acrylic resin was 14000, and the acid value was 125 mgKOH / g.

Synthesis Example 5 Synthesis of Acrylic Resin Solution (A-5) 3.00 g of 2,2′-azobis (isobutyronitrile) and 50.0 g of PGMEA were charged into a 500 mL flask. Thereafter, 30.0 g (0.349 mol) of methacrylic acid, 22.48 g (0.216 mol) of styrene and 33.21 g (0.149 mol) of isobornyl methacrylate were charged and stirred for a while at room temperature. After the replacement, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 8.88 g (0.089 mol) of vinyl glycidyl ether, 1 g of dimethylbenzylamine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. An acrylic resin solution was obtained. PGMEA was added to the obtained acrylic resin solution so that the solid content concentration was 40% by weight to obtain an acrylic resin solution (A-5). The weight average molecular weight of the acrylic resin was 13000, and the acid value was 102 mgKOH / g.

Synthesis Example 6 Synthesis of Acrylic Resin Solution (A-6) A 500 mL flask was charged with 3.00 g of 2,2′-azobis (isobutyronitrile) and 50.0 g of PGMEA. Thereafter, 15.0 g (0.174 mol) of methacrylic acid, 38.06 g (0.216 mol) of benzyl methacrylate, and 32.80 g (0.149 mol) of tricyclodecanyl methacrylate were charged and stirred at room temperature for a while. After replacing with nitrogen, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 15.0 g (0.106 mol) of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.200 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. An acrylic resin solution was obtained. PGMEA was added to the obtained acrylic resin solution so that the solid concentration was 40% by weight to obtain an acrylic resin solution (A-6). The weight average molecular weight of the acrylic resin was 25000, and the acid value was 98 mgKOH / g.

Synthesis Example 7 Synthesis of carboxyl group-containing silane compound (α) In a 300 mL eggplant flask, 23.23 g of p-aminobenzoic acid and 209.05 g of PGMEA were charged, and stirred at room temperature for 30 minutes to dissolve p-aminobenzoic acid. I let you. The obtained solution was charged with 46.53 g of isocyanatepropyltriethoxysilane and 1.19 g of dibutyltin dilaurate and stirred in an oil bath at 70 ° C. for 1 hour. Thereafter, the mixture was allowed to cool to room temperature, and the precipitated solid was collected by filtration with a glass filter and dried to obtain a carboxyl group-containing silane compound (α). The yield was 46.7g.

Synthesis Example 8 Synthesis of polysiloxane solution (P-1) In a 500 mL three-necked flask, 17.03 g (0.125 mol) of methyltrimethoxysilane, 19.83 g (0.100 mol) of phenyltrimethoxysilane, and carboxyl group-containing silane 38.42 g (0.100 mol) of compound (α), 25.91 g (0.175 mol) of vinyltrimethoxysilane and 109.61 g of diacetone alcohol (DAA) were charged, and the mixture was immersed in an oil bath at 40 ° C. and stirred. However, an aqueous phosphoric acid solution in which 0.237 g of phosphoric acid (0.200 wt% with respect to the charged monomer) was dissolved in 27.0 g of water was added with a dropping funnel over 10 minutes. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 55 g of methanol, ethanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polysiloxane concentration was 40% by weight to obtain a polysiloxane solution (P-1). When the carboxyl group content and the vinyl group content relative to the Si atom were measured by ²⁹ Si-NMR of polysiloxane, they were 20 mol% and 35 mol%, respectively. In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 8000 (polystyrene conversion).

Synthesis Example 9 Synthesis of Polysiloxane Solution (P-2) In a 500 mL three-necked flask, 47.67 g (0.350 mol) of methyltrimethoxysilane, 39.66 g (0.200 mol) of phenyltrimethoxysilane, 3-trimethoxy 26.23 g (0.100 mol) of silylpropyl succinic acid, 86.94 g (0.350 mol) of γ-acryloylpropyltrimethoxysilane, and 185.08 g of DAA were charged and immersed in an oil bath at 40 ° C. while stirring, An aqueous phosphoric acid solution in which 0.401 g of phosphoric acid (0.200 wt% with respect to the charged monomer) was dissolved in 55.8 g was added with a dropping funnel over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 8, 110 g in total of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polysiloxane concentration was 40% by weight to obtain a polysiloxane solution (P-2). The carboxyl group content and acryloyl group content relative to the Si atoms were measured by ²⁹ Si-NMR of polysiloxane, and were 20 mol% and 35 mol%, respectively. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 5500 (polystyrene conversion).

Synthesis Example 10 Synthesis of Polysiloxane Solution (P-3) In a 500 mL three-necked flask, 54.48 g (0.400 mol) of methyltrimethoxysilane, 46.88 g (0.200 mol) of γ-acryloylpropyltrimethoxysilane, DAA Was added in an oil bath at 40 ° C. and stirred, and a phosphoric acid aqueous solution in which 0.3617 g of phosphoric acid (0.200 wt% with respect to the charged monomer) was dissolved in 54.0 g of water was added with a dropping funnel. Added over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 8, 110 g in total of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained DAA solution of polysiloxane so that the polysiloxane concentration was 40% by weight to obtain a polysiloxane solution (P-3). When the acryloyl group content relative to the Si atoms was measured by ²⁹ Si-NMR of polysiloxane, it was 33.3 mol%. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 7500 (polystyrene conversion).

Synthesis Example 11 Synthesis of Polysiloxane Solution (P-4) In a 500 mL three-necked flask, 48.08 g of dimethyldimethoxysilane (0.400 mol), 23.44 g (0.100 mol) of γ-acryloylpropyltrimethoxysilane, and DAA were added. While adding 155.47 g in an oil bath at 40 ° C. and stirring, a phosphoric acid aqueous solution in which 0.3617 g of phosphoric acid (0.200 wt% with respect to the charged monomer) was dissolved in 54.0 g of water was added with a dropping funnel. Added over a minute. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 8, 100 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polysiloxane concentration was 40% by weight to obtain a polysiloxane solution (P-4). When the acryloyl group content relative to the Si atoms was measured by ²⁹ Si-NMR of polysiloxane, it was 20 mol%. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 6500 (polystyrene conversion).

Synthesis Example 12 Synthesis of Polysiloxane Solution (P-5) In a 500 mL three-necked flask, 20.43 g (0.150 mol) of methyltrimethoxysilane and 49.28 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.200 mol), 39.66 g (0.200 mol) of phenyltrimethoxysilane, 26.23 g (0.100 mol) of 3-trimethoxysilylpropyl succinic acid, 86.94 g (0 of γ-acryloylpropyltrimethoxysilane) Phosphoric acid in which 0.401 g of phosphoric acid (0.200% by weight with respect to the charged monomer) was dissolved in 59.4 g of water while stirring in an oil bath at 40 ° C. The aqueous solution was added with a dropping funnel over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 8, 110 g in total of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polysiloxane concentration was 40% by weight to obtain a polysiloxane solution (P-5). The carboxyl group content and acryloyl group content relative to the Si atoms were measured by ²⁹ Si-NMR of polysiloxane, and were 20 mol% and 35 mol%, respectively. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 5500 (polystyrene conversion).

  The compositions of the polymers of Synthesis Examples 1-6 and 8-12 are shown in Table 1.

Synthesis Example 13 Synthesis of Imidosilane Compound (I-1) 32.84 g (160 mmol) of isocyanatepropyltrimethoxysilane was added to 40.0 g of γ-butyrolactone (GBL), and dissolved by stirring. Hydrogenated pyromellitic dianhydride 17.93 g (80.0 mmol) was added and stirred for a while at room temperature, and then stirred at 140 ° C. for 2 hours. The resulting solution was diluted with GBL so that the solid content concentration was 20% by weight to obtain an imidosilane compound (I-1) solution represented by the following structure.

Synthesis Example 14 Synthesis of Imidosilane Compound (I-2) 34.46 g (160 mmol) of isocyanatepropyldiethylethoxysilane was added to 40 g of GBL, and dissolved by stirring. After adding 24.82 g (80.0 mmol) of 4,4′-oxydiphthalic dianhydride and stirring for a while at room temperature, the mixture was stirred at 140 ° C. for 2 hours. The resulting solution was diluted with GBL so that the solid content concentration was 20% by weight to obtain an imidosilane compound (I-2) solution represented by the following structure.

Synthesis Example 15 Synthesis of Imidosilane Compound (I-3) After adding 28.69 g (160 mmol) of aminopropyltrimethoxysilane and 23.70 g (160 mmol) of phthalic anhydride to 400 g of DAA, the mixture was stirred at room temperature for a while, then at 60 ° C. For 2 hours. Then, it heated up to 160 degreeC and made it react for 6 hours, making diacetone alcohol and water azeotrope. The resulting solution was diluted with DAA so that the solid content concentration was 20% by weight to obtain an imidosilane compound (I-3) solution represented by the following structure.

Synthesis Example 16 Synthesis of Imidosilane Compound (I-4) 34.46 g (160 mmol) of isocyanatepropyldiethylethoxysilane was added to 40 g of GBL, and dissolved by stirring. After adding 18.26 g (160 mmol) of glutaric anhydride and stirring at room temperature for a while, it stirred at 60 degreeC for 2 hours. Stir at 140 ° C. for 2 hours. The obtained solution was diluted with GBL so that the solid content concentration was 20% by weight to obtain an imidosilane compound (I-4) solution represented by the following structure.

Synthesis Example 17 Synthesis of imidosilane compound (I-5) To 400 g of propylene glycol monomethyl ether were added 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine, and the mixture was kept at room temperature for a while. And stirred at 60 ° C. for 2 hours. Then, it heated up to 140 degreeC and made it react for 6 hours, making propylene glycol monomethyl ether and water azeotrope. The resulting solution was diluted with DAA so that the solid content concentration was 20% by weight to obtain an imidosilane compound (I-5) solution represented by the following structure.

Synthesis Example 18 Synthesis of imidosilane compound (I-6) 23.71 g (80.0 mmol) of 2-trimethoxysilylethylphthalic anhydride and 4.89 g (80.0 mmol) of monoethanolamine were added to 400 g of DAA, and the mixture was allowed to warm to room temperature for a while. And stirred at 60 ° C. for 2 hours. Then, it heated up to 140 degreeC and made it react for 6 hours, making propylene glycol monomethyl ether and water azeotrope. The obtained solution was diluted with DAA so that the solid content concentration was 20% by weight to obtain an imidosilane compound (I-6) solution represented by the following structure.

Synthesis Example 19 Synthesis of Oxetane Compound (X-1) 27.84 g (100 mmol) of TMSOX (trade name, manufactured by Toa Gosei Co., Ltd.) and 0.54 g (30.0 mmol) of water were added to 80 g of DAA and stirred at room temperature for a while. Then, the mixture was stirred at 60 ° C. for 2 hours. Then, it heated up to 160 degreeC and made it react for 6 hours, making DAA and methanol azeotrope. The obtained solution was diluted with DAA so that the solid content concentration was 20% by weight to obtain an oxetane compound (X-1) solution represented by the following structure.

Synthesis Example 20 Synthesis of Oxetane Compound (X-2) To DAA 400 g, methyl silicate 53A (trade name, manufactured by Colcoat Co., Ltd.) 89.41 g (0.1 mol) and oxetane alcohol 209.09 g (1.8 mol) were added for a while. After stirring at room temperature, the mixture was stirred at 60 ° C. for 2 hours. Then, it heated up to 160 degreeC and made it react for 6 hours, making DAA and methanol azeotrope. The obtained solution was diluted with DAA so that the solid content concentration was 20% by weight to obtain an oxetane compound (X-2) solution represented by the following structure.

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

(1) Measurement of transmittance The negative photosensitive resin composition was applied to a 5 cm square Tempax glass substrate (Asahi Techno Glass plate Co., Ltd.) using a spin coater (Mikasa Co., Ltd. 1H-360S) at 50 rpm. After spinning at 1000 rpm for 4 seconds and spin-coating, pre-baking at 90 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), a film with a thickness of 2 μm Was made. The prepared film is exposed using PLA (Canon Co., Ltd. PLA-501F) as an ultra high pressure mercury lamp and cured using an oven (Espec Co., Ltd. IHPS-222) in air at 220 ° C. for 1 hour. Thus, a cured film was produced. About the obtained cured film, the transmittance | permeability of 400 nm was measured using ultraviolet-visible spectrophotometer UV-260 (made by Shimadzu Corp.). The film thickness was measured at a refractive index of 1.50 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. The same applies to the film thickness described below.

(2) Measurement of hardness About the cured film obtained by the method of said (1), pencil hardness was measured based on "JISK5600-5-4 (1999)." However, the load weight was 4.903325N.

(3) Evaluation of scratch resistance A cured film was produced on a 5 cm × 7 cm Tempax glass substrate by the method described in (1) above. On the obtained cured film, steel wool of # 0000 was subjected to 10 reciprocations in the long side direction under a load of 1.96133N, and then the cured film was observed. Judgment was made in the following five stages, and 4 or more were judged as acceptable.
5: The film is not damaged at all.
4: There are 1 to 10 scratches on the membrane.
3: There are 11-30 scratches on the membrane.
2: There are 31-50 scratches on the membrane.
1: There are 51 or more scratches on the membrane.

(4) Evaluation of heat resistance The cured film obtained by the method described in (1) above was further heat-treated at 250 ° C. for 3 hours, and then UV-visible spectrophotometer UV-260 (manufactured by Shimadzu Corporation). ) Was used to measure the transmittance at 400 nm, and the change rate of the transmittance before and after the heat treatment at 250 ° C. for 3 hours (the following formula) was calculated. When the rate of change was less than 10%, it was judged as good, and when it was 10% or more, it was judged as bad.
Change rate (%) = (1-250 ° C. × 400 nm transmittance of cured film after heat treatment for 3 hours ÷ 400 nm transmittance of cured film) × 100
(5) Evaluation of adhesiveness Using a negative photosensitive resin composition, cured on a Tempax glass substrate (manufactured by Asahi Techno Glass Sheet Co., Ltd.), an ITO substrate and a molybdenum substrate by the method described in (1) above. A membrane was prepared. After the cured film is treated under the following conditions (5-1) or (5-2), the cured film is made of glass, ITO or molybdenum according to JIS “K5400” 8.5.2 (1990) cross-cut tape method. Adhesion was evaluated. On the surface of the glass substrate, ITO or molybdenum on the glass substrate, 11 parallel vertical and horizontal straight lines are drawn at 1 mm intervals so as to reach the substrate of the glass substrate with a cutter knife. 100 were produced. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is affixed to the cut ITO surface and rubbed with an eraser (JIS S6050-qualified product). Hold one end of the tape and keep it perpendicular to the plate. The remaining number of squares when peeled instantaneously was visually evaluated. Judgment was made as follows according to the number of peeled squares, and 3 or more was determined to be acceptable.
5: Number of peeled pieces = 0
4: Less than 5 peeled off 3: Stripped number 5% or more and less than 15% 2: Stripped number 15% or more and less than 35% 1: Stripped number 35% or more and less than 65% 0: Stripped number 65% or more <0: Other than square All peeled off including the area.

(5-1) Adhesiveness in heat treatment A cured film prepared on a glass, ITO, and molybdenum substrate was heat-treated in an oven at 230 ° C. for 3 hours and 250 ° C. for 3 hours, and the adhesiveness was evaluated by the above method.

(5-2) Adhesiveness in chemical treatment (5-2-1) Adhesiveness to alkaline liquid A mixed film of monoethanolamine / dimethylsulfoxide = 70/30 (weight ratio) prepared on a glass, ITO or molybdenum substrate. After immersing in the inside at 60 ° C. for 5 minutes or at 80 ° C. for 3 minutes, rinsing with pure water was performed for 5 minutes, water was removed by nitrogen blowing, and the adhesiveness was evaluated by the above method.

(5-2-2) Adhesiveness to aqueous acid solution A cured film prepared on a glass, ITO or molybdenum substrate was immersed in a mixed solution of hydrochloric acid / nitric acid / water = 18/4/78 (weight ratio) at 40 ° C. for 80 seconds. Thereafter, rinsing with pure water was performed for 5 minutes, water was removed by nitrogen blowing, and the adhesiveness was evaluated by the above method.

(6) Sensitivity The negative photosensitive resin composition was spin-coated on a silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) for 10 seconds at 500 rpm and then for 4 seconds at 1000 rpm. Then, it prebaked for 2 minutes at 90 degreeC using the hotplate (Dainippon Screen Manufacturing Co., Ltd. SCW-636), and produced the film | membrane with a film thickness of 2 micrometers. The obtained pre-baked film was exposed with a gap of 100 μm through a gray scale mask for sensitivity measurement using PLA as an ultrahigh pressure mercury lamp as a light source. Thereafter, using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed for 90 seconds with a 0.4 wt% tetramethylammonium hydroxide aqueous solution ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Then rinsed with water for 30 seconds. After exposure and development, the exposure amount for forming a 30 μm line-and-space pattern with a one-to-one width (hereinafter referred to as the optimum exposure amount) was defined as sensitivity. The exposure amount was measured with an I-line illuminometer.

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

Example 1
Under a yellow light, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.5166 g, 4,4- 0.0272 g of bis (diethylamino) benzophenone (hereinafter abbreviated as EK) is dissolved in 2.9216 g of DAA and 2.4680 g of PGMEA, and dipentaerythritol hexaacrylate (trade name “Kayarad (registered trademark) DPHA”, Shin Nippon Kayaku ( PGMEA 50 wt% solution 4.33504 g, isocyanuric acid EO-modified triacrylate (trade name “Aronix” (registered trademark) M-315, manufactured by Toa Gosei Co., Ltd.) 0.54379 g, imidosilane compound ( I-1) 1.3595 g of solution, PG of 4-t-butylcatechol 1.6314 g of EA 1 wt% solution, 6.7974 g of acrylic resin solution (A-1), 0.2000 g of PGMEA 1 wt% solution of BYK-333 (manufactured by Big Chemie Japan Co., Ltd.) which is a silicone surfactant (concentration 100 ppm) Was added) and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the negative photosensitive resin composition. Evaluation of said (1)-(7) was performed about the obtained negative photosensitive resin composition.

Example 2
A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that the imidosilane compound (I-5) solution was used instead of the imidosilane compound (I-1) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 3
Instead of acrylic resin solution (A-1), acrylic resin solution (A-2), instead of “M-315” triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.), imidosilane compound (I-1) ) A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that the imidosilane compound (I-2) solution was used instead of the solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 4
A negative photosensitive resin composition was obtained in the same manner as in Example 3 except that the imidosilane compound (I-1) solution was used instead of the imidosilane compound (I-2) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 5
Instead of the acrylic resin solution (A-1), the acrylic resin solution (A-3) was reduced in the amount of “DPHA” added to 2.6189 g, and instead of 2,2- [9H-fluorene-9,9 -2.7189 g of PGMEA 50 wt% solution of diylbis (1,4-phenylene) bisoxy] diethanol diacrylate (trade name “BPEFA” manufactured by Osaka Gas Chemical Co., Ltd.) was added, and instead of “M-315”, tris- 0.1631 g of (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965” manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the imidosilane compound (I-1) solution. ) A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that 1.6314 g of the solution was used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 6
A negative photosensitive resin composition was obtained in the same manner as in Example 5 except that the imidosilane compound (I-1) solution was used instead of the imidosilane compound (I-3) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 7
A negative photosensitive resin composition was obtained in the same manner as in Example 5 except that the imidosilane compound (I-6) solution was used instead of the imidosilane compound (I-3) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 8
Instead of the acrylic resin solution (A-2), the acrylic resin solution (A-4) was replaced with 2.6189 g of a PGMEA 50 wt% solution of tetrapentaerythritol decaacrylate instead of “DPHA”, and 2,2- [9H-fluorene. 2.7189 g of a PGMEA 50 wt% solution of −9,9-diylbis (1,4-phenylene) bisoxy] diethanol diacrylate (trade name “BPEFA” manufactured by Osaka Gas Chemical Co., Ltd.) was added, and an imidosilane compound (I-2) A negative photosensitive resin composition was obtained in the same manner as in Example 3 except that 0.8157 g of the imidosilane compound (I-4) solution was used instead of the solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 9
A negative photosensitive resin composition was obtained in the same manner as in Example 8 except that the imidosilane compound (I-5) solution was used instead of the imidosilane compound (I-4) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 10
Instead of acrylic resin solution (A-4), acrylic resin solution (A-5), 0.1631 g of “X-12-965” instead of triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.), and imidosilane A negative photosensitive resin composition was obtained in the same manner as in Example 8 except that 1.6313 g of the imidosilane compound (I-5) solution was used instead of the compound (I-4) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 11
The same procedure as in Example 1 was conducted except that the polysiloxane solution (P-1) was used instead of the acrylic resin solution (A-1), and the imide silane compound (I-4) solution was used instead of the imide silane compound (I-1) solution. Thus, a negative photosensitive resin composition was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 12
A negative photosensitive resin composition was obtained in the same manner as in Example 11 except that the imidosilane compound (I-6) solution was used instead of the imidosilane compound (I-4) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 13
Example 8 except that the polysiloxane solution (P-2) was used instead of the acrylic resin solution (A-4), and 1.6313 g of the imidosilane compound (I-6) solution was used instead of the imidosilane compound (I-4) solution. In the same manner as above, a negative photosensitive resin composition was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 14
Negative photosensitive resin composition as in Example 11 except that the polysiloxane solution (P-2) was used instead of the polysiloxane solution (P-1) and 0.1359 g of the polysiloxane solution (P-3) was added. I got a thing. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 15
A negative photosensitive resin composition was obtained in the same manner as in Example 14 except that the polysiloxane solution (P-3) was not added. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 16
Negative photosensitive resin composition as in Example 5 except that the polysiloxane solution (P-2) was used instead of the acrylic resin solution (A-3) and 0.1359 g of the polysiloxane solution (P-4) was added. I got a thing. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 17
A negative photosensitive resin composition was obtained in the same manner as in Example 16 except that the polysiloxane solution (P-4) was not added. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 18
A negative photosensitive resin composition was obtained in the same manner as in Example 5 except that 0.1359 g of the polysiloxane solution (P-4) was added. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 19
A negative photosensitive resin composition was obtained in the same manner as in Example 10 except that the imidosilane compound (I-4) solution was used instead of the imidosilane compound (I-5) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 20
A negative photosensitive resin composition was obtained in the same manner as in Example 7 except that the acrylic resin solution (A-6) was used instead of the acrylic resin solution (A-3). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 21
Instead of the imidosilane compound (I-5) solution, 0.272 g of oxetane alcohol (trade name “Aron Oxetane” OXT-101, manufactured by Toa Gosei Co., Ltd.) was used, and X-12 was used instead of “M-315”. A negative photosensitive resin composition was obtained in the same manner as in Example 2 except that -965 was used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 22
A negative photosensitive resin composition was prepared in the same manner as in Example 20 except that 0.326 g of ““ Aron oxetane ”OXT-221” (manufactured by Toa Gosei Co., Ltd.) was used instead of the imidosilane compound (I-6) solution. Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 23
A negative photosensitive resin composition was obtained in the same manner as in Example 5 except that 0.326 g of ““ Aron oxetane ”OXT-121” was used instead of the imidosilane compound (I-3) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 24
A negative photosensitive resin composition was obtained in the same manner as in Example 20 except that 0.326 g of “TMSOX” was used instead of the imidosilane compound (I-6) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 25
Instead of the acrylic resin solution (A-4), the acrylic resin solution (A-6) was replaced with “X-12-965” instead of triallyl isocyanurate, and ““ A negative photosensitive resin composition was obtained in the same manner as in Example 9 except that 0.163 g of Aron oxetane “OXT-191” was used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 26
A negative photosensitive resin composition was obtained in the same manner as in Example 20 except that 0.326 g of OX-SQ (trade name, manufactured by Toa Gosei Co., Ltd.) was used instead of the imidosilane compound (I-6) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 27
A negative photosensitive resin composition was obtained in the same manner as in Example 20 except that the oxetane compound (X-1) solution was used instead of the imidosilane compound (I-6) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 28
A negative photosensitive resin composition was obtained in the same manner as in Example 20 except that the oxetane compound (X-2) solution was used instead of the imidosilane compound (I-6) solution. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 29
A negative photosensitive resin composition was obtained in the same manner as in Example 17 except that the polysiloxane solution (P-5) was used instead of the polysiloxane solution (P-2). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Example 30
1,2-octanedione instead of Irgacure 907 and EK, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name “Irgacure OXE01”, manufactured by Ciba Specialty Chemicals) A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that 5438 g was used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 1
A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that “M-315” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 2
A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that the imidosilane compound (I-1) solution was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 3
A negative photosensitive resin composition was obtained in the same manner as in Example 1 except that “M-315” and the imidosilane compound (I-1) solution were not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 4
A negative photosensitive resin composition was obtained in the same manner as in Example 5 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 5
A negative photosensitive resin composition was obtained in the same manner as in Example 5 except that the imidosilane compound (I-3) solution was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 6
A negative photosensitive resin composition was obtained in the same manner as in Example 5 except that “X-12-965” and the imidosilane compound (I-3) solution were not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (E3).

Comparative Example 7
A negative photosensitive resin composition was obtained in the same manner as in Example 10 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 8
A negative photosensitive resin composition was obtained in the same manner as in Example 10 except that the imidosilane compound (I-5) solution was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 9
A negative photosensitive resin composition was obtained in the same manner as in Example 10 except that “X-12-965” and the imidosilane compound (I-5) solution were not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 10
A negative photosensitive resin composition was obtained in the same manner as in Example 13 except that triallyl isocyanurate was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 11
A negative photosensitive resin composition was obtained in the same manner as in Example 13 except that the imidosilane compound (I-6) solution was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 12
A negative photosensitive resin composition was obtained in the same manner as in Example 13 except that the triallyl isocyanurate and the imidosilane compound (I-6) solution were not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 13
A negative photosensitive resin composition was obtained in the same manner as in Example 21 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 14
A negative photosensitive resin composition was obtained in the same manner as in Example 22 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 15
A negative photosensitive resin composition was obtained in the same manner as in Example 24 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 16
A negative photosensitive resin composition was obtained in the same manner as in Example 26 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 17
A negative photosensitive resin composition was obtained in the same manner as in Example 27 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 18
A negative photosensitive resin composition was obtained in the same manner as in Example 28 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 19
A negative photosensitive resin composition was obtained in the same manner as in Example 29 except that “X-12-965” was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 20
A negative photosensitive resin composition was obtained in the same manner as in Example 29 except that the imidosilane compound (I-3) was not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

Comparative Example 21
A negative photosensitive resin composition was obtained in the same manner as in Example 29 except that the imidosilane compound (I-3) and “X-12-965” were not used. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition.

  The compositions of Examples 1 to 30 and Comparative Examples 1 to 21 are shown in Tables 2 to 6, and the evaluation results are shown in Tables 7 to 10.

  The cured film obtained by curing the negative photosensitive resin composition of the present invention includes a flattening film for TFT of liquid crystal and organic EL displays, an insulating film, as well as various hard coat films such as a protective film for a touch panel and an insulating film. , Antireflection film, antireflection film, optical filter, overcoat for color filter, column material and the like.

Claims (6)

(A) a polymer having a carboxyl group and / or a phenolic hydroxyl group and an ethylenically unsaturated double bond group,
(B) a photo radical polymerization initiator,
(C) a compound having a (meth) acryloyl group and not containing a silicon atom and an isocyanurate structure,
(D) An isocyanurate compound represented by the following general formula (1) and (E) an imidosilane compound represented by any one of the following general formulas (3) to (5) , and / or oxetane alcohol, di [1 -An oxetane compound selected from the group consisting of ethyl (3-oxetanyl)] methyl ether, 1,4-bis [[(3-ethyl-3-oxetanyl) methoxy] methyl] benzene and an oxetane compound having a silicon atom A negative photosensitive resin composition characterized by comprising:

(In the general formula (1), R ^{1 to} R ³ may be the same or different, and represent an ethylenically unsaturated double bond-containing group or a group represented by the following general formula (2).)

(In the above general formula (2), each R ⁴ may be the same or different. Represents an alkylcarbonyloxy group or a substituted product thereof, and n represents an integer of 1 to 5.)

(In the above general formula (3), each R ⁵ and R ⁶ may be the same or different, each having a C 1-6 alkyl group, a C 1-6 alkoxyl group, a phenyl group, a phenoxy group, a carbon number R ⁷ and R ⁸ each represent a divalent organic group having 1 to 10 carbon atoms, R ⁹ does not include a silicon atom, and 2 to 30 carbon atoms. of it represents a tetravalent organic group. in formula (4), R ¹⁰ does not contain silicon atoms and ethylenically unsaturated double bond, .R ¹¹ representing a divalent organic group having 2 to 20 carbon atoms Represents a divalent organic group having 1 to 10 carbon atoms, and each R ¹² may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, An alkylcarbonyloxy group having 2 to 6 carbon atoms or Represents the those of the substituents. In formula ^{(5), R 13} is ^{.R 14} 2 to 20 carbon atoms represents a monovalent organic group having 1 to 20 carbon atoms containing no hydrogen atom or a silicon atom, Each R ¹⁵ may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or 2 to 6 carbon atoms. Represents an alkylcarbonyloxy group or a substituted product thereof.) The negative photosensitive resin composition according to claim 1, wherein the polymer (A) has a phenyl group and an alicyclic hydrocarbon group. 3. The negative photosensitive resin composition according to claim 1, further comprising (F) a polysiloxane having an ethylenically unsaturated double bond group and not containing a carboxyl group and a phenolic hydroxyl group. The material for touchscreens containing the negative photosensitive resin composition in any one of Claims 1-3 . Claim 1-3 or wherein the negative photosensitive resin composition touch panel protective film formed by curing the. The touch panel insulating film formed by curing the claims 1-3 negative-type photosensitive resin composition according to any one.