JP2018146958A - Negative type photosensitive resin composition and cured film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative type photosensitive resin composition providing a cured film which is excellent in pattern workability and storage stability and has high strength and high chemical resistance by UV curing and thermosetting.SOLUTION: A negative type photosensitive resin composition contains (A) an alkali soluble resin having a carboxylic group, (B) a photoradical polymerization initiator, (C) an epoxy or oxetane-containing monofunctional monomer having a specific structure, (D) an amine-based silane coupling agent having a specific structure and (E) a solvent having an alcoholic hydroxyl group, where (A) the alkali soluble resin having the carboxylic group contains (a-1) polysiloxane having a carboxyl group and a radical polymerizable group and/or (a-2) a modified acrylic resin being a reaction product of an acrylic resin having a carboxyl group and a mono-substituted epoxy compound having a radical polymerizable group, and the resin composition contains 25-70 wt.% of (E) the solvent having the alcoholic hydroxyl group.SELECTED DRAWING: None

Description

  The present invention relates to a negative photosensitive resin composition, a cured film using the same, a touch panel, and a color filter substrate.

  Currently, hard coat materials are used for various purposes, and are used for improving the surface hardness of, for example, containers for automobile parts and cosmetics, sheets, films, optical disks, thin displays, and the like. Properties required for the hard coat material include hardness, scratch resistance, heat resistance, weather resistance, adhesion, and the like. Typical examples of the hard coat material include a radical polymerization type UV curable hard coat containing a polymerizable group-containing oligomer, a monomer, a photopolymerization initiator, and other additives (for example, Non-Patent Document 1). reference). By UV irradiation, the oligomer and the monomer are radically polymerized to be cross-linked to obtain a high hardness film. This hard coat material has advantages such as a short time required for curing and excellent productivity, and a negative photosensitive material having a general radical polymerization mechanism can be used.

  The capacitive touch panel, which has been attracting attention in recent years, is one of the uses of hard coat materials. The structure of the capacitive touch panel has a wiring formed of ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) on a glass, and a protective film for protecting an insulating film and an element. Properties required for this insulating film and protective film include transparency, pattern processability for circuit connection, high hardness that does not cause scratches in the modularization process, and can withstand acid and alkali treatments performed in subsequent processes. There are chemical resistance and storage stability, and a photosensitive hard coat material satisfying these requirements is demanded.

  When the hard coat material described in Non-Patent Document 1 is used as such a photosensitive organic hard coat material, there is a problem in chemical resistance.

  On the other hand, as a technique for improving chemical resistance, particularly acid resistance, for example, a photosensitive resin composition containing a polymer having a film-forming ability and an organosilane compound (see, for example, Patent Document 1) or a specific A photosensitive composition comprising an alkali-soluble polymer obtained by copolymerizing a monomer having a structure with a radically polymerizable monomer having an epoxy, a compound having a polymerizable double bond, and a photopolymerization initiator ( For example, Patent Document 2) has been proposed.

JP 2000-187321 A JP 2009-53254 A

Noboru Ohara, “Material Design / Coating Technology and Improvement of Hardness in Hard Coat Films Centering on Plastic Substrates”, Technical Information Association, April 28, 2005, page 99

  When the photosensitive resin composition described in Patent Document 1 is used as an overcoat material for a touch panel, there is a problem that the storage stability is insufficient. On the other hand, when the photosensitive composition described in Patent Document 2 is used as an overcoat material for a touch panel, there has been a problem that chemical resistance used in touch panel production has been insufficient in recent years.

  An object of the present invention is to provide a negative photosensitive resin composition which is excellent in pattern processability and storage stability and gives a cured film having high hardness and high chemical resistance by UV curing and thermal curing.

In order to achieve the above object, the present invention employs the following configuration.
(A) an alkali-soluble resin having a carboxyl group, (B) a radical photopolymerization initiator, (C) an epoxy or oxetane-containing monofunctional monomer having a structure represented by the following general formula (1), (D) the following general formula (2) containing an amine silane coupling agent having a structure represented by (2) and (E) a solvent having an alcoholic hydroxyl group,
The (A) alkali-soluble resin having a carboxyl group has (a-1) a polysiloxane having a carboxyl group and a radical polymerizable group and / or (a-2) an acrylic resin having a carboxyl group and a radical polymerizable group. A negative photosensitive resin composition comprising a modified acrylic resin which is a reaction product with a monosubstituted epoxy compound, and containing 25 to 70% by weight of the solvent having the (E) alcoholic hydroxyl group.

In the general formula (1), X represents a divalent group having an alkylene oxide having 2 to 40 carbon atoms or a divalent group having an aromatic ring, and R ¹ represents hydrogen or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 2 carbon atoms.

In the general formula (2), R ³ and R ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, or a substituted or unsubstituted group having 6 to 12 carbon atoms. A substituted aryl group is shown.

  The negative photosensitive resin composition of the present invention is excellent in pattern processability and storage stability. With the negative photosensitive resin composition of the present invention, a cured film having high hardness and high chemical resistance can be obtained by UV curing and heat curing.

  The negative photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin having a carboxyl group, (B) a photo radical polymerization initiator, (C) an epoxy having a structure represented by the following general formula (1), or It contains an oxetane-containing monofunctional monomer, (D) an amine-based silane coupling agent having a structure represented by the following general formula (2), and (E) a solvent having an alcoholic hydroxyl group. Further, (A) the alkali-soluble resin having a carboxyl group is (a-1) a polysiloxane having a carboxyl group and a radical polymerizable group and / or (a-2) an acrylic resin having a carboxyl group and a radical polymerizable group. The negative type photosensitive resin composition contains 25 to 70% by weight of a solvent having an alcoholic hydroxyl group in the negative photosensitive resin composition. (C) containing an epoxy or oxetane-containing monofunctional monomer having a structure represented by the general formula (1) and an amine-based silane coupling agent having a structure represented by the general formula (2). Therefore, since these components are cross-linked by UV curing and heat curing, chemical resistance can be greatly improved, while there is a problem that storage stability is lowered. The present invention can also solve the problem of storage stability by setting the content of the solvent (E) having an alcoholic hydroxyl group to 25 to 70% by weight.

In the general formula (1), X represents a divalent group having an alkylene oxide having 2 to 40 carbon atoms or a divalent group having an aromatic ring, and R ¹ represents hydrogen or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 2 carbon atoms.

In the general formula (2), R ³ and R ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, or a substituted or unsubstituted group having 6 to 12 carbon atoms. A substituted aryl group is shown.

  The negative photosensitive resin composition of the present invention comprises (a-1) a polysiloxane having a carboxyl group and a radical polymerizable group (hereinafter sometimes referred to as “(a-1) polysiloxane”) and / or. (A-2) Modified acrylic resin (hereinafter referred to as “(a-2) modified acrylic resin”) which is a reaction product of an acrylic resin having a carboxyl group and a mono-substituted epoxy compound having a radical polymerizable group (A) containing an alkali-soluble resin having a carboxyl group. Here, the alkali-soluble resin refers to a resin having a carboxyl group. By containing (a-1) and / or (a-2), it becomes soluble in an alkaline developer, so that the pattern processability can be improved. Further, a cured film having high hardness and high transparency can be obtained by UV curing and heat curing. Chemical resistance can be improved by the radically polymerizable group of (a-1) and (a-2).

  (A-1) As polysiloxane, for example, an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group and an organosilane compound having a radical polymerizable group are hydrolyzed, and the hydrolyzate is condensed. What is obtained is mentioned. If necessary, together with an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group or an organosilane compound having a radical polymerizable group, it has a carboxyl group, a dicarboxylic anhydride group and a radical polymerizable group. No organosilane may be used.

  Examples of the organosilane compound having a carboxyl group include 3-trimethoxysilylpropyl succinic acid, 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropionic acid, and 3-dimethylethoxysilyl. Propionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 5-dimethyl Linear fats such as methoxysilylvaleric acid, 5-dimethylethoxysilylvaleric acid, 6-trimethoxysilylcaproic acid, 6-triethoxysilylcaproic acid, 6-dimethylmethoxysilylcaproic acid, 6-dimethylethoxysilylcaproic acid Tribe Carbo Acid compound; 4- (3-trimethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3-triethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3-dimethylmethoxysilylpropoxy) cyclohexanecarboxylic acid, 4- (3- Cycloaliphatic carboxylic acid-containing compounds such as dimethylethoxysilylpropoxy) cyclohexanecarboxylic acid; 4- (3-trichlorosilylpropoxy) benzoic acid, 4- (3-trimethoxysilylpropoxy) benzoic acid, 4- (3- Examples thereof include aromatic carboxylic acid compounds such as triethoxysilylpropoxy) benzoic acid, 4- (3-dimethylmethoxysilylpropoxy) benzoic acid, and 4- (3-dimethylethoxysilylpropoxy) benzoic acid. Two or more of these may be used. Among these, 4-trimethoxysilylbutyric acid is preferable from the viewpoint of improving solubility in a developer during pattern formation and suppressing pattern peeling during development.

  Examples of the organosilane compound having a dicarboxylic anhydride group include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, 3 -Dimethylethoxysilylpropyl succinic anhydride, 4- (2-trimethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-triethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride 4- (2-dimethylmethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-dimethylethoxysilylethyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-tri Methoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride 3- (3-triethoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-dimethylmethoxysilylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 3- (3-dimethylethoxy Silylpropyl) cyclohexyl-1,2-dicarboxylic anhydride, 4- (2-trimethoxysilylethyl) phthalic anhydride, 4- (2-triethoxysilylethyl) phthalic anhydride, 4- (2-dimethyl) Methoxysilylethyl) phthalic anhydride, 4- (2-dimethylethoxysilylethyl) phthalic anhydride, 3- (3-trimethoxysilylpropyl) phthalic anhydride, 3- (3-triethoxysilylpropyl) phthal Acid anhydride, 3- (3-dimethylmethoxysilylpropyl) phthalic anhydride, 3- (3-dimethylethoxy Rirupuropiru) and the like phthalic anhydride. Two or more of these may be used. Among these, 3-trimethoxysilylpropyl succinic anhydride is preferable from the viewpoint of improving solubility in a developer during pattern formation and suppressing pattern peeling during development.

  Examples of the radical polymerizable group include a vinyl group, an α-methylvinyl group, an allyl group, a styryl group, and a (meth) acryloyl group. You may have 2 or more types of these. Among these, a (meth) acryloyl group is preferable from the viewpoint of further improving the hardness of the cured film and the sensitivity during pattern processing. Here, the (meth) acryloyl group is a general term for a methacryloyl group and an acryloyl group.

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

  Examples of organosilanes that do not have any carboxyl group, dicarboxylic anhydride group, and radical polymerizable group include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and hexyltrimethoxysilane. , Octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N -Diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropi Trimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycyl Sidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidyl Sidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycyl Sidoxybutyl tri Toxisilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxy Silane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Phenoxysilane, -(3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4 -Epoxycyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiet Sisilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropyl Methyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycid Xypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetra Tokishishiran, trifluoromethyl trimethoxy silane, trifluoromethyl triethoxy silane, trifluoropropyl trimethoxy silane, such as trifluoropropyl triethoxy silane.

  (A-1) The total amount of the organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group with respect to 1 mol of all organosilanes constituting the polysiloxane is adjusted to a preferred range described later, and the pattern is formed. From the viewpoint of improving the solubility in the developer, 0.05 mol or more is preferable. On the other hand, 0.45 mol or less is preferable and 0.3 mol or less is more preferable from the viewpoint of adjusting the carboxylic acid equivalent to a preferable range described later and suppressing pattern peeling during development.

  (A-1) The total amount of the organosilane compound having a radical polymerizable group with respect to 1 mol of all organosilanes constituting the polysiloxane is preferably 0.05 mol or more from the viewpoint of adjusting the double bond equivalent to a preferable range described later. 0.50 mol or less is preferable.

  The conditions for the hydrolysis reaction can be appropriately set. For example, after adding an acid catalyst and water to the organosilane compound in a solvent over 1 to 180 minutes, the reaction temperature is from room temperature to 110 ° C. for 1 to 180 minutes. It is preferable to react. 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 amount of the solvent added 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 all organosilane compounds used during the hydrolysis reaction. By making the addition amount of a solvent into the said range, it can adjust easily so that a hydrolysis reaction may need and fully advance.

  The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water is preferably 1.0 to 4.0 mol with respect to 1 mol of silane atoms.

  The hydrolysis reaction is preferably performed in the presence of an acid catalyst. Examples of the acid catalyst include an acidic aqueous solution containing formic acid, acetic acid, and phosphoric acid. It is preferable to add 0.15 parts by weight of these acid catalysts with respect to 100 parts by weight of all organosilane compounds used in the hydrolysis reaction. By making the addition amount of an acid catalyst into the said range, it can adjust easily so that a hydrolysis reaction may need and fully advance.

  Examples of the condensation reaction include a method in which a silanol compound obtained by hydrolysis reaction of an organosilane compound is obtained, and then the reaction solution is heated as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours to be reacted. In order to increase the polymerization degree 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 can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the organosilane compound or polysiloxane.

  Examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and 3-methyl-3-methoxy. Alcohols such as -1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol di Ethers such as chill ether, ethylene glycol dibutyl ether, diethyl ether, propylene glycol mono-t-butyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone Amides such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Acetates such as butyl acetate, methyl lactate, ethyl lactate, butyl lactate; Emissions, xylene, hexane, aromatic or aliphatic hydrocarbons such as cyclohexane; .gamma.-butyrolactone; N- methyl-2-pyrrolidone; and dimethyl sulfoxide. Two or more of these may be used. From the viewpoint of compatibility with polysiloxane, 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 is preferred.

  When the solvent is generated by the hydrolysis reaction, the hydrolysis may be performed without a solvent. It is also preferable to adjust the polysiloxane solution to an appropriate concentration by adding a solvent after completion of the reaction. Further, depending on the purpose, after hydrolysis, an appropriate amount of the produced alcohol or the like may be removed by distillation under heating and / or reduced pressure, and then a desired solvent may be added.

(A-1) The carboxylic acid equivalent of polysiloxane is preferably 200 g / mol or more, more preferably 400 g / mol or more, from the viewpoint of suppressing pattern peeling during development. On the other hand, from the viewpoint of improving the solubility in a developer during pattern formation, it is preferably 1400 g / mol or less, more preferably 1000 g / mol or less. Here, the carboxylic acid equivalent of the polysiloxane can be calculated by measuring the silanol group / carboxyl group ratio in the polysiloxane by ¹ H-NMR and then measuring the acid value.

  (A-1) As a means for setting the carboxylic acid equivalent of polysiloxane to the above range, for example, an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group with respect to 1 mol of all organosilanes constituting the polysiloxane. And the like, and the like.

  (A-1) The content of the radical polymerizable group of the polysiloxane, so-called double bond equivalent, is preferably 150 to 10,000 g / mol, more preferably 200 to 1500 g / mol. By setting the double bond equivalent in the above range, the hardness and chemical resistance of the cured film can be further improved. Here, the double bond equivalent of polysiloxane can be calculated by measuring the iodine value.

  (A-1) As a means for bringing the double bond equivalent of polysiloxane within the above range, for example, the total amount of the organosilane compound having a radical polymerizable group with respect to 1 mol of all organosilanes constituting the polysiloxane is described above. And the like, and the like.

  (A-1) The weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 to 100,000, and can improve coating characteristics and solubility in a developer during pattern formation. Here, the weight average molecular weight of the polysiloxane refers to a polystyrene equivalent value measured by gel permeation chromatography (GPC).

  (A-2) As the acrylic resin having a carboxyl group constituting the modified acrylic resin, for example, an ethylenic monomer having a carboxyl group, a (meth) acrylic acid ester, a vinyl aromatic compound, an amide unsaturated compound and / or Alternatively, radical polymerization products with other vinyl compounds and the like can be mentioned.

  Examples of the ethylenic monomer having a carboxyl group include (meth) acrylic acid, itaconic acid, maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, Examples include 2- (meth) acryloyloxyethyl phthalic acid. Two or more of these may be used. Among these, (meth) acrylic acid is preferable from the viewpoint of improving the solubility in a developer during pattern formation and suppressing pattern peeling during development.

  Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) Cyclohexyl acrylate, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, (meth) 2-cyclohexyloxycarbonylethyl acrylate, 2-cyclohexylenylcarbonyl (meth) acrylate, 2- (4-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate, norbornyl (meth) acrylate, (meth) Isobornyl acrylate, tricyclodecanyl (meth) acrylate, tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, (meth ) 1-methyladamantyl acrylate and the like. Two or more of these may be used.

  Examples of the vinyl aromatic compound include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene. Two or more of these may be used. Among these, styrene is preferable from the viewpoint of further improving the chemical resistance of the cured film.

  Examples of the amide unsaturated compound include (meth) acrylamide, N-methylolacrylamide, N-vinylpyrrolidone and the like. Two or more of these may be used.

  Examples of other vinyl compounds include (meth) acrylonitrile, allyl alcohol, vinyl acetate, cyclohexyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, 2-hydroxy vinyl ether, 4 -Hydroxy vinyl ether etc. are mentioned.

  The monosubstituted epoxy compound having a radical polymerizable group in the present invention refers to a compound having a radical polymerizable group and one epoxy group in one molecule. Examples of the monosubstituted epoxy compound having a radical polymerizable group include glycidyl (meth) acrylate, 2- (glycidyloxy) ethyl (meth) acrylate, 3- (glycidyloxy) propyl (meth) acrylate, (meth ) 4- (glycidyloxy) butyl acrylate, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-5,6-epoxyhexyl, (meth) acrylic acid-6,7-epoxyheptyl, Allyl glycidyl ether, vinyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether Α-methyl-p-vini Benzyl glycidyl ether. Two or more of these may be used. Among these, glycidyl (meth) acrylate, 2- (glycidyloxy) ethyl (meth) acrylate, 3- (glycidyloxy) propyl (meth) acrylate, and 4- (glycidyloxy) butyl (meth) acrylate are Preferably, it is easy to adjust the reaction of the epoxy group, and the reactivity of the radical polymerizable group can be increased.

  (A-2) The total amount of the ethylenic monomer having a carboxyl group with respect to the total amount of 1 mol of the ethylenic monomer having a carboxyl group and the vinyl compound constituting the modified acrylic resin is a viewpoint of adjusting the carboxylic acid equivalent to a preferable range described later. Therefore, 0.05 mol or more is preferable and 0.50 mol or less is preferable.

  (A-2) The total amount of the mono-substituted epoxy compound having a radical polymerizable group relative to the total amount of 1 mol of the ethylenic monomer having a carboxyl group and the vinyl compound constituting the modified acrylic resin is a preferred range in which the double bond equivalent is described later. From the standpoint of adjusting to 0, 0.01 mol or more is preferable, and 0.45 mol or less is preferable.

  The conditions for radical polymerization can be set as appropriate. For example, after the inside of the reaction vessel is sufficiently substituted with nitrogen by bubbling or vacuum degassing, an ethylenic monomer having a carboxyl group, (meth) acrylic acid ester It is preferable to react the radical polymerization catalyst at 60 to 110 ° C. for 30 to 300 minutes.

  Examples of the radical polymerization catalyst include azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide.

  Examples of the catalyst used for the addition reaction of a monosubstituted epoxy compound having a radical polymerizable group include amino catalysts such as dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol, dimethylbenzylamine; 2-ethyl Tin-based catalysts such as tin hexanoate (II), dibutyltin laurate; titanium-based catalysts such as 2-ethylhexanoic acid titanium (IV); phosphorus-based catalysts such as triphenylphosphine; acetylacetonate chromium, chromium chloride, etc. Examples include chromium-based catalysts.

  (A-2) The carboxylic acid equivalent of the modified acrylic resin is preferably 50 g / mol or more and more preferably 100 g / mol or more from the viewpoint of suppressing pattern peeling during development. On the other hand, from the viewpoint of improving the solubility in a developer during pattern formation, it is preferably 1400 g / mol or less, more preferably 1000 g / mol or less. The carboxylic acid equivalent of the acrylic resin can be calculated by measuring the acid value.

  (A-2) As means for bringing the carboxylic acid equivalent of the modified acrylic resin into the above range, for example, it has a carboxyl group with respect to a total amount of 1 mol of an ethylenic monomer having a carboxyl group and a vinyl compound constituting the acrylic resin. Examples include a method in which the total amount of the ethylenic monomer and the total amount of the mono-substituted epoxy compound having a radical polymerizable group are within the above-described preferable range.

  (A-2) The double bond equivalent of the modified acrylic resin is preferably 150 to 10,000 g / mol, and more preferably 200 to 1500 g / mol. By setting the double bond equivalent in the above range, the hardness and chemical resistance of the cured film can be further improved. Here, the double bond equivalent of the acrylic resin can be calculated by measuring the iodine value.

  (A-2) As a means for setting the double bond equivalent of the modified acrylic resin in the above range, for example, the carboxyl group with respect to the total amount of the ethylenic monomer having a carboxyl group and the vinyl compound constituting the acrylic resin is 1 mol. Examples thereof include a method in which the total amount of the ethylenic monomer and the total amount of the monosubstituted epoxy compound having a radical polymerizable group are within the above-mentioned preferable ranges.

  (A-2) The weight average molecular weight (Mw) of the modified acrylic resin is preferably 1,000 to 100,000, and can improve the coating characteristics and the solubility in a developer during pattern formation. Here, the weight average molecular weight of the modified acrylic resin refers to a polystyrene equivalent value measured by GPC.

  In the negative photosensitive resin composition of the present invention, the content of (A) the alkali-soluble resin having a carboxyl group can be arbitrarily set depending on the desired film thickness and application, but the negative photosensitive resin composition 10 to 70% by weight in the solid content is generally.

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

  (B) Examples of the photo radical polymerization initiator 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, bis (2,4,4) 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide, 1- Phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (F Nylthio) -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), 4,4-bis (dimethylamino) benzophenone, 4 , 4-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, benzyldimethyl ketal, 1- (4-isopropylphenol) Nyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, benzoin, benzoin methyl ether Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkyl Benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) Oxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis ( η5-2,4-cyclopentadien-1-yl) -bis (2,6-di Fluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2- Phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, Anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexa Non, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, Examples include 4-dimethylthioxanthone and 2,4-diethylthioxanthone. Two or more of these may be contained. Among these, from the viewpoint of further improving the hardness of the cured film, 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) is preferred.

  The content of the (B) radical photopolymerization initiator in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by weight in the solid content of the negative photosensitive resin composition. (B) By setting the content of the photoradical polymerization initiator in the above range, radical curing can be sufficiently advanced, and elution of the remaining radical polymerization initiator is suppressed, and chemical resistance is further improved. be able to.

  The negative photosensitive resin composition of the present invention contains (C) an epoxy or oxetane-containing monofunctional monomer having a structure represented by the following general formula (1). Here, the monofunctional monomer refers to a compound having one (meth) acryl group. Polymerization of the (meth) acrylic group of the (C) epoxy or oxetane-containing monofunctional monomer proceeds by radicals generated from the (B) photoradical polymerization initiator by light irradiation. Furthermore, the chemical resistance of the resulting cured film is improved by crosslinking of the epoxy group or oxetane group and the (D) amine-based silane coupling agent described later by thermosetting.

In the general formula (1), X represents a divalent group having an alkylene oxide having 2 to 40 carbon atoms or a divalent group having an aromatic ring, and R ¹ represents hydrogen or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 2 carbon atoms.

  By having an alkylene oxide having 2 to 40 carbon atoms or an aromatic ring in X, (D) the reactivity with the amine-based silane coupling agent is increased, so that the chemical resistance of the cured film can be improved. As for carbon number of alkylene oxide, 2-5 are preferable.

  Examples of the group having an aromatic ring include divalent groups derived from bisphenols such as bisphenol A, bisphenol F, and bisphenol S. Among these, a divalent group derived from bisphenol A is preferable from the viewpoint of further improving the chemical resistance of the cured film.

  Examples of the epoxy-containing monofunctional monomer having the structure represented by the general formula (1) include 4-hydroxybutyl acrylate glycidyl ether, bisphenol A monoglycidyl ether mono (meth) acrylate, and bisphenol F monoglycidyl ether mono (meta). ) Acrylate, bisphenol S monoglycidyl ether mono (meth) acrylate, biphenyl monoglycidyl ether mono (meth) acrylate, naphthalene monoglycidyl ether mono (meth) acrylate, and the like. Two or more of these may be contained. Examples of the oxetane-containing monofunctional monomer having the structure represented by the general formula (1) include 3-butyl-oxetanylmethyl (meth) acrylate. Among these, bisphenol A monoglycidyl ether mono (meth) acrylate, bisphenol F monoglycidyl ether mono (meth) acrylate, and bisphenol S monoglycidyl ether mono (meth) acrylate are preferable, and chemical resistance can be further improved. Bisphenol A monoglycidyl ether mono (meth) acrylate is more preferred.

  In the negative photosensitive resin composition of the present invention, (C) the content of the epoxy or oxetane-containing monofunctional monomer having the structure represented by the general formula (1) is arbitrarily set depending on the desired film thickness and application. be able to. (D) From the viewpoint of improving the reactivity with the amine-based silane coupling agent, the solid content of the negative photosensitive resin composition is preferably 5% by weight or more, and more preferably 10% by weight or more. On the other hand, from the viewpoint of improving the solubility in a developing solution during pattern formation, the solid content of the negative photosensitive resin composition is preferably 60% by weight or less, and more preferably 50% by weight or less.

  The negative photosensitive resin composition of the present invention contains (D) an amine-based silane coupling agent having a structure represented by the following general formula (2). By containing such an amine-based silane coupling agent, (C) the reactivity with the epoxy or oxetane-containing monofunctional monomer having the structure represented by the general formula (1) is increased, and thus the resistance of the cured film is increased. Chemical properties can be improved.

In the general formula (2), R ³ and R ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, or a substituted or unsubstituted group having 6 to 12 carbon atoms. A substituted aryl group is shown. (C) From the viewpoint of further improving the reactivity with the epoxy or oxetane-containing monofunctional monomer having the structure represented by the general formula (1), the alkyl group and the vinyl group preferably have 2 to 4 carbon atoms.

  Examples of the amine silane coupling agent having a structure represented by the general formula (2) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 4- Aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldimethoxysilane, 5-aminopentyltrimethoxysilane, 5-aminopentyltriethoxysilane, 5-aminopentylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl -3-aminopropyltrime Kishishiran, N- phenyl-3-aminopropyltriethoxysilane, etc. N- phenyl-3-aminopropyl methyl dimethoxy silane. Two or more of these may be contained. Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Triethoxysilane is preferable, and chemical resistance can be further improved.

  In the negative photosensitive resin composition of the present invention, (D) the content of the amine-based silane coupling agent having the structure represented by the general formula (2) is a viewpoint of further improving the chemical resistance of the cured film. Therefore, 0.1% by weight or more is preferable in the solid content of the negative photosensitive resin composition, and 1.0% by weight or more is more preferable. On the other hand, from the viewpoint of further improving the storage stability, it is preferably 10% by weight or less, more preferably 3% by weight or less, based on the solid content of the negative photosensitive resin composition.

  The negative photosensitive resin composition of the present invention contains (E) a solvent having an alcoholic hydroxyl group. (E) Examples of the solvent having an alcoholic hydroxyl group 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), tetrahydrofurfuryl alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n -Butyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanedio And the like. Two or more of these may be contained.

  The content of the solvent having an (E) alcoholic hydroxyl group in the negative photosensitive resin composition of the present invention is 25% by weight or more and 70% by weight or less in the negative photosensitive resin composition. (E) Storage stability falls that content of the solvent which has alcoholic hydroxyl group is less than 25 weight%. (E) The content of the solvent having an alcoholic hydroxyl group is preferably 30% by weight or more. On the other hand, when the content of (E) the solvent having an alcoholic hydroxyl group exceeds 70% by weight, film thickness variation occurs due to unevenness due to drying during pre-baking, and pattern workability decreases. From the viewpoint of appropriately drying during pre-baking and further suppressing unevenness of the cured film, 50% by weight or less is preferable.

  The negative photosensitive resin composition of the present invention may further contain a monomer other than the above-mentioned (C) epoxy or oxetane-containing monofunctional monomer. (C) As monomers other than the epoxy or oxetane-containing monofunctional monomer, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1, 4-butanediol diacrylate, 1,4-butanediol dimethacrylate 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapenta Erythritol Acrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylation Bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4 -(2-Methacryloyloxyethoxy) -3-methylphenyl] fluorene, (2-acryloyloxypropoxy) -3- Methylphenyl] fluorene, 9,9-bis [4- (2-acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) -3,5- Dimethylphenyl] fluorene, ethoxylated isocyanuric acid triacrylate, and the like.

  The negative photosensitive resin composition of the present invention may further contain a silane coupling agent other than the above-mentioned (D) amine-based silane coupling agent. (D) The adhesiveness with a board | substrate can be improved by containing silane coupling agents other than an amine-type silane coupling agent. (D) Examples of silane coupling agents other than amine-based silane coupling agents include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. , Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyl Dimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Toxisilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3-oxetanyl ) Methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-trime Such as silyl propyl succinic acid.

  The negative photosensitive resin composition of the present invention may further contain a solvent other than the solvent (E) having an alcoholic hydroxyl group. (E) Examples of the solvent other than the solvent having an alcoholic hydroxyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, ethylene glycol dimethyl ether, and ethylene. Ethers such as glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; dimethylformamide, Amides such as dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol Ethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, acetate such as 3-methyl-3-methoxybutyl acetate.

  When the negative photosensitive resin composition of the present invention contains (E) a solvent other than the solvent having an alcoholic hydroxyl group, the content of the entire solvent including these can be appropriately set according to the coating method and the like. . For example, when film formation is performed by spin coating, the content is generally 50 to 95% by weight in the negative photosensitive resin composition.

  The negative photosensitive resin composition of the present invention preferably further contains a polyfunctional thiol chain transfer agent. By containing a polyfunctional thiol chain transfer agent, radical curing can be sufficiently advanced, and the hardness and chemical resistance of the cured film can be further improved.

  Examples of the polyfunctional thiol chain transfer agent include pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), tripentaerythritol hepta (3-mercaptobutyrate), 1,4 -Bis (3-mercaptobutyryloxy) butane, 1,4-bis (3-mercaptobutyryloxy) pentane, 1,4-bis (3-mercaptobutyryloxy) hexane, 1,4-bis (3- Mercaptobutyryloxy) heptane, 1,4-bis (3-mercaptobutyryloxy) octane, 1,4-bis (3-mercaptobutyryloxy) nonane, 1,3,5-tris (3-mercaptobutyryl) Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Limethylolethanetris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolbutanthris (3-mercaptobutyrate), trimethylolpentanthris (3-mercaptobutyrate), trimethylol Examples include hexanetris (3-mercaptobutyrate). Two or more of these may be contained.

  When the negative photosensitive resin composition of the present invention contains a polyfunctional thiol-based chain transfer agent, the content of the negative photosensitive resin composition from the viewpoint of further improving the hardness and chemical resistance of the cured film. The solid content is preferably 0.3% by weight or more, and more preferably 1.0% by weight or more. On the other hand, from the viewpoint of improving the resolution, it is preferably 5% by weight or less in the solid content of the negative photosensitive resin composition, and more preferably 3% by weight or less.

  The negative photosensitive resin composition of the present invention may further contain an ultraviolet absorber. By containing the ultraviolet absorber, the resolution during development and the light resistance of the cured film can be improved.

  As the ultraviolet absorber, a benzotriazole compound, a benzophenone compound, and a triazine compound are preferable from the viewpoints of transparency and non-colorability.

  Examples of the benzotriazole-based compound include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1) -Phenylethyl) phenol, 2- [5chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butylphenol), 2,4 di-tert-butyl-6- (5-chloro Benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H- Benzotriazol-2-yl-4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl -6-dodecyl-4-methylphenol, 2 [2-hydroxy-3- (3,4,5,6 tetrahydrophthalimide - methyl) -5-methylphenyl] benzotriazole and the like.

  Examples of the benzophenone compounds include octabenzone and 2-hydroxy-4-n-octoxybenzophenone.

  Examples of the triazine compound include 2- (4,6-diphenyl-1,3,5triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  The negative photosensitive resin composition of the present invention may further contain a filler. Examples of the filler include inorganic oxide particles such as silica, zirconia, alumina, titania, and barium sulfate; metal particles; resin particles such as acrylic, styrene, silicone, and fluorine-containing polymers. Among these, silica particles and barium sulfate particles are preferable from the viewpoint of dispersibility. The particle diameter (weight average particle diameter) of the filler is preferably 0.5 μm or more and 4 μm or less.

  The negative photosensitive resin composition of the present invention may further contain various curing agents that accelerate the curing of the resin composition or facilitate the curing. Examples of the curing agent include silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained. Of these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferred from the viewpoints of stability of the curing agent and processability of the coating film.

  Since curing of polysiloxane is promoted by acid, the negative photosensitive resin composition of the present invention may further contain a curing catalyst such as a thermal acid generator. Examples of the thermal acid generator include various onium salt compounds such as aromatic diazonium salts, sulfonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenium salts, sulfonic acid esters, and halogen compounds.

  The negative photosensitive resin composition of the present invention may further contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants, and can improve the flowability during coating. .

  Examples of the surfactant include “Megafac (registered trademark)” “F142D (trade name)”, “F172 (trade name)”, “F173 (trade name)”, “F183 (trade name)”, “F444 ( "Product Name)", "F445 (Product Name)", "F470 (Product Name)", "F475 (Product Name)", "F477 (Product Name)", "DS-21 (Product Name)" Nippon Ink Chemical Co., Ltd.), “NBX-15 (trade name)”, “FTX-218 (trade name)” (manufactured by Neos Co., Ltd.) and other fluorosurfactants, “BYK-333 (product) Name) ”,“ BYK-301 (product name) ”,“ BYK-331 (product name) ”,“ BYK-345 (product name) ”,“ BYK-348 (product name) ”,“ BYK-361 (product) Name) "," BYK-3550 (product name) "," BYK-307 ( Name) "(manufactured by BYK Japan KK) silicone surfactants, such as, polyalkylene oxide surfactant, poly (meth) acrylate surfactant, and the like. Two or more of these may be contained.

  The negative photosensitive resin composition of the present invention may further contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone polymerization inhibitors and catechol polymerization inhibitors. Examples of the hydroquinone polymerization inhibitor include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis (1,1-dimethylbutyl). ) Hydroquinone and the like, and examples of the catechol-based polymerization inhibitor include catechol and tert-butylcatechol.

  The content of the polymerization inhibitor is preferably 0.001% by weight or more in the solid content of the negative photosensitive resin composition from the viewpoint of suppressing development residue. On the other hand, from the viewpoint of improving the sensitivity and suppressing the stain on the film surface, 0.5% by weight or less in the solid content of the negative photosensitive resin composition is preferable.

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

  Next, the method for producing the negative photosensitive resin composition of the present invention will be described with examples. For example, (B) a radical photopolymerization initiator and, if necessary, other additives are added to (E) a solvent having an alcoholic hydroxyl group and, if necessary, other solvent, dissolved by stirring, An alkali-soluble resin having (C) an epoxy or oxetane-containing monofunctional monomer, (D) an amine-based silane coupling agent and other additives as necessary, and further stirring for 20 minutes to 3 hours, thereby negative-type photosensitivity A resin composition can be obtained. The resulting solution may be filtered.

  Next, the cured film of the present invention will be described. The cured film of this invention consists of the hardened | cured material of the above-mentioned negative photosensitive resin composition. As for the film thickness of the cured film of this invention, 0.1-15 micrometers is preferable. The resolution of the cured film of the present invention is preferably 20 μm or less. The hardness of the cured film of the present invention is preferably 4H or more at a film thickness of 1.5 μm. The transmittance of the cured film of the present invention at a wavelength of 400 nm is preferably 90% or more at a film thickness of 1.5 μm. In addition, the hardness and the transmittance | permeability of a cured film can be made into the above-mentioned range, for example by using the above-mentioned negative photosensitive resin composition of this invention.

  Next, an example is given and demonstrated about the manufacturing method of the cured film of this invention. For example, after applying the above-mentioned negative photosensitive resin composition of the present invention on a base substrate and pre-baking, a pattern is formed by patterning exposure and development, and then cured to obtain a cured film.

  Examples of the method for applying the negative photosensitive resin composition of the present invention include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, and inkjet coating. .

  Examples of the heating device for pre-baking the coating film include a hot plate and an oven. The prebake temperature is preferably 50 to 150 ° C., and the prebake time is preferably 30 seconds to 30 minutes. The film thickness after pre-baking is preferably 0.1 to 15 μm.

  Examples of the exposure machine used for patterning exposure include a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA). Examples of the exposure light source include ultraviolet rays such as i-line, h-line, and g-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like. The exposure amount is preferably about 1 to 4000 mJ / cm 2 (converted to a wavelength of 365 nm exposure amount). Exposure may be performed through a desired mask, or exposure may be performed without using a mask.

  After patterning exposure, the exposed portion can be dissolved by development to obtain a negative pattern. Examples of the developing method include methods such as showering, dipping, and paddle. The film after patterning exposure is preferably immersed in a developer for 5 seconds to 10 minutes. Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, and tetramethyl. Examples include alkaline developers such as aqueous solutions containing quaternary ammonium salts such as ammonium hydroxide and choline. After development, it is preferable to rinse with water, followed by dry baking in the range of 50 to 150 ° C.

  Examples of the heating device for thermosetting the film after development include a hot plate and an oven. The thermosetting temperature is preferably 120 to 280 ° C., and the thermosetting time is preferably about 1 hour.

  The cured film of the present invention includes a protective film for a touch panel, various hard coat materials, various protective films such as an overcoat for a color filter, an antireflection film, an optical filter, an insulating film for a touch sensor, a liquid crystal display element, and an organic EL display element. Suitable for thin film transistor (TFT) substrate planarization films, semiconductor device interlayer insulation films, solid-state imaging device planarization films and microlens array patterns, optical waveguide cores and cladding materials, color filter photo spacers, etc. be able to. Among these, since the cured film of the present invention is excellent in chemical resistance on the ITO substrate, it can be suitably used for a touch panel, and since it is excellent in pattern processability, it can be suitably used for a color filter.

  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 Polysiloxane solution (i)
In a 500 mL three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, and 26.23 g (0.25 mol) of 3-trimethoxysilylpropyl succinic anhydride. 10 mol), 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane and 180.56 g of diacetone alcohol (DAA) were charged, immersed in an oil bath at 40 ° C., and phosphoric acid in 55.8 g of water while stirring. An aqueous phosphoric acid solution in which 0.401 g (0.2 part by weight based on the charged monomers) was dissolved was added with a dropping funnel over 10 minutes. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 120 g of methanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain (a-1) a polysiloxane solution (i) having a carboxyl group and a radical polymerizable group. In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 5000 (polystyrene conversion). Moreover, when the silanol group / carboxyl group ratio in polysiloxane was computed by < ¹ > H-NMR and the acid value was measured, the carboxylic acid equivalent was 700 g / mol. Moreover, when the iodine value was measured, the double bond equivalent was 400 g / mol.

Synthesis Example 2 Polysiloxane solution (ii)
In a 500 mL three-necked flask, 34.05 g (0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 41.66 g (0.20 mol) of 4-trimethoxysilylbutyric acid, γ -82.04 g (0.40 mol) of acryloylpropyltrimethoxysilane and 182.22 g of DAA were charged, immersed in an oil bath at 40 ° C and stirred with 54.0 g of water and 0.395 g of phosphoric acid (based on the charged monomers). An aqueous solution of phosphoric acid in which 0.2 wt% was dissolved was added with a dropping funnel over 10 minutes. Next, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 120 g of methanol and water as by-products were distilled. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain (a-1) a polysiloxane solution (ii) having a carboxyl group and a radical polymerizable group. In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 6000 (polystyrene conversion). Moreover, when the silanol group / carboxyl group ratio in polysiloxane was computed by < ¹ > H-NMR and the acid value was measured, the carboxylic acid equivalent was 800 g / mol. Moreover, when the iodine value was measured, the double bond equivalent was 300 g / mol.

Synthesis Example 3 Polysiloxane solution (iii)
In a 500 mL three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, and 26.23 g (0.25 mol) of 3-trimethoxysilylpropyl succinic anhydride. 10 mol), 56.79 g (0.35 mol) of allyltrimethoxysilane, and 157.25 g of DAA (diacetone alcohol), which are immersed in an oil bath at 40 ° C. and stirred with 55.8 g of water and 0.341 g of phosphoric acid. A phosphoric acid aqueous solution in which (0.2 parts by weight with respect to the charged monomer) was dissolved was added with a dropping funnel over 10 minutes. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 120 g of methanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain (a-1) a polysiloxane solution (iii) having a carboxyl group and a radical polymerizable group. In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 5500 (polystyrene conversion). Moreover, when the silanol group / carboxyl group ratio in polysiloxane was computed by < ¹ > H-NMR and the acid value was measured, the carboxylic acid equivalent was 700 g / mol. Moreover, when the iodine value was measured, the double bond equivalent was 400 g / mol.

Synthesis Example 4 Polysiloxane solution (iv)
In a 500 mL three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 59.49 g (0.30 mol) of phenyltrimethoxysilane, 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane, Phosphoric acid charged with 174.65 g of DAA (Diacetone Alcohol), dissolved in 54.0 g of water and dissolved in 0.378 g of phosphoric acid (0.2 parts by weight with respect to the charged monomer) while immersed in an oil bath at 40 ° C. The aqueous solution was added with a dropping funnel over 10 minutes. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 120 g of methanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (iv). In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 4500 (polystyrene conversion). Moreover, when it tried to calculate the silanol group / carboxyl group ratio in polysiloxane by < ¹ > H-NMR, the carboxyl group was not detected. Moreover, when the iodine value was measured, the double bond equivalent was 400 g / mol.

Synthesis Example 5 Polysiloxane solution (v)
In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, and 26.23 g (0.20 mol) of 3-trimethoxysilylpropyl succinic anhydride. 10 mol), 166.03 g of DAA (Diacetone Alcohol) was added, and 0.391 g of phosphoric acid (0.2 parts by weight with respect to the charged monomer) was dissolved in 55.8 g of water while stirring in an oil bath at 40 ° C. The phosphoric acid aqueous solution was added with a dropping funnel over 10 minutes. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 120 g of methanol and water as by-products were distilled out. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (v). In addition, when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC, it was 6000 (polystyrene conversion). Moreover, when the silanol group / carboxyl group ratio in polysiloxane was computed by < ¹ > H-NMR and the acid value was measured, the carboxylic acid equivalent was 700 g / mol. Further, when the iodine value was measured, no double bond was detected.

Synthesis Example 6 Modified Acrylic Resin Solution (A)
In a 500 ml flask, 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of propylene glycol methyl ether acetate (PGMEA) were charged. Thereafter, 23.26 g of methacrylic acid, 18.59 g of styrene, and 32.80 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged, stirred for a while at room temperature, and bubbled in the flask. After sufficiently purging with nitrogen, the mixture was stirred with heating at 70 ° C. for 5 hours. Next, 12.69 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. ) A modified acrylic resin solution (A) which is a reaction product of an acrylic resin having a carboxyl group and a monosubstituted epoxy compound having a radical polymerizable group was obtained. PGMEA was added to the obtained acrylic resin solution (A) so that the solid content concentration was 50 wt%. The weight average molecular weight of the modified acrylic resin (A) was 24,000. Moreover, when the solid content acid value was measured based on JISK5601-2-1, the acid value was 120 g / mol. Moreover, when the iodine value was measured, the double bond equivalent was 1100 g / mol.

Synthesis Example 7 Modified acrylic resin solution (B)
A 500 ml flask was charged with 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 21.92 g of methacrylic acid, 17.67 g of styrene, and 31.18 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged, stirred for a while at room temperature, and bubbled in the flask. After sufficiently purging with nitrogen, the mixture was stirred with heating at 70 ° C. for 5 hours. Next, 17.00 g of 4- (glycidyloxy) butyl acrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. (A-2) A modified acrylic resin solution (B) which is a reaction product of an acrylic resin having a carboxyl group and a monosubstituted epoxy compound having a radical polymerizable group was obtained. PGMEA was added to the obtained acrylic resin solution (B) so that the solid content concentration was 50 wt%. The weight average molecular weight of the modified acrylic resin (B) was 23000. Moreover, when the solid content acid value was measured based on JISK5601-2-1, the acid value was 120 g / mol. Moreover, when the iodine value was measured, the double bond equivalent was 1100 g / mol.

Synthesis Example 8 Acrylic resin solution (C)
A 500 ml flask was charged with 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 6.33 g of methacrylic acid, 20.43 g of styrene, and 48.65 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature, and the inside of the flask was bubbled. After sufficiently purging with nitrogen, the mixture was stirred with heating at 70 ° C. for 5 hours. Next, 10.46 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution ( C) was obtained. PGMEA was added to the obtained acrylic resin solution (C) so that the solid content concentration was 50 wt%. The weight average molecular weight of the acrylic resin (C) was 22,000. Moreover, when the solid content acid value was measured based on JISK5601-2-1, it was less than 0.5 mgKOH / g and it confirmed that the carboxyl group did not remain | survive. Moreover, when the iodine value was measured, the double bond equivalent was 1100 g / mol.

Synthesis Example 9 Acrylic resin solution (D)
A 500 ml flask was charged with 2 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA. Thereafter, 15.69 g of methacrylic acid, 22.14 g of styrene, and 46.86 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature, and the inside of the flask was bubbled. After sufficiently purging with nitrogen, the mixture was stirred with heating at 70 ° C. for 5 hours. Next, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to obtain an acrylic resin solution (D). PGMEA was added to the obtained acrylic resin solution (D) so that the solid content concentration was 50 wt%. The weight average molecular weight of the acrylic resin (C) was 25000. Moreover, when the solid content acid value was measured based on JISK5601-2-1, the acid value was 300 g / mol. Further, when the iodine value was measured, no double bond was detected.

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

(1) Measurement of transmittance The composition prepared in each Example and Comparative Example was applied to a 5 cm square Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.) and a spin coater (Mikasa Co., Ltd. “1H-360S”). (Trade name) ”) was rotated at 500 rpm for 10 seconds, and then was rotated at 1000 rpm for 4 seconds and spin-coated. Subsequently, prebaking was performed at 90 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a prebaked film having a thickness of 2 μm. The prepared pre-baked film was exposed using a parallel light mask aligner (hereinafter referred to as PLA) (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source, and then an oven (ESPEC Corporation). ) “IHPS-222”), and cured in air at 230 ° C. for 1 hour to prepare a cured film having a thickness of 1.5 μm. The film thickness was measured at a refractive index of 1.55 using “Lambda Ace STM-602 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd. The same applies to the film thickness described below.

  About the obtained cured film, the transmittance | permeability of 400 nm was measured using the ultraviolet-visible spectrophotometer "UV-260 (brand name)" (made by Shimadzu Corporation).

(2) Measurement of hardness Pencil hardness was measured according to "JIS K5600-5-4 (1999)" about the cured film with a film thickness of 1.5 micrometers obtained by the method of said (1) description.

(3) Evaluation of pattern workability (3-1) Measurement of sensitivity The composition produced in each Example and Comparative Example was applied to a silicon wafer with a spin coater ("1H-360S (trade name)" manufactured by Mikasa Co., Ltd.). ) For 10 seconds at 500 rpm, followed by spin coating at 1000 rpm for 4 seconds. Subsequently, prebaking was performed at 90 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a prebaked film having a thickness of 2 μm. The obtained pre-baked film was exposed with a gap of 100 μm using PLA and a gray scale mask for sensitivity measurement using an ultrahigh pressure mercury lamp as a light source. After that, using an automatic developing device (“AD-2000 (trade name)”, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with 0.045 wt% potassium hydroxide aqueous solution for 90 seconds, followed by rinsing with water for 30 seconds.

  After exposure and development, the exposure amount for forming a 30 μm line-and-space pattern with a one-to-one width (hereinafter referred to as the optimum exposure amount) was defined as sensitivity. The exposure amount was measured with an I-line illuminometer.

(3-2) Measurement of resolution The resolution after development at the optimum exposure amount was measured. It should be noted that the minimum pattern among the patterns in which a hole diameter of 95% or more with respect to the mask diameter is resolved is defined as the resolution.

(4) Evaluation of chemical resistance (ITO substrate adhesion)
A cured film having a thickness of 1.5 μm was formed on a glass substrate (hereinafter referred to as “ITO substrate”) having ITO sputtered on the surface by the method described in (1) above.

(4-1) Evaluation of adhesion of ITO substrate after alkali treatment An ITO substrate having a cured film obtained by the method described in (4) above is monoethanolamine / diethylene glycol monobutyl ether = 30/70 (weight ratio). After being immersed in a mixed aqueous solution at 70 ° C. for 10 minutes, the adhesion between ITO and the cured film was evaluated according to JIS “K5600-5-6 (established April 20, 1999)”. That is, on the ITO surface on the ITO substrate, 100 parallel squares of 11 vertical and horizontal lines are drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm × 1 mm are produced. did. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is applied to the cut cured film surface, and it is rubbed with an eraser (JIS S6050 passed product) to hold it, hold one end of the tape, and make a right angle to the plate. The remaining number of squares when peeled instantaneously while keeping was counted visually to calculate the peeled area. Evaluation was made based on the following criteria from the peeled area of the cells, and 3 or more was judged as acceptable.
5: Peel area = 0%
4: Peeling area = 1 to 4%
3: Peel area = 5-14%
2: Peel area = 15-34%
1: Peel area = 35-64%
0: Peeling area = 65 to 100%.

(4-2) Evaluation of adhesion of ITO substrate after acid treatment An ITO substrate having a cured film obtained by the method described in (4) above is HCl / HNO3 / H2O = 18/4/78 (weight ratio). After being immersed in an aqueous solution at 70 ° C. mixed for 10 minutes, the adhesion between ITO and the cured film was evaluated in the same manner as in (4-1).

(5) Evaluation of storage stability (ITO substrate adhesion)
After the compositions prepared in each Example and Comparative Example were stored at 30 ° C. for 168 hours, a cured film having a thickness of 1.5 μm was prepared by the method described in (4), and the composition described in (4) The method was subjected to acid or alkali treatment to evaluate adhesion. The smaller the difference from the evaluation result of (4), the better the storage stability.

  In addition, after the compositions prepared in Example 1, Examples 12 to 13 and Example 24 were stored at 30 ° C. for 168 hours, a cured film having a thickness of 1.5 μm was formed by the method described in (4) above. An acid or alkali treatment was performed by the method described in (4) above except that the temperature of the aqueous solution was changed from 70 ° C. to 80 ° C., and the adhesion was evaluated. The smaller the difference from the evaluation result of (4), the better the storage stability.

(6) Evaluation of unevenness The method described in (1) above, using the compositions prepared in each of Examples and Comparative Examples on a 10 cm square glass substrate (hereinafter referred to as “Cr substrate”) having Cr sputtered on the surface. In the same manner, a cured film having a thickness of 1.5 μm was formed. Regarding the 8 cm square area portion excluding the 1 cm edge of the substrate, the film thickness was measured at intervals of 1 cm, unevenness was evaluated according to the following criteria, and 3 or more were determined to be acceptable.

5: The value obtained by subtracting the minimum film thickness from the maximum film thickness is less than 0.05 μm. 4: The value obtained by subtracting the minimum film thickness from the maximum film thickness is 0.05 μm or more and less than 0.7 μm. The subtracted value is 0.07 μm or more and less than 0.10 μm 2: The value obtained by subtracting the minimum film thickness from the maximum film thickness is 0.10 μm or more and less than 0.15 μm 1: The value obtained by subtracting the minimum film thickness from the maximum film thickness is 0.00. 15 μm or more.

  Monomers and polyfunctional thiol chain transfer agents used in the examples are shown below.

EA-1010N (trade name) (manufactured by Shin-Nakamura Chemical Co., Ltd.)
4HBAGE (trade name) (manufactured by Nippon Kasei Co., Ltd.)
Kayalad (registered trademark) DPHA (trade name) (manufactured by Nippon Kayaku Co., Ltd.)
Karenz MT-PE1 (trade name) (manufactured by Showa Denko KK).

Example 1
1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (“Irgacure® OXE-01 (trade name)” Ciba Specialty under a yellow light Chemical) 0.931 g and 4-t-butylcatechol 0.056 g are dissolved in a mixed solvent of DAA 18.041 g, 3-methoxy-1-butanol 8.000 g, PGMEA 40.000 g, and it is a silicone surfactant. Add 0.03 g of “BYK” (registered trademark) -333 (trade name) ”(manufactured by Big Chemie Japan Co., Ltd.) and 0.372 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and stir. did. 9.306 g of bisphenol A monoglycidyl ether monoacrylate (“EA-1010N (trade name)” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 23.264 g of polysiloxane solution (i) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter, and the composition 1 was obtained. About the obtained composition 1, the transmittance | permeability, hardness, pattern workability, chemical resistance, storage stability, and nonuniformity were evaluated by the said method.

Example 2
A composition 2 was obtained in the same manner as in Example 1 except that the polysiloxane solution (ii) was used instead of the polysiloxane solution (i). Using the obtained composition 2, it evaluated by the said method.

Example 3
A composition 3 was obtained in the same manner as in Example 1 except that the polysiloxane solution (iii) was used instead of the polysiloxane solution (i). Using the obtained composition 3, it evaluated by the said method.

Example 4
A composition 4 was prepared in the same manner as in Example 1 except that 4-hydroxybutyl acrylate glycidyl ether (“4HBAGE (trade name)” manufactured by Nippon Kasei Co., Ltd.) was used instead of “EA-1010N (trade name)”. Obtained. The obtained composition 4 was used for evaluation by the above method.

Example 5
A composition 5 was obtained in the same manner as in Example 1 except that 3-aminopropyltrimethoxysilane was used instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. Using the obtained composition 5, it evaluated by the said method.

Example 6
The DAA addition amount in the mixed solvent is changed from 18.041 g to 10.041 g, the 3-methoxy-1-butanol addition amount is changed from 8.000 g to 6.000 g, and the PGMEA addition amount is changed from 40.000 g to 50.000 g. In the same manner as in Example 1, a composition 6 was obtained. Using the obtained composition 6, it evaluated by the said method.

Example 7
Composition 7 was carried out in the same manner as in Example 1 except that the amount of 3-methoxy-1-butanol added in the mixed solvent was changed from 8.000 g to 18.000 g, and the amount of PGMEA added was changed from 40.000 g to 30.000 g. Obtained. Using the obtained composition 7, it evaluated by the said method.

Example 8
Composition 8 was obtained in the same manner as in Example 1 except that the DAA addition amount in the mixed solvent was changed from 18.041 g to 3.042 g and the PGMEA addition amount was changed from 40.000 g to 55.000 g. Using the obtained composition 8, it evaluated by the said method.

Example 9
The DAA addition amount in the mixed solvent is changed from 18.041 g to 18.042 g, the 3-methoxy-1-butanol addition amount is changed from 8.000 g to 38.000 g, and the PGMEA addition amount is changed from 40.000 g to 10.000 g. In the same manner as in Example 1, a composition 9 was obtained. Using the obtained composition 9, it evaluated by the said method.

Example 10
Under a yellow light, 0.914 g of ““ Irgacure ”OXE-01 (trade name)” and 0.054 g of 4-t-butylcatechol were added to 18.297 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 40.000 PGMEA. 000 g of a mixed solvent, 0.030 g of ““ BYK ”-333 (trade name)”, 0.365 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, pentaerythritol tetrakis (3-mercapto (Butyrate) ("Karenz MT-PE1 (trade name)" manufactured by Showa Denko KK) 0.365 g was added and stirred. Thereto, 9.135 g of “EA-1010N (trade name)” and 22.839 g of polysiloxane solution (i) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the composition 10. FIG. Using the obtained composition 10, it evaluated by the said method.

Example 11
A composition 11 was obtained in the same manner as in Example 10 except that “4HBAGE (trade name)” was used instead of “EA-1010N (trade name)”. Using the obtained composition 11, it evaluated by the said method.

Example 12
A composition 12 was obtained in the same manner as in Example 1 except that 2-methyl-1,3-propanediol was used instead of DAA. Using the obtained composition 12, it evaluated by the said method.

Example 13
Under yellow light, 0.931 g of ““ Irgacure ”OXE-01 (trade name) and 0.056 g of 4-t-butylcatechol were added to 32.000 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 30.000 PGMEA. It was dissolved in 694 g of a mixed solvent, 0.030 g of ““ BYK ”-333 (trade name)” and 0.372 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane were added and stirred. 9.306 g of “EA-1010N (trade name)” and 18.611 g of the modified acrylic resin solution (A) were added and stirred. Subsequently, it filtered with a 0.45-micrometer filter, and obtained the composition 13. Using the obtained composition 13, it evaluated by the said method.

Example 14
A composition 14 was obtained in the same manner as in Example 13 except that the modified acrylic resin solution (B) was used instead of the modified acrylic resin solution (A). Using the obtained composition 14, it evaluated by the said method.

Example 15
A composition 15 was obtained in the same manner as in Example 13 except that 3-aminopropyltrimethoxysilane was used instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. Using the obtained composition 15, it evaluated by the said method.

Example 16
A composition 16 was obtained in the same manner as in Example 15 except that the modified acrylic resin solution (B) was used instead of the modified acrylic resin solution (A). Using the obtained composition 16, it evaluated by the said method.

Example 17
A composition 17 was obtained in the same manner as in Example 15 except that “4HBAGE (trade name)” was used instead of “EA-1010N (trade name)”. Using the obtained composition 17, it evaluated by the said method.

Example 18
The DAA addition amount in the mixed solvent was changed from 32.000 g to 24.000 g, the 3-methoxy-1-butanol addition amount was changed from 8.000 g to 6.000 g, and the PGMEA addition amount was changed from 30.694 g to 40.694 g. In the same manner as in Example 13, a composition 18 was obtained. Using the obtained composition 18, it evaluated by the said method.

Example 19
The same procedure as in Example 13 was followed, except that the 3-methoxy-1-butanol addition amount in the mixed solvent was changed from 8.000 g to 18.000 g, and the PGMEA addition amount was changed from 30.694 g to 20.694 g. Obtained. Using the obtained composition 19, it evaluated by the said method.

Example 20
A composition 20 was obtained in the same manner as in Example 13, except that the DAA addition amount in the mixed solvent was changed from 32.000 g to 17.000 g, and the PGMEA addition amount was changed from 30.694 g to 45.694 g. Using the obtained composition 20, it evaluated by the said method.

Example 21
The same procedure as in Example 13 was conducted, except that the amount of 3-methoxy-1-butanol added in the mixed solvent was changed from 8.000 g to 38.000 g, and the amount of PGMEA added was changed from 30.694 g to 0.694 g. Obtained. Using the obtained composition 21, it evaluated by the said method.

Example 22
Under a yellow light, 0.914 g of ““ Irgacure ”OXE-01 (trade name) and 0.055 g of 4-t-butylcatechol, 32.000 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 30.865 g of PGMEA In a mixed solvent of 0.030 g of “BYK” -333 (trade name) solution, 0.365 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, “Karenz MT-PE1 (product) Name) ”was added and stirred. Thereto, 9.135 g of “EA-1010N (trade name)” and 18.271 g of the modified acrylic resin solution (A) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and the composition 22 was obtained. Using the obtained composition 22, it evaluated by the said method.

Example 23
A composition 23 was obtained in the same manner as in Example 22 except that “4HBAGE (trade name)” was used instead of “EA-1010N (trade name)”. The obtained composition 23 was used and evaluated by the above method.

Example 24
A composition 24 was obtained in the same manner as in Example 13 except that 2-methyl-1,3-propanediol was used instead of DAA. The obtained composition 24 was used for evaluation by the above method.

Comparative Example 1
Under yellow light, 0.948 g of ““ Irgacure ”OXE-01 (trade name)” and 0.057 g of 4-t-butylcatechol were added to DAA 17.776 g, 3-methoxy-1-butanol 8.000 g, PGMEA 40. It was dissolved in 000 g of a mixed solvent, 0.030 g of ““ BYK ”-333 (trade name)” solution was added and stirred. Thereto, 9.482 g of dipentaerythritol hexaacrylate (“Kayarad (registered trademark)” DPHA (trade name) manufactured by Nippon Kayaku Co., Ltd.) and 23.706 g of polysiloxane solution (i) were added and stirred. . Subsequently, it filtered with a 0.45 micrometer filter and the composition 25 was obtained. The obtained composition 25 was used for evaluation by the above method.

Comparative Example 2
Under a yellow light, 0.931 g of ““ Irgacure ”OXE-01 (trade name)” and 0.056 g of 4-t-butylcatechol were added to 18.042 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 40.000 PGMEA. The solution was dissolved in 000 g of a mixed solvent, 0.030 g of a “BYK” -333 (trade name) solution and 0.372 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane were added and stirred. 9.306 g of ““ Kayarad (registered trademark) ”DPHA (trade name)” and 23.264 g of the polysiloxane solution (i) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and the composition 26 was obtained. The obtained composition 26 was used for evaluation by the above method.

Comparative Example 3
A composition 27 was obtained in the same manner as in Comparative Example 1 except that “EA-1010N (trade name)” was used instead of “Kayarad” DPHA (trade name). The obtained composition 27 was used for evaluation by the above method.

Comparative Example 4
The DAA addition amount in the mixed solvent is changed from 18.041 g to 2.042 g, the 3-methoxy-1-butanol addition amount is changed from 8.000 g to 4.000 g, and the PGMEA addition amount is changed from 40.000 g to 60.000 g. In the same manner as in Example 1, a composition 28 was obtained. The obtained composition 28 was used for evaluation by the above method.

Comparative Example 5
A composition 29 was obtained in the same manner as in Example 1, except that the DAA addition amount in the mixed solvent was changed from 18.041 g to 53.042 g and the PGMEA addition amount was changed from 40.000 g to 5.000 g. The obtained composition 29 was used for evaluation by the above method.

Comparative Example 6
A composition 30 was obtained in the same manner as in Example 1 except that the polysiloxane solution (iv) was used instead of the polysiloxane solution (i). Using the obtained composition 30, it evaluated by the said method.

Comparative Example 7
A composition 31 was obtained in the same manner as in Example 1 except that the polysiloxane solution (v) was used instead of the polysiloxane solution (i). Using the obtained composition 31, it evaluated by the said method.

Comparative Example 8
Under yellow light, 0.948 g of ““ Irgacure ”OXE-01 (trade name) and 0.057 g of 4-t-butylcatechol were added to DAA 32.000 g, 3-methoxy-1-butanol 8.000 g, PGMEA 30. It was dissolved in 518 g of a mixed solvent, 0.030 g of ““ BYK ”-333 (trade name)” solution was added and stirred. Thereto, 9.482 g of ““ Kayarad ”DPHA (trade name)” and 18.965 g of the modified acrylic resin solution (A) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and the composition 32 was obtained. The obtained composition 32 was used for evaluation by the above method.

Comparative Example 9
Under a yellow light, 0.931 g of ““ Irgacure ”OXE-01 (trade name)” and 0.056 g of 4-t-butylcatechol were added to 32.000 g of DAA, 38.000 g of 3-methoxy-1-butanol, and PGMEA. It was dissolved in 694 g of a mixed solvent, 0.030 g of ““ BYK ”-333 (trade name)” solution and 0.372 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane were added and stirred. Thereto, 9.306 g of ““ Kayarad ”DPHA (trade name)” and 18.611 g of the modified acrylic resin solution (A) were added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and the composition 33 was obtained. The obtained composition 33 was used and evaluated by the above method.

Comparative Example 10
A composition 34 was obtained in the same manner as in Comparative Example 8, except that “EA-1010N (trade name)” was used instead of “Kayarad” DPHA (trade name). Using the obtained composition 34, it evaluated by the said method.

Comparative Example 11
The DAA addition amount in the mixed solvent was changed from 18.4.01 g to 16.000 g, the 3-methoxy-1-butanol addition amount was changed from 8.000 g to 4.000 g, and the PGMEA addition amount was changed from 40.000 g to 50.694 g. In the same manner as in Example 13, a composition 35 was obtained. Using the obtained composition 35, it evaluated by the said method.

Comparative Example 12
A composition 36 was obtained in the same manner as in Example 13 except that the acrylic resin solution (C) was used instead of the modified acrylic resin solution (A). The obtained composition 36 was used for evaluation by the above method.

Comparative Example 13
A composition 37 was obtained in the same manner as in Example 13 except that the acrylic resin solution (D) was used instead of the modified acrylic resin solution (A). The obtained composition 37 was used for evaluation by the above method.

  Tables 1 to 3 show main compositions of Examples and Comparative Examples, and Tables 4 to 6 show evaluation results. In addition, among the evaluations of storage stability, the evaluation results after acid or alkali treatment at a temperature of 80 ° C. were 4 in Example 1 and Example 13, while 5 in Example 12 and Example 24. Met.

  The cured film of the present invention includes a protective film for a touch panel, various hard coat materials, various protective films such as an overcoat for a color filter, an antireflection film, an optical filter, an insulating film for a touch sensor, a liquid crystal display element, and an organic EL display element. Suitable for thin film transistor (TFT) substrate planarization films, semiconductor device interlayer insulation films, solid-state imaging device planarization films and microlens array patterns, optical waveguide cores and cladding materials, color filter photo spacers, etc. Used.

Claims (5)

(A) an alkali-soluble resin having a carboxyl group, (B) a radical photopolymerization initiator, (C) an epoxy or oxetane-containing monofunctional monomer having a structure represented by the following general formula (1), (D) the following general formula (2) containing an amine silane coupling agent having a structure represented by (2) and (E) a solvent having an alcoholic hydroxyl group,
The (A) alkali-soluble resin having a carboxyl group has (a-1) a polysiloxane having a carboxyl group and a radical polymerizable group and / or (a-2) an acrylic resin having a carboxyl group and a radical polymerizable group. A negative photosensitive resin composition comprising a modified acrylic resin which is a reaction product with a monosubstituted epoxy compound, and containing 25 to 70% by weight of the solvent having the (E) alcoholic hydroxyl group.

(In the above general formula (1), X represents a divalent group having an alkylene oxide having 2 to 40 carbon atoms or a divalent group having an aromatic ring, R ¹ represents hydrogen or a methyl group. R ² represents (A divalent hydrocarbon group having 1 to 2 carbon atoms is shown.)

(In the general formula (2), R ³ and R ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted vinyl group, or a substituted or unsubstituted group having 6 to 12 carbon atoms. Represents an unsubstituted aryl group.) The negative photosensitive resin composition according to claim 1, wherein X in the general formula (1) is a group derived from bisphenols. Furthermore, the negative photosensitive resin composition of Claim 1 or 2 containing a polyfunctional thiol type | system | group chain transfer agent. The cured film which consists of hardened | cured material of the negative photosensitive resin composition as described in any one of Claims 1-3. A touch panel or a color filter substrate having the cured film according to claim 4.