JP7119390B2 - Negative photosensitive resin composition and cured film using the same - Google Patents

Description

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

Hard coat materials are currently used in a wide variety of applications, and are used, for example, to improve the surface hardness of automobile parts, containers for cosmetics, sheets, films, optical discs, thin displays, and the like. Properties required for the hard coat material include hardness, scratch resistance, heat resistance, weather resistance, and adhesiveness. Representative examples of hard coat materials include radical polymerization type UV curable hard coats containing polymerizable group-containing oligomers, monomers, photopolymerization initiators and other additives (e.g., Non-Patent Document 1 reference). By UV irradiation, oligomers and monomers are radically polymerized to crosslink, and a highly rigid film can be obtained. This hard coat material has advantages such as a short time required for curing and excellent productivity, and the ability to use a negative photosensitive material based on a general radical polymerization mechanism.

A capacitive touch panel, which has been attracting attention in recent years, is one of the applications of hard coat materials. The structure of a capacitive touch panel has wiring formed of ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) on glass, and a protective film for protecting an insulating film and elements. The characteristics required for this insulating film and protective film include transparency, pattern processability for circuit connection, hardness high enough to prevent scratches during the modularization process, and resistance to acid and alkali treatment performed in the post-process. There is a demand for a photosensitive hard coat material that satisfies chemical resistance and storage stability.

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

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

JP-A-2000-187321 JP 2009-53254 A

Noboru Ohara et al., "Improvement of material design, coating technology and hardness in hard coat films centered 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 of insufficient storage stability. 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 the chemical resistance used in touch panel production in recent years is insufficient.

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

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

In general formula (1) above, 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 above 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 A substituted aryl group is shown.

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

The negative photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin having a carboxyl group, (B) a photoradical polymerization initiator, and (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, the (A) alkali-soluble resin having a carboxyl group is (a-1) a polysiloxane having a carboxyl group and a radically polymerizable group and/or (a-2) an acrylic resin having a carboxyl group and a radically polymerizable group. 25 to 70% by weight of (E) a solvent having an alcoholic hydroxyl group in the negative photosensitive resin composition. Containing (C) an epoxy- or oxetane-containing monofunctional monomer having a structure represented by the general formula (1) and (D) an amine-based silane coupling agent having a structure represented by the general formula (2) As a result, these components are crosslinked by UV curing and heat curing, so that the chemical resistance can be greatly improved, but there is a problem that the storage stability is lowered. The present invention can also solve the storage stability problem by adjusting the content of (E) the solvent having an alcoholic hydroxyl group to 25 to 70% by weight.

In general formula (1) above, 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 above 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 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 radically polymerizable group (hereinafter sometimes referred to as "(a-1) polysiloxane") and/or (a-2) a modified acrylic resin that is a reaction product of an acrylic resin having a carboxyl group and a monosubstituted epoxy compound having a radically polymerizable group (hereinafter sometimes referred to as "(a-2) modified acrylic resin"); contains (A) an alkali-soluble resin having a carboxyl group. Here, the alkali-soluble resin refers to a resin having a carboxyl group. Inclusion of the above (a-1) and/or (a-2) makes it soluble in an alkaline developer, so that pattern workability can be improved. Moreover, a cured film having high hardness and high transparency can be obtained by UV curing and heat curing. The radically polymerizable groups (a-1) and (a-2) can improve the chemical resistance.

(a-1) Polysiloxane is obtained by, for example, hydrolyzing an organosilane compound having a carboxyl group and/or a dicarboxylic anhydride group and an organosilane compound having a radically polymerizable group, and condensing the hydrolyzate. What can be obtained is mentioned. If necessary, an organosilane compound having a carboxyl group and/or a dicarboxylic anhydride group or an organosilane compound having a radically polymerizable group, together with a carboxyl group, a dicarboxylic anhydride group, and a radically polymerizable group. You may use the organosilane which does not have.

Organosilane compounds having a carboxyl group include, for example, 3-trimethoxysilylpropylsuccinic 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-trimethoxysilylvalerate, 5-triethoxysilylvalerate, 5-dimethyl Linear fats such as methoxysilylvalerate, 5-dimethylethoxysilylvalerate, 6-trimethoxysilylcaproic acid, 6-triethoxysilylcaproic acid, 6-dimethylmethoxysilylcaproic acid, 6-dimethylethoxysilylcaproic acid Group carboxylic acid compounds; 4-(3-trimethoxysilylpropoxy) cyclohexanecarboxylic acid, 4-(3-triethoxysilylpropoxy) cyclohexanecarboxylic acid, 4-(3-dimethylmethoxysilylpropoxy) cyclohexanecarboxylic acid, 4-( Alicyclic aliphatic carboxylic acid-containing compounds such as 3-dimethylethoxysilylpropoxy)cyclohexanecarboxylic acid; 4-(3-trichlorosilylpropoxy)benzoic acid, 4-(3-trimethoxysilylpropoxy)benzoic acid, 4-( 3-triethoxysilylpropoxy)benzoic acid, 4-(3-dimethylmethoxysilylpropoxy)benzoic acid, 4-(3-dimethylethoxysilylpropoxy)benzoic acid and other aromatic carboxylic acid compounds. You may use 2 or more types of these. 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.

Organosilane compounds having a dicarboxylic anhydride group include, for example, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3 -dimethylethoxysilylpropylsuccinic 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-dimethylethoxysilylpropyl)cyclohexyl-1,2-dicarboxylic anhydride, 4-(2-trimethoxysilylethyl)phthalic anhydride, 4-(2-triethoxy silylethyl)phthalic anhydride, 4-(2-dimethylmethoxysilylethyl)phthalic anhydride, 4-(2-dimethylethoxysilylethyl)phthalic anhydride, 3-(3-trimethoxysilylpropyl)phthalic acid anhydride, 3-(3-triethoxysilylpropyl) phthalic anhydride, 3-(3-dimethylmethoxysilylpropyl) phthalic anhydride, 3-(3-dimethylethoxysilylpropyl) phthalic anhydride, etc. be done. You may use 2 or more types of these. Among these, 3-trimethoxysilylpropylsuccinic anhydride is preferable from the viewpoint of improving solubility in a developer during pattern formation and suppressing pattern peeling during development.

Examples of radically polymerizable groups include vinyl groups, α-methylvinyl groups, allyl groups, styryl groups, and (meth)acryloyl groups. 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, a (meth)acryloyl group is a generic term for a methacryloyl group and an acryloyl group.

Organosilane compounds having a radically polymerizable group include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi(methoxyethoxy)silane, allyl trimethoxysilane, allyltriethoxysilane, allyltri(methoxyethoxy)silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi(methoxyethoxy)silane, styryltrimethoxysilane, styryltriethoxysilane, styryltri(methoxyethoxy)silane , styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, styrylmethyldi(methoxyethoxy)silane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-acryloylpropyltri(methoxyethoxy)silane, γ- methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-methacryloylpropyltri(methoxyethoxy)silane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-methacryloylpropyl(methoxyethoxy)silane and the like. You may use 2 or more types of these. Among them, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-methacryloylpropyltrimethoxysilane are used from the viewpoint of further improving the hardness of the cured film and the sensitivity during pattern processing. Ethoxysilane is preferred.

Examples of organosilanes having neither a carboxyl group, a dicarboxylic anhydride group, nor a radically polymerizable group include 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-aminopropyltrimethoxysilane Silane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxy Ethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxy Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxysilane Butyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxy Butyltriethoxysilane, (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) ) ethyl tripe noxysilane, 3-(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-glycidoxyethylmethyldiethoxysilane Silane, 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, tetraethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltrimethoxysilane, fluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and the like.

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

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

The conditions for the hydrolysis reaction can be appropriately set. For example, after adding an acid catalyst and water to an organosilane compound in a solvent over 1 to 180 minutes, the reaction temperature is room temperature to 110° C. for 1 to 180 minutes. It is preferable to react. By carrying out 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 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 the organosilane compounds used in the hydrolysis reaction. By adjusting the amount of the solvent to be added within the above range, it is possible to easily adjust the hydrolysis reaction to proceed as necessary and sufficiently.

The water used for the hydrolysis reaction is preferably ion-exchanged water. The amount of water is preferably 1.0 to 4.0 mol per 1 mol of silane atoms.

The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. Acid catalysts include, for example, acidic aqueous solutions containing formic acid, acetic acid, and phosphoric acid. It is preferable to add 0.15 parts by weight of these acid catalysts to 100 parts by weight of all the organosilane compounds used during the hydrolysis reaction. By setting the amount of the acid catalyst to be added within the above range, it is possible to easily adjust so that the hydrolysis reaction proceeds as necessary and sufficiently.

The condensation reaction includes, for example, a method of obtaining a silanol compound by hydrolysis reaction of an organosilane compound, then heating the reaction solution as it is at 50° C. or higher and below the boiling point of the solvent for 1 to 100 hours to react. In order to increase the degree of polymerization of polysiloxane, it may be reheated or a basic catalyst may be added.

Solvents used in the hydrolysis reaction of the organosilane compound and the condensation reaction of the hydrolyzate can be appropriately selected in consideration of the stability, wettability and volatility of the organosilane compound and polysiloxane.

Examples of solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy. -1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol and other alcohols; ethylene glycol, propylene glycol and other glycols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, propylene glycol mono-t-butyl ether; methyl ethyl ketone, acetylacetone, methyl propyl ketones such as ketones, 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 mono Acetates such as ethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate and butyl lactate; aromatics such as toluene, xylene, hexane and cyclohexane or aliphatic hydrocarbons; γ-butyrolactone; N-methyl-2-pyrrolidone; dimethylsulfoxide and the like. You may use 2 or more types of these. 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 and the like are preferred.

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

The carboxylic acid equivalent of (a-1) 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, it is preferably 1400 g/mol or less, more preferably 1000 g/mol or less, from the viewpoint of improving solubility in a developer during pattern formation. Here, the carboxylic acid equivalent of polysiloxane can be calculated by measuring the acid value after calculating the silanol group/carboxyl group ratio in the polysiloxane by ¹ H-NMR.

(a-1) As a means for adjusting 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 per 1 mol of all organosilanes constituting the polysiloxane. The total amount of the above-mentioned preferable range, and the like.

(a-1) The content of radically polymerizable groups in the polysiloxane, the 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 within 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 adjusting the double bond equivalent of polysiloxane to the above range, for example, the total amount of organosilane compounds having a radically polymerizable group per 1 mol of all organosilanes constituting polysiloxane is and the like.

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

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

Examples of ethylenic monomers having a carboxyl group include (meth)acrylic acid, itaconic acid, maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalate and the like. You may use 2 or more types of these. Among these, (meth)acrylic acid is preferable from the viewpoint of improving solubility in a developer during pattern formation and suppressing pattern peeling during development.

Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, and (meth)acrylate. Cyclohexyl Acrylate, Cyclohexenyl (Meth)acrylate, 4-Methoxycyclohexyl (Meth)acrylate, 2-Cyclopropyloxycarbonylethyl (Meth)acrylate, 2-Cyclopentyloxycarbonylethyl (Meth)acrylate, (Meth)acrylate 2-cyclohexyloxycarbonylethyl acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, (meth)acrylic isobornyl acid, tricyclodecanyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, adamantylmethyl (meth)acrylate, (meth)acrylic acid and 1-methyladamantyl acrylate. You may use 2 or more types of these.

Examples of vinyl aromatic compounds include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene and α-methylstyrene. You may use 2 or more types of these. Among these, styrene is preferable from the viewpoint of further improving the chemical resistance of the cured film.

Examples of unsaturated amide compounds include (meth)acrylamide, N-methylolacrylamide, N-vinylpyrrolidone and the like. You may use 2 or more types of these.

Other vinyl compounds include, for example, (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-hydroxyvinyl ether, 4 - hydroxy vinyl ether and the like.

A monosubstituted epoxy compound having a radically polymerizable group in the present invention refers to a compound having a radically polymerizable group and one epoxy group in one molecule. Monosubstituted epoxy compounds having a radically polymerizable group include, for example, glycidyl (meth)acrylate, 2-(glycidyloxy)ethyl (meth)acrylate, 3-(glycidyloxy)propyl (meth)acrylate, (meth) ) 4-(glycidyloxy)butyl acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether , α-methyl-p-vinylbenzyl glycidyl ether and the like. You may use 2 or more types of these. Among these, glycidyl (meth)acrylate, 2-(glycidyloxy)ethyl (meth)acrylate, 3-(glycidyloxy)propyl (meth)acrylate, and 4-(glycidyloxy)butyl (meth)acrylate are Preferably, the reaction of the epoxy group can be easily adjusted, and the reactivity of the radically polymerizable group can be enhanced.

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

(a-2) The total amount of the monosubstituted epoxy compound having a radically polymerizable group per 1 mol of the total amount of the ethylenic monomer having a carboxyl group and the vinyl-based compound constituting the modified acrylic resin is a preferable range described below for the double bond equivalent. from the viewpoint of adjusting to 0.01 mol or more, preferably 0.45 mol or less.

The conditions for radical polymerization can be appropriately set. and the radical polymerization catalyst are preferably reacted at 60 to 110° C. for 30 to 300 minutes.

Examples of radical polymerization catalysts 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 radically polymerizable group include amino catalysts such as dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, dimethylbenzylamine; 2-ethyl tin-based catalysts such as tin hexanoate and dibutyltin laurate; titanium-based catalysts such as titanium (IV) 2-ethylhexanoate; phosphorus-based catalysts such as triphenylphosphine; Chromium-based catalysts and the like are included.

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

(a-2) As a means for adjusting the carboxylic acid equivalent of the modified acrylic resin to the above range, for example, the ethylenic monomer having a carboxyl group and the vinyl compound constituting the acrylic resin For example, the total amount of the ethylenic monomers and the total amount of the monosubstituted epoxy compound having a radically polymerizable group are set within the preferred ranges described above.

(a-2) The modified acrylic resin preferably has a double bond equivalent weight of 150 to 10,000 g/mol, more preferably 200 to 1500 g/mol. By setting the double bond equivalent within 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 adjusting the double bond equivalent of the modified acrylic resin to the above range, for example, 1 mol of the total amount of ethylenic monomers and vinyl compounds having a carboxyl group constituting the acrylic resin has a carboxyl group. Examples include a method in which the total amount of the ethylenic monomers and the total amount of the monosubstituted epoxy compound having a radically polymerizable group are set within the preferred ranges described above.

(a-2) The weight average molecular weight (Mw) of the modified acrylic resin is preferably 1,000 to 100,000, which can improve coating properties and 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. is generally 10 to 70% by weight of the solid content.

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

(B) Photoradical polymerization initiators include, for example, 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, 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-(phenylthio)-2-(o-benzoyloxime)], 1-phenyl-1 , 2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-,1-(0-acetyloxime), 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, ethyl p-dimethylaminobenzoate, 2 -ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)- 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-diphenylsulfide, alkylated benzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propene Niloxy)ethyl]benzenemetanaminium 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 derivatives, bis( η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 4-benzoyl-4-methylphenylketone, dibenzyl Ketones, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal , anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 2- methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and the like. You may contain 2 or more types of these. 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-butadione-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 (B) photoradical polymerization initiator in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by weight based on the solid content of the negative photosensitive resin composition. (B) By setting the content of the photoradical polymerization initiator within the above range, it is possible to sufficiently promote radical curing, suppress the elution of the remaining radical polymerization initiator, etc., and further improve the chemical resistance. 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, a monofunctional monomer refers to a compound having one (meth)acrylic group. Radicals generated from the radical photopolymerization initiator (B) by light irradiation cause the polymerization of the (meth)acrylic group of the (C) epoxy- or oxetane-containing monofunctional monomer to proceed. Furthermore, the thermal curing promotes cross-linking between the epoxy group or the oxetane group and the amine-based silane coupling agent (D), which will be described later, thereby improving the chemical resistance of the resulting cured film.

In general formula (1) above, 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, the reactivity with (D) the amine-based silane coupling agent is increased, so that the chemical resistance of the cured film can be improved. The alkylene oxide preferably has 2 to 5 carbon atoms.

Examples of groups 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 epoxy-containing monofunctional monomers having a structure represented by the general formula (1) include 4-hydroxybutyl acrylate glycidyl ether, bisphenol A monoglycidyl ether mono (meth) acrylate, bisphenol F monoglycidyl ether mono (meth) ) acrylate, bisphenol S monoglycidyl ether mono(meth)acrylate, biphenyl monoglycidyl ether mono(meth)acrylate, naphthalene monoglycidyl ether mono(meth)acrylate and the like. You may contain 2 or more types of these. 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.

The content of (C) the epoxy- or oxetane-containing monofunctional monomer having the structure represented by the general formula (1) in the negative photosensitive resin composition of the present invention 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, it is preferably 5% by weight or more, more preferably 10% by weight or more, in the solid content of the negative photosensitive resin composition. On the other hand, from the viewpoint of improving the solubility in a developer during pattern formation, it is preferably 60% by weight or less, more preferably 50% by weight or less, of the solid content of the negative photosensitive resin composition.

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, the reactivity with (C) the epoxy- or oxetane-containing monofunctional monomer having the structure represented by the general formula (1) is increased, so that the resistance of the cured film is increased. Chemical properties can be improved.

In the above 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 A substituted aryl group is shown. (C) The number of carbon atoms in the alkyl group and vinyl group is preferably 2 to 4 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).

Examples of the amine-based silane coupling agent having the 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-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane and the like. You may contain 2 or more types of these. Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Triethoxysilane is preferred and can further improve chemical resistance.

The content of (D) the amine-based silane coupling agent having the structure represented by the general formula (2) in the negative photosensitive resin composition of the present invention is from the viewpoint of further improving the chemical resistance of the cured film. Therefore, it is preferably 0.1% by weight or more, more preferably 1.0% by weight or more, in the solid content of the negative photosensitive resin composition. 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, in 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) Solvents having an alcoholic hydroxyl group include, for example, 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-butane and diols. You may contain 2 or more types of these.

The content of (E) the solvent having an 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) When the content of the solvent having an alcoholic hydroxyl group is less than 25% by weight, the storage stability is lowered. (E) The content of the solvent having an alcoholic hydroxyl group is preferably 30% by weight or more. On the other hand, if the content of (E) the solvent having an alcoholic hydroxyl group exceeds 70% by weight, unevenness due to drying during prebaking will cause variations in film thickness, and pattern workability will deteriorate. 50% by weight or less is preferable from the viewpoint of appropriately promoting drying during prebaking and further suppressing unevenness of the cured film.

The negative photosensitive resin composition of the present invention may further contain monomers other than the aforementioned (C) epoxy- or oxetane-containing monofunctional monomer. (C) Monomers other than epoxy- or oxetane-containing monofunctional monomers include, 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, pentapentaerythritol dodecaacrylate, tripentaerythritol hepta methacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nona methacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate , pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-( 2-methacryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-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 (D) the amine-based silane coupling agent described above. (D) By containing a silane coupling agent other than an amine-based silane coupling agent, the adhesiveness to the substrate can be improved. (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-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 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-trimethoxysilylpropylsuccinic acid and the like.

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 solvents other than solvents 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 and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; Amides such as dimethylacetamide; Acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like.

When the negative photosensitive resin composition of the present invention contains (E) a solvent other than a solvent having an alcoholic hydroxyl group, the content of the entire solvent containing these can be appropriately set according to the coating method and the like. . For example, when forming a film by spin coating, it 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-based chain transfer agent, radical curing can be sufficiently advanced, and the hardness and chemical resistance of the cured film can be further improved.

Polyfunctional thiol-based chain transfer agents include, for example, 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, trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate) , trimethylolbutanetris (3-mercaptobutyrate), trimethylolpentanetris (3-mercaptobutyrate), trimethylolhexanetris (3-mercaptobutyrate), and the like. You may contain 2 or more types of these.

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

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

Benzotriazole compounds, benzophenone compounds, and triazine compounds are preferable as the ultraviolet absorber from the viewpoint of transparency and non-coloring properties.

Examples of benzotriazole compounds include 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4-6-bis(1-methyl-1 -phenylethyl)phenol, 2-[5-chloro(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 tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole and the like.

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

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

The negative photosensitive resin composition of the present invention may further contain a filler. Examples of fillers 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 preferred from the viewpoint of dispersibility. The particle size (weight average particle size) 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 or facilitate curing of the resin composition. Examples of curing agents include silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and their polymers, methylolated melamine derivatives, methylolated urea derivatives, and the like. You may contain 2 or more types of these. Among them, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferable from the viewpoint of the stability of the curing agent and the workability of the coating film.

Since curing of polysiloxane is accelerated 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 thermal acid generators include various onium salt compounds such as aromatic diazonium salts, sulfonium salts, diaryliodonium salts, triarylsulfonium salts and triarylselenium 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 flowability during application. .

Examples of surfactants 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 Industry Co., Ltd.), fluorine-based surfactants such as "NBX-15 (trade name)", "FTX-218 (trade name)" (manufactured by Neos Co., Ltd.), "BYK-333 (trade name)" name)”, “BYK-301 (product name)”, “BYK-331 (product name)”, “BYK-345 (product name)”, “BYK-348 (product name)”, “BYK-361 (product name)”, “BYK-3550 (trade name)”, “BYK-307 (trade name)” (manufactured by BYK-Chemie Japan Co., Ltd.), silicone-based surfactants, polyalkylene oxide-based surfactants, poly ( meth)acrylate-based surfactants and the like. You may contain 2 or more types of these.

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

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 sensitivity and suppressing stains on the film surface, it is preferably 0.5% by weight or less in the solid content of the negative photosensitive resin composition.

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

Next, an example is given and demonstrated about the manufacturing method of the negative photosensitive resin composition of this invention. 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, another solvent, and dissolved by stirring, and then (A) a carboxyl group is added. Alkali-soluble resin having, (C) an epoxy or oxetane-containing monofunctional monomer and (D) an amine-based silane coupling agent and if necessary other additives are added, and further stirred for 20 minutes to 3 hours to obtain a negative photosensitive 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 the present invention comprises a cured product of the negative photosensitive resin composition described above. The film thickness of the cured film of the present invention is preferably 0.1 to 15 μm. 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. The hardness and transmittance of the cured film can be made within the ranges described above, for example, by using the above-described negative photosensitive resin composition of the present invention.

Next, an example is given and demonstrated about the manufacturing method of the cured film of this invention. For example, a cured film can be obtained by applying the negative photosensitive resin composition of the present invention described above onto a base substrate, pre-baking it, forming a pattern by patterning exposure and development, and heat-curing it.

Examples of the method of applying the negative photosensitive resin composition of the present invention include methods such as 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 prebaking is preferably 0.1 to 15 μm.

Exposure machines used for patterning exposure include, for example, steppers, mirror projection mask aligners (MPA), parallel light mask aligners (PLA), and the like. 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 dose is preferably about 1 to 4000 mJ/cm 2 (converted to the exposure dose at a wavelength of 365 nm). Exposure may be performed through a desired mask, or may be performed without a mask.

After patterning exposure, a negative pattern can be obtained by dissolving the exposed portion by development. Examples of the developing method include methods such as showering, dipping, and puddle, and it is preferable to immerse the film after patterning exposure 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; Alkaline developers such as aqueous solutions containing ammonium hydroxide and quaternary ammonium salts such as choline are included. After development, rinsing with water is preferred, followed by drying baking in the range of 50 to 150°C.

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

The cured film of the present invention includes protective films for touch panels, various hard coating materials, overcoats for color filters, various protective films such as antireflection films, optical filters, insulating films for touch sensors, liquid crystal display elements and organic EL display elements. etc., flattening films for thin film transistor (TFT) substrates, interlayer insulating films for semiconductor devices, flattening films and microlens array patterns for solid-state imaging devices, core and clad materials for optical waveguides, photospacers for color filters, etc. be able to. Among these, the cured film of the present invention is excellent in chemical resistance on an ITO substrate, so it can be suitably used for touch panels, and excellent in pattern workability, so it can be suitably used for color filters.

EXAMPLES The present invention will be described below using examples, but the aspects of the present invention are not limited to these examples.

Synthesis Example 1 Polysiloxane solution (i)
47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, and 26.23 g (0.20 mol) of 3-trimethoxysilylpropylsuccinic anhydride were placed in a 500 mL three-necked flask. 10 mol), 82.04 g (0.35 mol) of γ-acryloylpropyltrimethoxysilane, and 180.56 g of diacetone alcohol (DAA) were charged, and the phosphoric acid was added to 55.8 g of water while being immersed in an oil bath at 40° C. and stirred. An aqueous solution of phosphoric acid in which 0.401 g (0.2 parts by weight based on the charged monomer) was dissolved was added with a dropping funnel over 10 minutes. After stirring at 40° C. for 1 hour, the temperature of the oil bath was set to 70° C., stirring was continued for 1 hour, and the temperature of the oil bath was increased to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.). A total of 120 g of methanol and water, which are by-products, were distilled during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt % to obtain (a-1) polysiloxane solution (i) having a carboxyl group and a radically polymerizable group. The weight average molecular weight (Mw) of the obtained polymer was measured by GPC and found to be 5000 (converted to polystyrene). Further, when the silanol group/carboxyl group ratio in the polysiloxane was calculated by ¹ H-NMR and the acid value was measured, the carboxylic acid equivalent was 700 g/mol. Also, when the iodine value was measured, the double bond equivalent was 400 g/mol.

Synthesis Example 2 Polysiloxane solution (ii)
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 are charged, immersed in an oil bath at 40 ° C. and stirred while stirring 54.0 g of water with 0.395 g of phosphoric acid (relative to the charged monomer 0.2 wt %) was added with a dropping funnel over 10 minutes. Then, 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, which are by-products, were distilled off. DAA was added to the resulting polysiloxane DAA solution so that the polymer concentration was 40 wt % to obtain (a-1) polysiloxane solution (ii) having a carboxyl group and a radically polymerizable group. The weight average molecular weight (Mw) of the obtained polymer was measured by GPC and found to be 6000 (converted to polystyrene). Further, when the silanol group/carboxyl group ratio in the polysiloxane was calculated by ¹ H-NMR and the acid value was measured, the carboxylic acid equivalent was 800 g/mol. Further, when the iodine value was measured, the double bond equivalent was 300 g/mol.

Synthesis Example 3 Polysiloxane solution (iii)
47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, and 26.23 g (0.20 mol) of 3-trimethoxysilylpropylsuccinic anhydride were placed in a 500 mL three-necked flask. 10 mol), 56.79 g (0.35 mol) of allyltrimethoxysilane, and 157.25 g of DAA (diacetone alcohol) were charged, and 0.341 g of phosphoric acid was added to 55.8 g of water while stirring in an oil bath at 40°C. (0.2 parts by weight with respect to the charged monomers) in an aqueous phosphoric acid solution was added with a dropping funnel over 10 minutes. After stirring at 40° C. for 1 hour, the temperature of the oil bath was set to 70° C., stirring was continued for 1 hour, and the temperature of the oil bath was increased to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.). A total of 120 g of methanol and water, which are by-products, were distilled during the reaction. DAA was added to the resulting polysiloxane DAA solution so that the polymer concentration was 40 wt % to obtain (a-1) polysiloxane solution (iii) having a carboxyl group and a radically polymerizable group. The weight average molecular weight (Mw) of the obtained polymer was measured by GPC and found to be 5500 (converted to polystyrene). Further, when the silanol group/carboxyl group ratio in the polysiloxane was calculated by ¹ H-NMR and the acid value was measured, the carboxylic acid equivalent was 700 g/mol. Also, when the iodine value was measured, the double bond equivalent was 400 g/mol.

Synthesis Example 4 Polysiloxane solution (iv)
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, 174.65 g of DAA (diacetone alcohol) was charged, and 0.378 g of phosphoric acid (0.2 parts by weight based on the charged monomer) was dissolved in 54.0 g of water while being immersed in an oil bath at 40°C and stirred. The aqueous solution was added with a dropping funnel over 10 minutes. After stirring at 40° C. for 1 hour, the temperature of the oil bath was set to 70° C., stirring was continued for 1 hour, and the temperature of the oil bath was increased to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.). A total of 120 g of methanol and water, which are by-products, were distilled during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt % to obtain a polysiloxane solution (iv). The weight average molecular weight (Mw) of the obtained polymer was measured by GPC and found to be 4500 (converted to polystyrene). Further, when an attempt was made to calculate the silanol group/carboxyl group ratio in the polysiloxane by ¹ H-NMR, no carboxyl group was detected. Also, when the iodine value was measured, the double bond equivalent was 400 g/mol.

Synthesis Example 5 Polysiloxane solution (v)
54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, and 26.23 g (0.50 mol) of 3-trimethoxysilylpropylsuccinic anhydride were placed in a 500 mL three-necked flask. 10 mol), and 166.03 g of DAA (diacetone alcohol) were charged, and 0.391 g of phosphoric acid (0.2 parts by weight based on the charged monomer) was dissolved in 55.8 g of water while stirring in an oil bath at 40 ° C. An aqueous solution of phosphoric acid was added with a dropping funnel over 10 minutes. After stirring at 40° C. for 1 hour, the temperature of the oil bath was set to 70° C., stirring was continued for 1 hour, and the temperature of the oil bath was increased to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.). A total of 120 g of methanol and water, which are by-products, were distilled during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40 wt % to obtain a polysiloxane solution (v). The weight average molecular weight (Mw) of the obtained polymer was measured by GPC and found to be 6000 (converted to polystyrene). Further, when the silanol group/carboxyl group ratio in the polysiloxane was calculated 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)
A 500 ml flask was charged with 2 g of 2,2′-azobis(isobutyronitrile) and 50 g of propylene glycol methyl ether acetate (PGMEA). After that, 23.26 g of methacrylic acid, 18.59 g of styrene, and 32.80 g of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate were charged, and the mixture was stirred at room temperature for a while to cause bubbling in the flask. After sufficiently purging with nitrogen, the mixture was heated and stirred at 70° C. for 5 hours. Next, 12.69 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA are added to the resulting solution, and the mixture is heated and stirred at 90° C. for 4 hours, (a-2 ) A modified acrylic resin solution (A) was obtained as a reaction product of an acrylic resin having a carboxyl group and a monosubstituted epoxy compound having a radically polymerizable group. 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. Further, when the solid content acid value was measured according to JIS K5601-2-1, the acid value was 120 g/mol. Further, 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). After that, 21.92 g of methacrylic acid, 17.67 g of styrene, and 31.18 g of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate were added, and the mixture was stirred at room temperature for a while to cause bubbling in the flask. After sufficiently purging with nitrogen, the mixture was heated and stirred at 70° C. for 5 hours. Next, 17.00 g of 4-(glycidyloxy)butyl acrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA are added to the obtained solution, and the mixture is heated and stirred at 90° C. for 4 hours. (a-2) to obtain 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 radically polymerizable group. 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 23,000. Further, when the solid content acid value was measured according to JIS K5601-2-1, the acid value was 120 g/mol. Further, 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). After that, 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 added, and the mixture was stirred at room temperature for a while to cause bubbling in the flask. After sufficiently purging with nitrogen, the mixture was heated and stirred at 70° C. for 5 hours. Next, 10.46 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours to form 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 acrylic resin (C) was 22,000. Further, when the solid content acid value was measured according to JIS K5601-2-1, it was found to be less than 0.5 mgKOH/g, confirming that no carboxyl group remained. Further, 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. After that, 15.69 g of methacrylic acid, 22.14 g of styrene, and 46.86 g of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate were charged, stirred at room temperature for a while, and bubbled in the flask. After sufficiently purging with nitrogen, the mixture was heated and stirred at 70° C. for 5 hours. Next, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to obtain an acrylic resin solution (D). PGMEA was added to the obtained acrylic resin solution (D) so that the solid content concentration was 50 wt %. The acrylic resin (C) had a weight average molecular weight of 25,000. Further, when the solid content acid value was measured according to JIS K5601-2-1, the acid value was 300 g/mol. Further, when the iodine value was measured, no double bond was detected.

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.) on a spin coater (manufactured by Mikasa Co., Ltd. "1H-360S (trade name)") was spun at 500 rpm for 10 seconds, and then spun at 1000 rpm for 4 seconds for spin coating. Subsequently, using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.), pre-baking was performed at 90° C. for 2 minutes to prepare a pre-baked film having a thickness of 2 μm. The prepared pre-baked film is exposed using a parallel light mask aligner (hereinafter referred to as PLA) (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source, and then placed in an oven (Espec Inc. ) manufactured by "IHPS-222") and cured in the air at 230° C. for 1 hour to prepare a cured film having a thickness of 1.5 μm. The film thickness was measured with a refractive index of 1.55 using "Lambda Ace STM-602 (trade name)" manufactured by Dainippon Screen Mfg. Co., Ltd. The same applies to film thicknesses described below.

The transmittance at 400 nm of the resulting cured film was measured using an ultraviolet-visible spectrophotometer "UV-260 (trade name)" (manufactured by Shimadzu Corporation).

(2) Measurement of Hardness The cured film having a thickness of 1.5 μm obtained by the method described in (1) above was measured for pencil hardness according to “JIS K5600-5-4 (1999)”.

(3) Evaluation of pattern processability (3-1) Measurement of sensitivity The composition prepared in each example and comparative example was coated on a silicon wafer by a spin coater ("1H-360S (trade name)" manufactured by Mikasa Co., Ltd.). ) at 500 rpm for 10 seconds and then at 1000 rpm for 4 seconds for spin coating. Subsequently, using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.), pre-baking was performed at 90° C. for 2 minutes to prepare a pre-baked film having a thickness of 2 μm. The obtained prebaked film was exposed to light with a gap of 100 μm through a gray scale mask for sensitivity measurement using PLA with an ultra-high 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 a 0.045 wt % potassium hydroxide aqueous solution for 90 seconds, followed by rinsing with water for 30 seconds.

After exposure and development, the sensitivity was defined as the amount of exposure for forming a 30 μm line-and-space pattern with a width of 1:1 (hereinafter referred to as optimum exposure amount). The amount of exposure was measured with an I-line illuminometer.

(3-2) Measurement of Resolution The resolution after development was measured at the optimum exposure dose. Note that the resolution was defined as the smallest pattern among the patterns in which 95% or more of the hole diameter was resolved with respect to the mask diameter.

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

(4-1) Evaluation of Adhesion to ITO Substrate after Alkali Treatment The ITO substrate having the cured film obtained by the method described in (4) above was treated with monoethanolamine/diethylene glycol monobutyl ether=30/70 (weight ratio). After dipping in the mixed aqueous solution at 70° C. for 10 minutes, the adhesion between the ITO and the cured film was evaluated according to JIS "K5600-5-6 (established on April 20, 1999)". That is, on the ITO surface of the ITO substrate, parallel straight lines of 11 orthogonal vertical and horizontal lines were drawn at intervals of 1 mm so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm × 1 mm were prepared. did. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is attached to the surface of the cut cured film, rubbed with an eraser (JIS S6050 acceptable product) to adhere, hold one end of the tape, and hold it at a right angle to the plate. The number of remaining squares when the film was held and instantaneously peeled off was visually counted, and the peeled area was calculated. Evaluation was made according to the following criteria from the peeling area of the squares, and 3 or more was regarded as acceptable.
5: Peeling area = 0%
4: Peeling area = 1 to 4%
3: Peeling area = 5 to 14%
2: Peeling area = 15 to 34%
1: Peeling area = 35 to 64%
0: Peeling area = 65 to 100%.

(4-2) Evaluation of adhesion to ITO substrate after acid treatment The ITO substrate having the cured film obtained by the method described in (4) above was treated with HCl/HNO3/H2O=18/4/78 (weight ratio). After dipping for 10 minutes in the aqueous solution at 70° C. mixed in (4-1), the adhesion between the ITO and the cured film was evaluated.

(5) Evaluation of storage stability (ITO substrate adhesion)
After storing the composition prepared in each example and comparative example under the conditions of 30° C. and 168 hours, a cured film having a thickness of 1.5 μm was prepared by the method described in (4) above. Acid or alkali treatment was performed according to the method, and adhesion was evaluated. The smaller the difference from the evaluation result in (4) above, the better the storage stability.

Further, after storing the compositions prepared in Examples 1, 12 to 13 and 24 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 adhesion was evaluated. The smaller the difference from the evaluation result in (4) above, the better the storage stability.

(6) Evaluation of unevenness Using the composition prepared in each example and comparative example on a 10 cm square glass substrate (hereinafter referred to as "Cr substrate") having Cr sputtered on the surface, the method described in (1) above. A cured film having a film thickness of 1.5 μm was formed in the same manner as above. The film thickness was measured at intervals of 1 cm for an 8 cm square area excluding the 1 cm edge of the substrate, and the unevenness was evaluated according to the following criteria.

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 3: The value obtained by subtracting the minimum film thickness from the maximum film thickness is 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 0.07 μm or more and less than 0.10 μm. 15 μm or more.

The 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.)
Kayarad (registered trademark) DPHA (trade name) (manufactured by Nippon Kayaku Co., Ltd.)
Karenz MT-PE1 (trade name) (manufactured by Showa Denko KK).

Example 1
Under a yellow light, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)] (“Irgacure” (registered trademark) OXE-01 (trade name), Ciba Specialty chemical) 0.931 g and 0.056 g of 4-t-butylcatechol are dissolved in a mixed solvent of 18.041 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 40.000 g of PGMEA, and a silicone surfactant " “BYK” (registered trademark)-333 (trade name)” (manufactured by BYK Chemie Japan Co., Ltd.) 0.03 g and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane 0.372 g are added and stirred. 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 thereto and stirred. Then, filtration was performed with a 0.45 μm filter to obtain composition 1. The transmittance, hardness, pattern workability, chemical resistance, storage stability, and unevenness of composition 1 obtained were evaluated by the methods described above.

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, evaluation was performed by the method described above.

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, evaluation was performed by the method described above.

Example 4
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)”, composition 4 was prepared. Obtained. Using the obtained composition 4, evaluation was performed by the method described above.

Example 5
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, evaluation was performed by the method described above.

Example 6
Except for changing the amount of DAA added in the mixed solvent from 18.041 g to 10.041 g, the amount of 3-methoxy-1-butanol added from 8.000 g to 6.000 g, and the amount of PGMEA added from 40.000 g to 50.000 g. A composition 6 was obtained in the same manner as in Example 1. Using the obtained composition 6, evaluation was performed by the method described above.

Example 7
Composition 7 was prepared 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, evaluation was performed by the method described above.

Example 8
A composition 8 was obtained in the same manner as in Example 1 except that the amount of DAA added in the mixed solvent was changed from 18.041 g to 3.042 g, and the amount of PGMEA added was changed from 40.000 g to 55.000 g. Using the obtained composition 8, evaluation was performed by the method described above.

Example 9
Except for changing the amount of DAA added in the mixed solvent from 18.041 g to 18.042 g, the amount of 3-methoxy-1-butanol added from 8.000 g to 38.000 g, and the amount of PGMEA added from 40.000 g to 10.000 g. A composition 9 was obtained in the same manner as in Example 1. Using the obtained composition 9, evaluation was performed by the method described above.

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 g of PGMEA. 000 g of mixed solvent, ""BYK"-333 (trade name)" 0.030 g, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane 0.365 g, pentaerythritol tetrakis (3-mercapto Butyrate) (“Karenzu MT-PE1 (trade name)” manufactured by Showa Denko KK) (0.365 g) was added and stirred. 9.135 g of "EA-1010N (trade name)" and 22.839 g of polysiloxane solution (i) were added thereto and stirred. Filtration was then carried out with a 0.45 μm filter to obtain Composition 10. Using the obtained composition 10, evaluation was performed by the method described above.

Example 11
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, evaluation was performed by the method described above.

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, evaluation was performed by the method described above.

Example 13
Under a yellow light, 0.931 g of "Irgacure" OXE-01 (trade name) and 0.056 g of 4-t-butylcatechol were mixed with 32.000 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 30.0 g of PGMEA. It was dissolved in 694 g of mixed solvent, and 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 modified acrylic resin solution (A) were added thereto and stirred. Then, filtration was performed with a 0.45 μm filter to obtain composition 13. Using the obtained composition 13, evaluation was performed by the method described above.

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, evaluation was performed by the method described above.

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, evaluation was performed by the method described above.

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, evaluation was performed by the method described above.

Example 17
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, evaluation was performed by the method described above.

Example 18
Except for changing the amount of DAA added in the mixed solvent from 32.000 g to 24.000 g, the amount of 3-methoxy-1-butanol added from 8.000 g to 6.000 g, and the amount of PGMEA added from 30.694 g to 40.694 g. A composition 18 was obtained in the same manner as in Example 13. Using the obtained composition 18, evaluation was performed by the method described above.

Example 19
Composition 19 was prepared in the same manner as in Example 13 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 30.694 g to 20.694 g. Obtained. Using the obtained composition 19, evaluation was performed by the method described above.

Example 20
Composition 20 was obtained in the same manner as in Example 13, except that the amount of DAA added in the mixed solvent was changed from 32.000 g to 17.000 g, and the amount of PGMEA added was changed from 30.694 g to 45.694 g. Using the obtained composition 20, evaluation was performed by the method described above.

Example 21
Composition 21 was prepared in the same manner as in Example 13 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, evaluation was performed by the method described above.

Example 22
Under a yellow light, 0.914 g of "Irgacure" OXE-01 (trade name) and 0.055 g of 4-t-butylcatechol were added to 32.000 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 30.865 g of PGMEA. 0.030 g of “BYK”-333 (trade name) solution, 0.365 g of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and Karenz MT-PE1 (trade name). name)” was added and stirred. 9.135 g of "EA-1010N (trade name)" and 18.271 g of modified acrylic resin solution (A) were added thereto and stirred. Then, filtration was performed with a 0.45 μm filter to obtain composition 22. Using the obtained composition 22, evaluation was performed by the method described above.

Example 23
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)". Using the obtained composition 23, evaluation was performed by the method described above.

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. Using the obtained composition 24, evaluation was performed by the method described above.

Comparative example 1
Under a yellow light, 0.948 g of "Irgacure" OXE-01 (trade name) and 0.057 g of 4-t-butylcatechol were mixed with 17.776 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 40 g of PGMEA. 000 g of mixed solvent, and 0.030 g of "BYK"-333 (trade name) solution was added and stirred. 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 thereto and stirred. . Then, filtration was performed with a 0.45 μm filter to obtain composition 25. Using the obtained composition 25, evaluation was performed by the method described above.

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 40.0 g of PGMEA. 000 g of 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. 9.306 g of "Kayarad (registered trademark)" DPHA (trade name) and 23.264 g of polysiloxane solution (i) were added thereto and stirred. Filtration was then carried out with a 0.45 μm filter to obtain Composition 26. Using the obtained composition 26, evaluation was performed by the method described above.

Comparative example 3
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). Using the obtained composition 27, evaluation was performed by the method described above.

Comparative example 4
Except for changing the amount of DAA added in the mixed solvent from 18.041 g to 2.042 g, the amount of 3-methoxy-1-butanol added from 8.000 g to 4.000 g, and the amount of PGMEA added from 40.000 g to 60.000 g. A composition 28 was obtained in the same manner as in Example 1. Using the obtained composition 28, evaluation was performed by the method described above.

Comparative example 5
Composition 29 was obtained in the same manner as in Example 1 except that the amount of DAA added in the mixed solvent was changed from 18.041 g to 53.042 g and the amount of PGMEA added was changed from 40.000 g to 5.000 g. Using the obtained composition 29, evaluation was performed by the method described above.

Comparative example 6
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, evaluation was performed by the method described above.

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, evaluation was performed by the method described above.

Comparative example 8
Under a yellow light, 0.948 g of "Irgacure" OXE-01 (trade name) and 0.057 g of 4-t-butylcatechol were added to 32.000 g of DAA, 8.000 g of 3-methoxy-1-butanol, and 30.0 g of PGMEA. It was dissolved in 518 g of mixed solvent, and 0.030 g of "BYK"-333 (trade name) solution was added and stirred. 9.482 g of "Kayarad" DPHA (trade name) and 18.965 g of modified acrylic resin solution (A) were added thereto and stirred. Then, filtration was performed with a 0.45 μm filter to obtain composition 32. Using the obtained composition 32, evaluation was performed by the method described above.

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 0.000 g of PGMEA. It was dissolved in 694 g of mixed solvent, and 0.030 g of "BYK"-333 (trade name) solution and 0.372 g of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane were added and stirred. 9.306 g of "Kayarad" DPHA (trade name) and 18.611 g of modified acrylic resin solution (A) were added thereto and stirred. Then, filtration was performed with a 0.45 μm filter to obtain composition 33. Using the obtained composition 33, evaluation was performed by the method described above.

Comparative example 10
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, evaluation was performed by the method described above.

Comparative example 11
Except for changing the amount of DAA added in the mixed solvent from 18.041 g to 16.000 g, the amount of 3-methoxy-1-butanol added from 8.000 g to 4.000 g, and the amount of PGMEA added from 40.000 g to 50.694 g. A composition 35 was obtained in the same manner as in Example 13. Using the obtained composition 35, evaluation was performed by the method described above.

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). Using the obtained composition 36, evaluation was performed by the method described above.

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). Using the obtained composition 37, evaluation was performed by the method described above.

Tables 1 to 3 show the main compositions of each example and comparative example, and Tables 4 to 6 show the evaluation results. In addition, in the evaluation of storage stability, the evaluation result after acid or alkali treatment at a temperature of 80 ° C. was 4 in Examples 1 and 13, whereas 5 in Examples 12 and 24. Met.

The cured film of the present invention includes protective films for touch panels, various hard coating materials, overcoats for color filters, various protective films such as antireflection films, optical filters, insulating films for touch sensors, liquid crystal display elements and organic EL display elements. etc., flattening films for thin film transistor (TFT) substrates, interlayer insulating films for semiconductor devices, flattening films and microlens array patterns for solid-state imaging devices, core and clad materials for optical waveguides, photo spacers for color filters, etc. Used.

Claims (4)

(A) an alkali-soluble resin having a carboxyl group, (B) a photoradical polymerization initiator, (C) an epoxy- or oxetane-containing monofunctional monomer having a structure represented by the following general formula (1), and (D) the following general formula (2) containing an amine-based silane coupling agent having a structure represented by (E) and 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 radically polymerizable group and/or (a-2) an acrylic resin having a carboxyl group and a radically polymerizable group. A negative photosensitive resin composition containing a modified acrylic resin which is a reaction product with a monosubstituted epoxy compound and containing 25 to 70% by weight of (E) a solvent having an 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 bivalent group having an aromatic ring, and R ¹ represents hydrogen or a methyl group. R ² represents Indicates a divalent hydrocarbon group with 1 to 2 carbon atoms.)

(In the above 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 Indicates an unsubstituted aryl group.) 2. The negative photosensitive resin composition according to claim 1, wherein X in said general formula (1) is a group derived from bisphenols. 3. The negative photosensitive resin composition according to claim 1, further comprising a polyfunctional thiol-based chain transfer agent. A method for producing a cured film in which the negative photosensitive resin composition according to any one of claims 1 to 3 is applied onto a base substrate, pre-baked, patterned by exposure and development to form a pattern, and thermally cured. .