CN112162462A

CN112162462A - Photosensitive resin composition for touch panel, cured film thereof, and touch panel having the cured film

Info

Publication number: CN112162462A
Application number: CN202011101671.9A
Authority: CN
Inventors: 小野悠树
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2014-09-30
Filing date: 2015-09-29
Publication date: 2021-01-01
Also published as: CN105467761B; KR20160038797A; KR102470292B1; CN105467761A; JP6822758B2; JP2016071359A; TWI696888B; JP7168696B2; TW201612634A; JP2021061056A

Abstract

The invention provides a photosensitive resin composition for a touch screen, a cured film thereof and a touch screen with the cured film, wherein the photosensitive resin composition for the touch screen comprises the following components: (A-1) an alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or anhydride thereof and (b) a tetracarboxylic acid or acid dianhydride thereof with a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol and a monocarboxylic acid having an unsaturated group; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) metal oxide particles of at least one selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium; (E) a surfactant; and (F) a silane compound. The photosensitive resin composition can be used for forming patterns by photoetching, has excellent developing property, forms a cured film with high transparency, improves the refractive index, and prevents the pattern visibility of an ITO wiring pattern.

Description

Photosensitive resin composition for touch panel, cured film thereof, and touch panel having the cured film

This application is a divisional application, the application number of the parent: 201510634814.5, filing date: 29/09/2015, title of the invention: photosensitive resin composition for touch panel, cured film thereof, and touch panel having the cured film.

Technical Field

The present invention relates to a photosensitive resin composition for a touch panel, a cured film thereof, and a touch panel having the cured film.

Background

Currently, in addition to large-sized displays such as personal computers (personal computers) and televisions (televisions), the demand for liquid crystal displays (liquid crystal displays) is expanding to small-sized displays such as mobile phones, smart phones (smartphones), and tablet terminals (tablet terminals). Recently, as a data input mechanism in a display device such as a liquid crystal display, a touch panel is widely used, and among them, a capacitive touch panel is used. The capacitive touch panel has the following structure in a screen: mosaic (mosaic) electrode patterns made of a transparent conductive material such as Indium Tin Oxide (ITO) are disposed on both surfaces of the transparent insulating film. The two-layer electrode patterns disposed on both surfaces show shapes connected in the x-axis direction and the y-axis direction, respectively, and are connected to an external control circuit via extraction wirings made of metal or the like. When a finger touches the screen, the capacitance of the electrode pattern in the vicinity thereof changes, and the control circuit can detect the change as coordinate information to recognize the position of the finger (see, for example, patent document 1).

In the case where the touch panel having such a structure is used in a display device such as a display, there are problems as follows: the electrode pattern is visible due to the difference in optical properties between the portion having the electrode pattern and the portion not having the electrode pattern, and the visibility is reduced by the so-called "pattern visibility". In order to reduce the visibility of the pattern, a transparent conductive material in which the thickness of the electrode pattern is reduced or ITO is substituted has been proposed (see patent document 2). Further, a method of disposing a high refractive index layer for reducing the difference in optical properties has been proposed, but there remain problems such as lack of pattern formability and lack of heat resistance, and development of a high-performance material has been desired (see patent documents 3 and 4). Further, recently, after forming a high refractive index layer on an electrode pattern, the height of a portion having the electrode pattern is different from that of a portion not having the electrode pattern, thereby generating color unevenness. Therefore, it is desired to develop a material for forming a high refractive index layer, which can ensure flatness after formation of the high refractive index layer even if the material has irregularities between electrode patterns.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2011-

[ patent document 2] Japanese patent laid-open No. 2012-209030

[ patent document 3] WO2013/038718 Manual

[ patent document 4] Japanese patent laid-open publication No. 2013-140229

Disclosure of Invention

[ problems to be solved by the invention ]

Accordingly, an object of the present invention is to provide a photosensitive resin composition for a touch panel, a cured film using the same, and a touch panel having the cured film, which can suppress a decrease in visibility due to pattern visibility. Further, the use of an alkali-soluble resin having a specific structure and containing a non-polymerizable saturated group is effective as a technique for forming a pattern and for requiring heat resistance, and a cured film using this technique can be applied to an overcoat (over coat) or an insulating film having good heat resistance, and thus can be used as a component of a touch panel or a color filter having good heat resistance. Further, the present invention provides a photosensitive resin composition for a touch panel for forming a high refractive index layer, which has good flatness after the formation of the high refractive index layer and can reduce the possibility of problems occurring in the subsequent steps after the formation of the high refractive index layer.

[ means for solving problems ]

The present inventors have made extensive studies to solve the above-mentioned problems, and as a result, have found that a photosensitive resin composition which can suppress a decrease in visibility due to pattern visibility, has excellent pattern formability, and can satisfy the requirement of heat resistance can be obtained by using a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure, a specific metal oxide, or the like. Further, it has been found that a photosensitive resin composition for forming a high refractive index layer, which has excellent flatness after formation of a high refractive index layer, can be obtained.

That is, the gist of the present invention is as follows.

(1) The present invention is a photosensitive resin composition for a touch panel, comprising: (A-1) an alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or anhydride thereof and (b) a tetracarboxylic acid or acid dianhydride thereof with a reactant of an epoxy compound having two glycidyl ether groups derived from a bisphenol and a monocarboxylic acid having an unsaturated group; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) metal oxide particles of at least one selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium; (E) a surfactant; and (F) a silane compound, and the photosensitive resin composition for a touch screen: the photosensitive resin composition contains 0.001 to 5 mass% of the component (E), and the photosensitive resin composition contains 0.01 to 20 mass% of the component (F) in a solid component which becomes a solid component after photo-curing.

(2) A photosensitive resin composition for a touch panel, comprising: (A-2) an unsaturated group-containing alkali-soluble resin represented by the general formula (I); (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) metal oxide particles of at least one selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium; (E) a surfactant; and (F) a silane compound, and the photosensitive resin composition for a touch screen: the photosensitive resin composition contains 0.001 to 5 mass% of the component (E), and the photosensitive resin composition contains 0.01 to 20 mass% of the component (F) in a solid component which becomes a solid component after photo-curing,

[ solution 1]

(wherein, R₁Represents a hydrogen atom or a methyl group; x represents a single bond or a divalent organic group having 1 to 20 carbon atoms and containing a hetero element therein, Y represents a tetravalent carboxylic acid residue, Z represents a hydrogen atom or a substituent represented by the following general formula (II), and G represents a hydrogen atom or a substituent represented by the following general formula (III); n represents an average value of 1 to 20);

[ solution 2]

(wherein, R₁Represents a hydrogen atom or a methyl group, R₂Represents a C2-10 divalent hydrocarbon group, L represents a divalent or trivalent carboxylic acid residue; m represents 0 or 1; p and q are each 0 or 1 or 2, and p + q is 1 or 2);

[ solution 3]

(wherein, R₁Represents a hydrogen atom or a methyl group, R₂Represents a C2-10 divalent hydrocarbon group; m represents 0 or 1).

(3) The photosensitive resin composition for touch panels of the present invention is (1) or (2): the photosensitive resin composition for touch panels comprises (A-1) and/or (A-2) in an amount of 5 to 100 parts by mass of (B), and (C) in an amount of 0.1 to 40 parts by mass based on 100 parts by mass of the total amount of (A-1) and/or (A-2) and (B), and further comprises (D) in an amount of 1 to 60% by mass in the solid content (including a monomer component which becomes a solid content by a photo-curing reaction).

(4) The present invention also provides the photosensitive resin composition according to any one of (1) to (3), wherein the component (E) is a surfactant having a surface tension of 20 to 28mN/m, as measured with respect to a propylene glycol monomethyl ether acetate solution in which the concentration of the component (E) is 0.1 mass%.

(5) The present invention also provides the photosensitive resin composition according to any one of (1) to (3), wherein the component (F) is a silane compound having any one of an epoxy group, an oxetanyl group, an isocyanate group, and a urea group.

(6) The present invention also provides a cured film obtained by curing the photosensitive resin composition according to any one of (1) to (5).

(7) The present invention is also a touch panel having the cured film of (6).

[ Effect of the invention ]

The photosensitive resin composition for a touch panel of the present invention can be patterned by photolithography (photolithography), and particularly, is excellent in developing properties, and the cured film formed therefrom has high transparency and can have a high refractive index, so that a good cured film which can prevent pattern visibility of an ITO wiring pattern and is excellent in flatness after the cured film is formed can be obtained as a transparent insulating film or a protective film for a touch panel.

The touch panel of the present invention is obtained by disposing the cured film of the photosensitive resin composition for a touch panel on a mosaic-like electrode pattern formed of a transparent conductive material such as ITO.

Detailed Description

The present invention will be described in detail below.

The (a-1) in the photosensitive resin composition for a touch panel of the present invention is an alkali-soluble resin obtained by reacting a reactant of (a) a dicarboxylic acid or tricarboxylic acid or an anhydride thereof and (b) a tetracarboxylic acid or an acid dianhydride thereof, an epoxy compound having two glycidyl ether groups derived from a bisphenol, and a monocarboxylic acid having an unsaturated group. The alkali-soluble resin is preferably obtained by reaction at a molar ratio of (a)/(b) in the range of 0.01 to 10.

The bisphenols as the raw material of (A-1) include: bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone, bis (4-hydroxy-3, 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3, 5-dimethylphenyl) sulfone, bis (4-hydroxy-3, 5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane, Bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-dibromophenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dimethylphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 4 '-biphenol, 3' -biphenol, etc., and derivatives thereof. Among these compounds, a compound having a fluorene-9, 9-diyl group can be particularly suitably used.

Then, the bisphenols are reacted with epichlorohydrin to obtain epoxy compounds having two glycidyl ether groups. Since the reaction is usually accompanied by oligomerization of the diglycidyl ether compound, an epoxy compound of the following general formula (IV) can be obtained.

[ solution 4]

Here, in the formula of the general formula (I), R₃、R₄、R₅And R₆Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, A represents-CO-, -SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-, -O-, fluorene-9, 9-diyl or a direct bond. l is an integer of 0 to 10 in each molecule. Superior foodSelected R₃、R₄、R₅、R₆As a hydrogen atom, preferred A is fluorene-9, 9-diyl. Since l is an integer of 1 to 10 per molecule, and a plurality of values are usually mixed, the average value thereof is 0 to 10 (not limited to an integer), and preferably, l is 0 to 3. If the average value of l exceeds the upper limit, the viscosity of the composition becomes too high to be smoothly applied, or alkali solubility cannot be sufficiently imparted to the composition when a photosensitive resin composition is produced using an alkali-soluble resin synthesized using the epoxy compound, and the alkali developability becomes very poor.

Then, acrylic acid or methacrylic acid or both of them is reacted as an unsaturated group-containing monocarboxylic acid with a compound of the general formula (IV) to obtain a reactant having a hydroxyl group, and (a) a dicarboxylic acid or tricarboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof are reacted with the resultant reactant having a hydroxyl group in a molar ratio of (a)/(b) of preferably 0.01 to 10, to obtain an alkali-soluble resin having a structure of an epoxy (meth) acrylate acid adduct represented by the following general formula (V).

[ solution 5]

[ in the formula, R₃、R₄、R₅And R₆Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R₁Represents a hydrogen atom or a methyl group, A represents-CO-, -SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-, -O-, fluorene-9, 9-diyl or a direct bond, Y represents a tetravalent carboxylic acid residue, and W each independently represents a hydrogen atom or-OC-L- (COOH) s (wherein L represents a divalent or trivalent carboxylic acid residue, and s represents an integer of 1 or 2). In addition, r is an integer of 1 to 20 per molecule, and r represents an average value of 1 to 20]

The epoxy (meth) acrylate acid adduct (V) is an alkali-soluble resin having both an ethylenically unsaturated double bond and a carboxyl group, and therefore, as (a-1) of the photosensitive resin composition for a touch panel of the present invention, excellent photocurability, good developability, and pattern formation characteristics are imparted, and a good transparent cured film pattern for a touch panel can be obtained.

As the (a) dicarboxylic acid or tricarboxylic acid or anhydride thereof used as the epoxy (meth) acrylate acid adduct of the general formula (V) of (A-1) of the present invention, chain type hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride thereof, alicyclic dicarboxylic acid or tricarboxylic acid or anhydride thereof, aromatic dicarboxylic acid or tricarboxylic acid or anhydride thereof can be used. Examples of the chain-type hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride thereof include compounds such as succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid (citramalic acid), malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and further dicarboxylic acid or tricarboxylic acid having an optional substituent introduced therein, or anhydride thereof. The alicyclic dicarboxylic acid or tricarboxylic acid or an anhydride thereof may be a compound such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, or a dicarboxylic acid or tricarboxylic acid or an anhydride thereof having an arbitrary substituent introduced thereto. Further, examples of the aromatic dicarboxylic acid, tricarboxylic acid or anhydride thereof include compounds such as phthalic acid, isophthalic acid, trimellitic acid, and the like, and further, dicarboxylic acid, tricarboxylic acid or anhydride thereof into which an arbitrary substituent is introduced may be used.

As the tetracarboxylic acid or acid dianhydride thereof (b) used as the epoxy (meth) acrylate acid adduct of general formula (V) of (A-1) of the present invention, a chain hydrocarbon tetracarboxylic acid or acid dianhydride thereof, an alicyclic tetracarboxylic acid or acid dianhydride thereof, or an aromatic polycarboxylic acid or acid dianhydride thereof can be used. Examples of the chain hydrocarbon tetracarboxylic acid or acid dianhydride thereof include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and the like, and further, may be a tetracarboxylic acid or acid dianhydride thereof into which a substituent is introduced. Examples of the alicyclic tetracarboxylic acid or acid dianhydride thereof include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and the like, and further, may include a tetracarboxylic acid having a substituent introduced therein or an acid dianhydride thereof. Further, examples of the aromatic tetracarboxylic acid or acid dianhydride thereof include: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, or acid dianhydride thereof, and further, tetracarboxylic acid having a substituent introduced therein or acid dianhydride thereof may be used.

The molar ratio (a)/(b) of the (a) dicarboxylic acid or tricarboxylic acid or anhydride thereof to the (b) tetracarboxylic acid or acid dianhydride thereof used as the epoxy (meth) acrylate acid adduct of the general formula (V) of (A-1) of the present invention is 0.01 to 10, preferably 0.1 to 3.0. If the molar ratio (a)/(b) is out of the above range, the optimum molecular weight cannot be obtained, and the photosensitive resin composition using (A-1) is not preferable because it is inferior in terms of alkali developability, heat resistance, solvent resistance, pattern shape, and the like. Further, the smaller the molar ratio (a)/(b), the larger the alkali solubility and the larger the molecular weight tend to be.

The epoxy (meth) acrylate acid adduct of the general formula (V) of (A-1) of the present invention preferably has a weight average molecular weight (Mw) of 2000 to 10000, particularly preferably 3000 to 7000. If the weight average molecular weight (Mw) is less than 2000, pattern adhesion is not maintained during development using the photosensitive resin composition of (A-1), pattern peeling occurs, and if the weight average molecular weight (Mw) exceeds 10000, development residue or residual film at unexposed portions tends to remain. Further, it is preferable that the acid value of (A-1) is in the range of 30mgKOH/g to 200 mgKOH/g. If the value is less than 30mgKOH/g, the alkali development using the photosensitive resin composition (A-1) cannot be smoothly performed, or special development conditions such as strong alkali are required, and if it exceeds 200mgKOH/g, the alkali developer penetrates into the photosensitive resin composition (A-1) too quickly to cause peeling development, which is not preferable.

The epoxy (meth) acrylate acid adduct of the general formula (V) used in the present invention can be produced by the above-mentioned steps by a known method, for example, a method described in Japanese patent laid-open No. 8-278629 or Japanese patent laid-open No. 2008-9401. First, as a method for reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (IV), for example, the following method can be mentioned: the monocarboxylic acid containing an unsaturated group in an amount equimolar to the epoxy group of the epoxy compound is added to a solvent, and the mixture is heated to 90 to 120 ℃ while blowing air in the presence of a catalyst (triethylbenzylammonium chloride, 2, 6-diisobutylphenol, etc.) and stirred to perform a reaction. Then, as a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product, there is a method of: an epoxy acrylate compound is added to a solvent together with a predetermined amount of acid dianhydride and acid monoanhydride, and the mixture is heated and stirred at 90 to 130 ℃ in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, or the like) to react.

In the photosensitive resin composition for a touch panel of the present invention, (a-2) is an unsaturated group-containing alkali-soluble resin represented by general formula (I) (hereinafter referred to as "alkali-soluble resin of general formula (I)"). The following details show the method for producing the alkali-soluble resin of the general formula (I).

First, an epoxy (meth) acrylate compound is obtained by reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound having two epoxycycloalkyl groups in one molecule represented by the general formula (VI), and suitably (meth) acrylic acid. The unsaturated group-containing monocarboxylic acid compound includes, in addition to acrylic acid and methacrylic acid, a compound obtained by reacting an acid monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride with acrylic acid or methacrylic acid.

[ solution 6]

(wherein X has the same meaning as that shown in the general formula (I))

The reaction of such an epoxy compound with (meth) acrylic acid can be carried out by a well-known method, for example, by using about 2 moles of (meth) acrylic acid with respect to 1 mole of the epoxy compound having two epoxy groups. The reactant obtained by the above reaction is described in, for example, Japanese patent laid-open No. 4-355450. The reactant obtained by the reaction is a diol compound containing a polymerizable unsaturated group, and is an epoxy (meth) acrylate compound represented by the following general formula (VII).

[ solution 7]

(wherein, R₁X has the same meaning as that shown in the general formula (I)

The epoxy compound having two epoxycycloalkyl groups in the molecule represented by the general formula (VI) has X which is a single bond or a divalent organic group having 1 to 20 carbon atoms and containing a hetero element in the interior thereof. The divalent organic group having 1 to 20 carbon atoms which may contain a hetero element in the interior includes: a divalent hydrocarbon group, a divalent group having a carboxyl group at one or both ends of the hydrocarbon group, and the like, and the hydrocarbon group may contain an oxygen atom or an ester bond having an ether bond therein. Examples of such divalent hydrocarbon groups include: linear hydrocarbon groups such as methylene, ethylene, propylene, isopropylene (isopropylidene), sec-butylene, methylisobutylene, hexylene, decylene, and dodecylene.

Specific examples of the epoxy compound having two epoxycycloalkyl groups in the molecule represented by the general formula (VI) include epoxy compounds represented by the following general formulae (VIII) to (XIV), and two or more of them may be used in combination. From the viewpoint of ease of obtaining and physical properties of the cured product, the epoxy compound represented by the general formula (XI) or the general formula (XII) is preferable, and g is 1, h is 5, and i is 1.

[ solution 8]

(wherein g represents an integer of 1 to 20, h represents an integer of 2 to 20, i represents an integer of 0 to 10, j represents an integer of 1 to 20, and k represents an integer of 0 to 18.)

In the case of producing the alkali-soluble resin of the general formula (I) by synthesizing an epoxy (meth) acrylate compound represented by the general formula (VII), followed by addition reaction of a polycarboxylic acid or an anhydride thereof, and further reaction with a monofunctional epoxy compound having a polymerizable unsaturated group reactive with a carboxyl group, the reaction is usually carried out in a solvent using a catalyst as needed. The reaction conditions of the solvent, catalyst and the like used herein are not particularly limited, and for example, a solvent having no hydroxyl group and a boiling point higher than the reaction temperature is preferably used as the main component of the reaction solvent, and such a solvent is preferably, for example, the following solvents: cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, ether or ester solvents with high boiling point such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate, and ketone solvents such as cyclohexanone and diisobutyl ketone. In addition, in the reaction of carboxyl and epoxy, preferably using a catalyst, the catalyst used can be used for example: and known catalysts such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine. These catalysts are described in detail in Japanese patent laid-open No. 9-325494.

As the second reaction, an epoxy (meth) acrylate compound (c) obtained by the reaction of an epoxy compound and (meth) acrylic acid is reacted with an acid component (a) and an acid component (b) to obtain a polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (XV) (hereinafter referred to as "alkali-soluble resin of the general formula (XV)").

[ solution 9]

(wherein, R₁Represents a hydrogen atom or a methyl group. X represents a single bond or a divalent organic group having 1 to 20 carbon atoms and containing a hetero element therein, Y represents a tetravalent carboxylic acid residue, W represents each independently a hydrogen atom or-OC-L- (COOH) s (wherein L represents a divalent or trivalent carboxylic acid residue, and s represents an integer of 1 or 2), n is an integer of 1 to 20 per molecule, and the alkali-soluble resin of the general formula (XV) is a mixture of these. That is, n in the general formula (XV) represents an average value of 1 to 20)

The acid component used for synthesizing the alkali-soluble resin of the general formula (XV) is a polybasic acid component reactive with hydroxyl groups in the molecule of the epoxy (meth) acrylate compound, and it is necessary to use (a) a dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof and (b) a tetracarboxylic acid or acid dianhydride thereof in combination. Examples of the (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof and the (b) tetracarboxylic acid or acid dianhydride thereof include the same group of compounds as those used for the epoxy (meth) acrylate acid adduct of the general formula (V).

The method for the reaction of the epoxy (meth) acrylate compound (c) with the acid component (a) and the acid component (b) is not particularly limited, and a known method of reacting an epoxy (meth) acrylate compound with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ℃ can be employed, as described in Japanese patent laid-open No. 9-325494. It is preferable that the molar ratio of the epoxy (meth) acrylate compound (c), the dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (a) and the tetracarboxylic dianhydride (b) is (c): (a) the method comprises the following steps (b) 1: 0.01-1.0: the reaction is carried out in a manner of 0.2 to 1.0. Here, in the case of using (b) an acid monoanhydride and (c) an acid dianhydride as an example for quantitative description, it is preferable that the reaction is carried out so that the molar ratio [ (c)/[ (a)/2+ (b) ] ] between the number of moles of the diol compound (epoxy (meth) acrylate compound) (c) containing a polymerizable unsaturated group and the number of moles of the acid component [ (a)/2+ (b) ] becomes 0.5 to 1.0. When the molar ratio exceeds 1.0, the content of unreacted diol compound containing a polymerizable unsaturated group increases, and the stability of the alkali-soluble resin composition with time may decrease. On the other hand, when the molar ratio is less than 0.5, the terminal of the alkali-soluble resin represented by the general formula (1) becomes an acid anhydride, and the content of unreacted acid dianhydride increases, which may lower the stability of the alkali-soluble resin composition with time. (c) The molar ratio of each component (a), (b) and (c) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and the molecular weight of the alkali-soluble resin represented by the general formula (XV).

As the third reaction, the monofunctional epoxy compound having a polymerizable unsaturated group of the general formula (XVI) is reacted with the carboxyl group of the alkali-soluble resin of the general formula (XV), thereby obtaining the alkali-soluble resin of the general formula (I).

[ solution 10]

(wherein, R₁Represents a hydrogen atom or a methyl group, R₂Represents a C2-10 divalent hydrocarbon group, m is 0 or 1)

The molar ratio of the epoxy group of the unsaturated group-containing epoxy compound represented by the general formula (XVI) to the carboxyl group of the general formula (XV) can be arbitrarily changed for the purpose of adjusting the sensitivity of photoreaction (the size depending on the amount of polymerizable double bonds) or acid value of the alkali-soluble resin represented by the general formula (I). When the molar number of the general formula (XVI) is 90% or less based on the total molar number of 2 times the molar number of the component (a) and the molar number of the component (b), alkali developability can be imparted and the composition can be used for a photosensitive resin composition having photopatterning properties. In addition, when the sensitivity-improving effect of photoreaction is to be imparted, it is necessary to set the sensitivity-improving effect to 10% or more, and therefore, 10% to 90% is preferable. Further, more preferably 30% to 70%. The acid value of the alkali-soluble resin of the general formula (I) to be used is preferably 20 to 180, more preferably 30 to 120.

The weight average molecular weight (Mw) of the alkali-soluble resin of the general formula (I) of the present invention in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is usually 1000 to 100000, preferably 2000 to 20000. When the weight average molecular weight is less than 1000, pattern adhesion may decrease during alkali development. When the weight average molecular weight exceeds 100000, it is difficult to adjust the solution viscosity of the photosensitive resin composition suitable for application, and it takes too long time for alkali development, which is not preferable.

The photopolymerizable monomer (B) having at least one ethylenically unsaturated bond in the photosensitive resin composition for touch panels of the present invention includes, for example: (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, or ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, and mixtures thereof, (meth) acrylates such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa (meth) acrylate; in addition, in order to increase the refractive index of the cured product, there are included: examples of the compound having a plurality of aromatic rings include monomers having a polycyclic aromatic skeleton such as a bisphenol skeleton and a naphthalene skeleton, monomers containing an element having a large atomic refraction such as S, and the like, and specific examples thereof include ethylene oxide diacrylate of bisphenol a and 2,2 '-bis (2-acryloyloxyethoxy) -1,1' -binaphthyl. One or two or more of these compounds can be used, and monomers having a plurality of aromatic rings or polycyclic aromatic skeletons or monomers containing an element such as S are preferably used. In addition, the photopolymerizable monomer having at least one ethylenically unsaturated bond is preferably a monomer having two or more photopolymerizable groups and capable of crosslinking molecules of the unsaturated group-containing alkali-soluble resin with each other. The photopolymerizable monomer (B) having at least one ethylenically unsaturated bond does not have a free carboxyl group.

Examples of the photopolymerization initiator (C) in the photosensitive resin composition for touch panels of the present invention include: acetophenone compounds such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoprophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylbenzone, benzophenone compounds such as benzophenone, 2-chlorobenzophenone and p, p' -bisdimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, biimidazole compounds such as 2- (o-chlorophenyl) -4, 5-phenylbisimidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole and 2,4, 5-triarylbiimidazole, halogenated methyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanophenylvinyl) -1,3, 4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole, 2,4, 6-tris (trichloromethyl) -1,3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1, halogenated methyl-s-triazine compounds such as 3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3,4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyloxime), 1- (4-phenylthiophenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1, 2-dione-2-oxime-O-acetate, 1- (4-methylthiophenyl) butane-1-one oxime-O-acetate, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) ], [ 2- (O-benzoyloxime ] -,2- (O-benzoyloxime), 1- (4-methyl-ethyl-6-nitro-9H-carbazol-3-yl) or O-acyloxime-based compounds such as 4- (2-methoxy-1-methylethoxy) -2-methylphenyl ] -, O-acetyloxime, methanone, (2-methylphenyl) (7-nitro-9, 9-dipropyl-9H-fluoren-2-yl) -, acetyloxime, ethanone, 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] -,1- (O-acetyloxime), ethanone, 1- (-9, 9-dibutyl-7-nitro-9H-fluoren-2-yl) -, 1-O-acetyloxime and the like, benzildimethylketal, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and other sulfur compounds, 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone and other anthraquinones, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide and other organic peroxides, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and other thiol compounds, triethanolamine, triethylamine and other tertiary amines. Among them, from the viewpoint of easily obtaining a photosensitive resin composition with high sensitivity, O-acyloxime-based compounds are preferably used, and among them, from the viewpoint of easily controlling the line width in the case of obtaining a pattern of a transparent film by photolithography, a compound of the general formula (XVII) is particularly preferably used. Two or more of these photopolymerization initiators may be used. In the present invention, the photopolymerization initiator is used in a sense including a sensitizer.

[ solution 11]

In the formula (XVII), R₇Represents an alkyl group having 1 to 20 carbon atoms (which may be a straight chain or branched chain, may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain. in addition, a substituent such as a cycloalkyl group having 5 to 8 carbon atoms or a phenyl group may be present), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), or a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom). In addition, R₈Represents an alkanoyl group having 2 to 12 carbon atoms (which may be substituted with one or more halogen atoms or cyano groups), an alkenoyl group having 4 to 6 carbon atoms whose double bond is not conjugated with a carbonyl group, a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group), an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxycarbonyl group (which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms or a halogen atom). Preferred R₇An alkyl group having 1 to 20 carbon atoms (which may be straight or branched and may have a substituent such as a cycloalkyl group having 5 to 8 carbon atoms or a phenyl group), preferably R₈Is an alkanoyl group having 2 to 12 carbon atoms (which may be substituted with one or more halogen atoms or cyano groups), or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group).

In the photosensitive resin composition for a touch panel of the present invention, (D) is at least one metal oxide particle selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium, and an oxide of zirconium or titanium is preferably used, and particularly titanium oxide is preferably used. The shape of the metal oxide particles is not particularly limited, and particles having an average particle diameter of 5nm to 200nm in a dynamic scattering method (cumulant method), more preferably 10nm to 100nm, can be used. When the particle diameter is less than 5nm, the particles tend to aggregate and are difficult to be uniformly dispersed, or a large amount of a dispersant is required, and the desired physical properties cannot be obtained when the particles are cured, and a cured film having a particle diameter of more than 200nm has a large haze, which is not preferable.

The (E) in the photosensitive resin composition for a touch panel of the present invention is a surfactant having a surface tension of 20 to 28mN/m as measured with a propylene glycol monomethyl ether acetate solution having a concentration of 0.1 mass% of the (E), and examples thereof include a fluorine-based surfactant and a silicone-based surfactant. From the viewpoint of ensuring flatness after formation of a high refractive index layer even when irregularities between electrode patterns are present, a surfactant having a surface tension of 20 to 28mN/m in a 0.1 mass% propylene glycol monomethyl ether acetate solution is preferred, and a fluorine-based surfactant is particularly preferred.

The silane compound (F) in the photosensitive resin composition for a touch panel of the present invention includes silane compounds of the general formula (XVIII), and specific examples of the compounds include: 3- (glycidyloxy) propyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc. A ureido group-containing silane compound such as 3-ureidopropyltriethoxysilane is preferable in that the adhesiveness between the electrode pattern and the cured film as the high refractive index layer can be improved.

[ solution 12]

(wherein, R₉A hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule, and may have a reactive group containing an unsaturated bond, an epoxy group (including an alicyclic epoxy group such as a 3, 4-epoxycyclohexyl group), an oxetanyl group, an isocyanate group, an amino group or a ureido group as a substituent, R₁₀Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R₁₁Each independently represents an alkyl group having 1 to 4 carbon atoms, and t is 1 to 3. Preferred R₉A hydrocarbon group having 1 to 10 carbon atoms and having an epoxy group, an oxetanyl group, an isocyanate group or a ureido group as a substituent, preferably R₁₀、R₁₁Is methyl or ethyl)

In the photosensitive resin composition of the present invention, it is preferable to adjust the viscosity by using a solvent other than the above (a) to (F). Examples of the solvent include: alcohols such as methanol, ethanol, N-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol, terpenes such as α -terpineol and β -terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, glycol ethers such as ethyl acetate, butyl acetate, ethyl lactate, cellosolve acetate, ethyl cellosolve acetate, and the like, Esters such as butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, and the like can be dissolved and mixed using these solvents to prepare a uniform solution composition.

The photosensitive resin composition of the present invention may contain a compound having at least two epoxy groups in one molecule in order to adjust physical properties and the like when the composition is formed into a cured film. Specific examples of the compound include: bisphenol a type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, bis (3, 4-epoxycyclohexyl) methane, 2' -bis (3, 4-epoxycyclohexyl) propane, 3, 4-epoxycyclohexanecarboxylic acid (3',4' -epoxycyclohexyl) methyl ester, 1, 2-ethylene-bis (3, 4-epoxycyclohexylcarboxylate), bis (3, 4-epoxycyclohexylmethyl) adipate and other alicyclic epoxy compounds, a dicyclopentadiene skeleton-containing polyfunctional epoxy compound (for example, HP7200 series manufactured by diesei corporation), 1, 2-epoxy-4- (2-oxetanyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (for example, "EHPE 3150" manufactured by Daicel corporation), epoxidized polybutadiene (for example, "NISSO-PB. JP-100" manufactured by Nissad corporation), epoxy compound having a silicone skeleton, and the like. These components are preferably compounds having an epoxy equivalent of 90 to 500g/eq and a number average molecular weight of 100 to 5000.

In addition, the photosensitive resin composition of the present invention may contain additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a leveling agent, and an antifoaming agent, if necessary. Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, biphenyltriol, t-butyl catechol, phenothiazine, hindered phenol compounds, and the like, and plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like, and examples of the leveling agent or defoaming agent include: silicone, fluorine, and acrylic compounds.

The preferred composition ratio of each component (a) to (F) in the photosensitive resin composition is 5 to 100 parts by mass of (B) with respect to 100 parts by mass of (a), and 0.1 to 40 parts by mass of (C) with respect to 100 parts by mass of the total amount of (a) and (B). Further, in the solid content (including the monomer component which becomes the solid content by the photo-curing reaction) of the composition, (D) is 1 to 60% by mass. Further, in the photosensitive resin composition (including the solvent), (E) is 0.001 to 5% by mass, preferably 0.001 to 1.0% by mass. When (E) is less than 0.001 mass%, unevenness between electrode patterns becomes large and color unevenness may occur. When (E) exceeds 5 mass%, shrinkage or unevenness may occur in the cured film. Further, in the solid content (including the monomer component which becomes the solid content by the photo-curing reaction) of the composition, (F) is 0.01 to 20% by mass, preferably 0.01 to 10% by mass. When (F) is less than 0.01% by mass, there is a fear that the adhesiveness is particularly lowered under high temperature and high humidity. When (F) exceeds 20 wt%, foreign matter may be generated in the cured film or the stability of the photosensitive resin composition may be reduced with time.

The photosensitive resin composition for a touch panel of the present invention contains the components (A) to (F) as main components. In the photosensitive resin composition solution, the total amount of the components (a) to (F) other than the solvent (including the monomer component which becomes a solid component after photo-curing) is preferably 70 mass% or more, preferably 80 mass% or more, and more preferably 90 mass% or more. The amount of the solvent varies depending on the target viscosity, and is preferably in the range of 60 to 90% by mass in the photosensitive resin composition solution.

The method of using the photosensitive resin composition for a touch panel of the present invention can be used for coating and film-forming a transparent conductive metal oxide film for wiring formed on a substrate such as glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, or the like), curing an exposed portion by irradiating ultraviolet rays through a photomask on the coating film, forming a pattern by developing an unexposed portion with an alkaline aqueous solution, and post-baking the pattern to form a resist pattern by such a photolithography method, and forming a protective film such as an insulating film between wirings or the like having transparency.

The method for applying the photosensitive resin composition solution to the substrate may be any method such as a method using a roll coater, a plane coater (land coater), a slit coater, or a rotary coater, in addition to the well-known solution dipping method and spraying method. After coating to a desired thickness by these methods, the coating film is formed by removing the solvent (prebaking). The prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and the heating time of the prebaking are appropriately selected depending on the solvent used, and are, for example, carried out at a temperature of 60 to 110 ℃ for 1 to 3 minutes. The film thickness of the photosensitive resin composition after prebaking is preferably 0.1 μm to 5 μm, and when the film thickness is less than 0.1 μm, the adhesiveness to the substrate at the time of alkali development in the subsequent step is lowered. On the other hand, if the film thickness exceeds 5 μm, flatness is lowered, and warpage may occur when the substrate is a transparent film.

The exposure after the prebaking is performed by an exposure machine, and only the portion of the photosensitive resin composition corresponding to the pattern is exposed to light through a photomask. The exposure machine and the exposure irradiation conditions are appropriately selected, and the photosensitive resin composition in the coating film is cured by exposure using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp.

The alkali development after the exposure is performed to remove the unexposed portion of the photosensitive resin composition, and a desired pattern is formed by the development. Examples of the developer suitable for the alkali development include: an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of a hydroxide of an alkali metal, or the like, and particularly, a weakly alkaline aqueous solution containing 0.03 to 1 mass% of a carbonate of sodium carbonate, potassium carbonate, or the like is preferably used for development at a temperature of 23 to 27 ℃.

After the development, the resultant is heat-treated at a temperature of 150 to 250 ℃ for 30 to 120 minutes (post-baking). The post-baking is performed to obtain desired physical properties of the cured film.

[ examples ]

The present invention will be described in more detail below with reference to synthetic examples and examples, but the present invention is not limited to these examples. Unless otherwise specified, evaluation of the resin in the following synthetic examples was performed as follows.

[ solid content concentration ]

1g of the resin solution obtained in the following synthesis example was impregnated in a glass filter [ weight: w₀(g)]Neutralization and weighing [ W₁(g)]According to the weight [ W ] after heating at 160 ℃ for 2 hours₂(g)]The solid content concentration was determined by the following equation.

The solid content concentration (wt%) was 100 × (W)₂-W₀)/(W₁-W₀)

[ acid value ]

The resin solution obtained in the following synthesis example was dissolved in dioxane, and titrated with an 1/10N-KOH aqueous solution using a potentiometric titrator (product name COM-1600 manufactured by heimian industries, inc.), and the amount of KOH necessary for 1g of the solid content was defined as the acid value.

[ molecular weight ]

HLC-8220GPC manufactured by Gel Permeation Chromatography (GPC) [ Tosoh (thon) (thigh), solvent: tetrahydrofuran, column: TSK gel Super H-2000(2 pieces) + TSK gel Super H-3000(1 piece) + TSK gel Super H-4000(1 piece) + TSK gel Super H-5000 (1 piece) [ manufactured by Tosoh (Strand) ], temperature: 40 ℃, speed: 0.6ml/min, and the molecular weight was determined as a weight average molecular weight (Mw) in terms of a PS-oligomer set manufactured by Tosoh (Strand) standard polystyrene.

[ surface tension ]

The surface tension of a propylene glycol monomethyl ether acetate solution having a surfactant concentration of 0.1 mass% was measured at an air temperature of 23 ℃ and a humidity of 50% by using a plate (plate) automatic surface tensiometer (Model: CBVP-Z manufactured by Kyowa interface science).

[ Synthesis example 1]

A500 ml four-necked flask equipped with a reflux condenser was charged with 0.23mol of a bisphenol fluorene type epoxy compound, 0.46mol of acrylic acid, 161.0g of propylene glycol monomethyl ether acetate and 0.48g of tetraethylammonium bromide (TEAB), and the mixture was stirred at 100 to 105 ℃ for 20 hours under heating to effect a reaction. Then, 0.08mol of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 0.18mol of 1,2,3, 6-tetrahydrophthalic anhydride were added to the flask, and the mixture was stirred at 120 to 125 ℃ for 6 hours under heating to obtain an alkali-soluble resin solution 1 represented by the general formula (V). The resin solution thus obtained had a solid content of 55.6 wt%, an acid value (in terms of solid content) of 101mgKOH/g, and Mw according to GPC analysis was 2400.

The bisphenol fluorene type epoxy compound used is a compound of the general formula (IV) in which A is fluorene-9, 9-diyl and R is₃～R₆Is a hydrogen atom. Synthesis example2. The same compound was used in synthesis example 3.

[ Synthesis example 2]

A500 ml four-necked flask equipped with a reflux condenser was charged with 0.23mol of a bisphenol fluorene-based epoxy compound, 0.46mol of acrylic acid, 161.0g of propylene glycol monomethyl ether acetate and 0.48g of tetraethylammonium bromide (TEAB), and the mixture was stirred at 100 to 105 ℃ for 20 hours under heating to effect a reaction. Then, 0.12mol of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 0.12mol of 1,2,3, 6-tetrahydrophthalic anhydride were added to the flask, and the mixture was stirred at 120 to 125 ℃ for 6 hours under heating to obtain an alkali-soluble resin solution 2 represented by the general formula (V). The resin solution thus obtained had a solid content of 55.6 wt%, an acid value (in terms of solid content) of 103mgKOH/g, and Mw of 3600 as determined by GPC analysis.

[ Synthesis example 3]

A500 ml four-necked flask equipped with a reflux condenser was charged with 0.23mol of a bisphenol fluorene type epoxy compound, 0.46mol of acrylic acid, 156.0g of propylene glycol monomethyl ether acetate and 0.48g of tetraethylammonium bromide (TEAB), and the mixture was stirred at 100 to 105 ℃ for 20 hours under heating to effect a reaction. Then, 0.15mol of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 0.005mol of 1,2,3, 6-tetrahydrophthalic anhydride were added to the flask, and the mixture was stirred at 120 to 125 ℃ for 6 hours under heating to obtain an alkali-soluble resin solution 3 represented by the general formula (V). The resin solution thus obtained had a solid content of 55.6 wt%, an acid value (in terms of solid content) of 93mgKOH/g, and Mw according to GPC analysis of 8300.

[ Synthesis example 4]

0.34mol of 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate, 0.68mol of acrylic acid, 139.0g of propylene glycol monomethyl ether acetate and 2.15g of tetraethylammonium bromide (TEAB) were added to a 500ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 100 ℃ to 105 ℃ for 20 hours under heating to effect a reaction. Then, 0.12mol of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 0.27mol of 1,2,3, 6-tetrahydrophthalic anhydride were added to the flask, and the mixture was stirred at 120 to 125 ℃ for 8 hours under heating to effect a reaction. Further, 0.28mol of glycidyl methacrylate was added thereto, and the mixture was stirred at 100 to 105 ℃ for 8 hours under heating to obtain an alkali-soluble resin solution 4. The resin solution thus obtained had a solid content of 57.0 wt%, an acid value (in terms of solid content) of 82mgKOH/g, and an Mw of 3500 according to GPC analysis.

[ comparative Synthesis example 1]

51.65g (0.60mol) of methacrylic acid, 38.44g (0.38mol) of methyl methacrylate, 38.77g (0.22mol) of benzyl methacrylate, 5.91g of azobisisobutyronitrile and 370g of diethylene glycol dimethyl ether were added to a 1000ml four-necked flask equipped with a nitrogen inlet and a reflux tube, and polymerization was carried out by stirring under a nitrogen stream at 80 ℃ to 85 ℃ for 8 hours. 39.23g (0.28mol) of glycidyl methacrylate, 1.44g of triphenylphosphine and 0.055g of 2, 6-di-tert-butyl-p-cresol were added to the flask, and the mixture was stirred at 80 ℃ to 85 ℃ for 16 hours to obtain an alkali-soluble resin solution 5. The resin solution thus obtained had a solid content of 32% by mass, an acid value (in terms of solid content) of 110mgKOH/g, and Mw of 18100 as determined by GPC analysis.

(preparation of photosensitive resin composition)

Photosensitive resin compositions of examples 1 to 11 and comparative examples 1 to 7 were prepared by blending the compositions shown in tables 1 and 2. The ingredients used for formulation were as follows.

Alkali-soluble resin solution 1 to alkali-soluble resin solution 5: synthesis examples 1 to 4 and comparative Synthesis example 1

Photopolymerizable monomer

Photopolymerizable monomer 1: mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [ trade name DPHA manufactured by Nippon Kagaku Kogyo ]

Photopolymerizable monomer 2: 2,2 '-bis (2-acryloyloxyethoxy) -1,1' -binaphthyl

Photopolymerization initiator: 1, 2-octanedione, 1- [4- (phenylthio) -,2- (O-benzoyloxime) ] [ Irgacure (OXE) 01, trade name of BASF corporation ]

Metal oxide dispersion: titanium oxide Dispersion of propylene glycol monomethyl ether acetate solvent having a titanium oxide concentration of 19.6% by mass and a dispersant of 9.3% by mass (average particle diameter by cumulative amount of titanium oxide: 62nm)

Solvent(s)

Solvent 1: propylene Glycol Monomethyl Ether Acetate (PGMEA)

Solvent 2: diethylene glycol methyl ethyl ether

Surfactants

Surfactant 1: a1 mass% solution (surface tension of 25.9mN/m when measured as a PGMEA solution having a concentration of 0.1 mass% of polyether-modified polydimethylsiloxane) obtained by diluting polyether-modified polydimethylsiloxane [ BYK (BYK)302 manufactured by BYK Chemie Japan ] 100 times with PGMEA

Surfactant 2: a1 mass% solution prepared by 100-fold dilution of a perfluoroalkyl group-containing oligomer [ F-477 manufactured by Diegon (DIC) ] with PGMEA (surface tension of 27.0mN/m measured with a PGMEA solution having a perfluoroalkyl group-containing oligomer concentration of 0.1 mass%)

Silane coupling agent

Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane

Silane coupling agent 2: 3-ureidopropyltriethoxysilane

[ Table 1]

[ Table 2]

Add 100% surfactant. (100 times without solvent dilution)

The following are the evaluation methods for evaluating various properties using the photosensitive resin composition solutions of examples 1 to 11 and comparative examples 1 to 7, and the evaluation results are shown in tables 3 and 4.

(transmittance and refractive index)

A photosensitive resin composition solution was applied onto a degreased and cleaned glass substrate having a thickness of 1.2mm and a size of 125mm X125 mm by using a spin coater, and dried, and then irradiated with ultraviolet light having a wavelength of 365nm and an illuminance of 10mW/cm2 for 10 seconds using a high-pressure mercury lamp of 500W without using a photomask. After exposure, the resultant was developed at 23 ℃ under a pressure of 0.1MPa for 60 seconds using a 0.4% aqueous solution of sodium carbonate, and then heat-hardened at 230 ℃ for 30 minutes using a hot air dryer. The glass substrate on which the cured film was formed was evaluated for transmittance and refractive index.

As for the transmittance, the light transmittance at 400nm was measured using a spectrophotometer (apparatus: Japanese electrochromic SD 5000). O: 85% or more, and x: less than 85 percent

The refractive index was measured at 633nm using a prism coupler film thickness refractometer (Model 2010/M manufactured by Metricon corporation).

(developability)

A photosensitive resin composition solution was applied onto a degreased and cleaned ITO film-forming glass substrate having a thickness of 1.2mm and a size of 125mm X125 mm by using a spin coater, and dried, and then a photomask having an L/S (line width/space width) in a predetermined range was closely attached, and a high-pressure mercury lamp of 500W was used to irradiate an illumination intensity of 10mW/cm at a wavelength of 365nm²Ultraviolet light for 10 seconds. After exposure, the coating film was developed with a 0.4% sodium carbonate aqueous solution at 23 ℃ under a pressure of 0.1MPa for 60 seconds to remove the unexposed portion, and then heat-cured at 230 ℃ for 30 minutes using a hot air dryer.

The formation of thin lines in the formed resist film pattern was confirmed with a microscope, and evaluated as follows.

O: forming a pattern with L/S of 15 μm/15 μm or more without residue

X: no pattern with L/S less than 15 μm/15 μm is formed, or burr or residue of the pattern is conspicuous

(evaluation of pattern visibility of ITO pattern)

On an ITO film-forming glass substrate having a thickness of 1.2mm and a size of 125mm X125 mm, a space of 3mm was formedA polyimide tape 3mm wide was attached in a stripe pattern. Then, the substrate was immersed in a glass dish (schale) containing aqua regia at room temperature for 2 minutes, and then washed with pure water to remove the ITO film on the portion to which the polyimide tape was not attached, and the polyimide tape was peeled off to form a striped ITO pattern. On the glass substrate on which the striped ITO pattern was formed, a photosensitive resin composition solution was applied by a spin coater in a condition that the dry film thickness was 1.0 μm, and then dried, a photomask having a predetermined range of L/S (line width/space width) was closely attached, and a 500W high-pressure mercury lamp was used to irradiate the glass substrate with an illuminance of 10mW/cm at a wavelength of 365nm²Ultraviolet light for 10 seconds. After exposure, the coating film was developed with a 0.4% aqueous solution of sodium carbonate at 23 ℃ under a pressure of 0.1MPa for 60 seconds to remove the unexposed portion, and then heat-cured at 230 ℃ for 30 minutes using a hot air dryer to form a cured film on the exposed portion. In the glass substrate with an ITO stripe pattern on which the cured film was formed, the cured film forming part and the non-formed part were compared visually, and whether the ITO pattern could be confirmed in the non-formed part but the ITO pattern could also be seen in the formed part (pattern visible) or could not be seen in the formed part (pattern invisible) was evaluated.

O: it was observed that the ITO pattern was not conspicuous and was not visible due to the hardened film

X: even if the cured film is present, the ITO pattern is conspicuous and the pattern is clearly visible

(color unevenness)

A polyimide tape 3mm wide was attached in stripes to an ITO film-forming glass substrate 1.2mm thick and 125mm × 125mm in size with a 3mm interval. Then, the glass dish with the aqua regia added was immersed at room temperature for 2 minutes, and then washed with pure water to remove the ITO film on the portion to which the polyimide tape was not attached, and further the polyimide tape was peeled off to form a striped ITO pattern. On the glass substrate on which the striped ITO pattern was formed, a photosensitive resin composition solution was applied by a spin coater in a condition that the dry film thickness was 1.0 μm, and then dried, and then irradiated with 365nm light from a 500W high-pressure mercury lamp without using a photomaskIlluminance of 10mW/cm²Ultraviolet light for 10 seconds. After exposure, the coating film was developed with a 0.4% aqueous solution of sodium carbonate at 23 ℃ under a pressure of 0.1MPa for 60 seconds to remove the unexposed portion, and then heat-cured at 230 ℃ for 30 minutes using a hot air dryer to form a cured film on the exposed portion. In the ITO striped pattern glass substrate on which the cured film was formed, color unevenness due to unevenness between ITO patterns was evaluated visually.

Very good: no color inhomogeneity was observed at all

O: color unevenness was observed in the region below 1/4 of the ITO stripe-patterned glass substrate

And (delta): color unevenness was observed in the region below 1/3 of the ITO stripe-patterned glass substrate

X: when color difference was observed on the entire surface of the glass substrate having the ITO stripe pattern, or when shrinkage or unevenness occurred in the cured film

(moisture resistance reliability)

The photosensitive resin composition solution was applied to a degreased and cleaned glass substrate having a thickness of 1.2mm and a size of 125mm X125 mm under a condition that the dry film thickness became 1.0 μm using a spin coater, and dried, and then the illuminance at a wavelength of 365nm of 10mW/cm was measured using a 500W high pressure mercury lamp without using a photomask²Is irradiated for 10 seconds. After exposure, the resultant was developed at 23 ℃ under a pressure of 0.1MPa for 60 seconds using a 0.4% aqueous solution of sodium carbonate, and then heat-cured at 230 ℃ for 30 minutes using a hot air dryer. The glass substrate on which the cured film was formed was left at a temperature of 121 ℃, a humidity of 100%, and a pressure of 2atm for 5 hours. Further, a tape peeling test was performed in which a Super Cutter Guide (Super Cutter Guide) manufactured by taiyoumachine materials ltd was used to cut the set hardened material so as to form 100 square meshes of 1mm × 1mm, and a cellophane tape (manufactured by Nichiban) was attached to the meshes, followed by peeling.

Very good: the hardened material in the grid is not peeled off

O: less than 1/4 peeling of hardened substance in grid

And (delta): less than 1/3 peeling of hardened substance in grid

X: 1/3 or more, or foreign matter, or deterioration of the stability of the photosensitive resin composition with time

(resistance to Heat discoloration)

After a photosensitive resin composition solution was applied onto a degreased and cleaned glass plate having a thickness of 1.2mm under a condition that the dry film thickness became 1.2 μm using a spin coater and dried, the entire surface of the glass plate on which the white film was formed was irradiated with a 500W high-pressure mercury lamp at an illuminance of 10mW/cm at a wavelength of 365nm without using a photomask²Ultraviolet light for 10 seconds. After exposure, a developing solution treatment was performed for 60 seconds at 23 ℃ under a pressure of 0.1MPa using a 0.4% aqueous solution of sodium carbonate. Then, heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer. In order to confirm the thermal discoloration resistance, the resultant was further subjected to heat treatment at 230 ℃ for 150 minutes, and the yellowness was measured with a spectrophotometer (apparatus: Japanese electrochromic SD 5000).

[ Table 3]

[ Table 4]

As is clear from the results of examples 1 to 11, it was found that when a cured film was formed on an ITO pattern using the photosensitive resin composition of the present invention, the cured film had alkali-developable pattern formability of the cured film for forming a desired pattern, and that the cured film had no ITO pattern visible, had color unevenness and excellent moisture-proof reliability, and also had excellent thermal discoloration resistance. When the specific alkali-soluble resin of the present invention was not used as in comparative example 1, a cured film having excellent pattern formability and no pattern visibility of an ITO pattern could be obtained by increasing the refractive index, but only a cured film having poor thermal discoloration resistance could be obtained with a yellow index of more than 1 after heating at 230 ℃ for 180 minutes. In addition, if the metal oxide for high refraction is not added as in comparative example 2, the refractive index cannot be sufficiently increased although the pattern formability and the thermal discoloration resistance are sufficient, and the pattern of the ITO pattern cannot be eliminated. Further, as in comparative examples 4 to 7, when the surfactant or the silane compound in the photosensitive resin composition of the present invention exceeds a predetermined range, color unevenness and moisture resistance reliability are observed.

[ Industrial Applicability ]

The photosensitive resin composition of the present invention can suppress a decrease in visibility due to pattern visibility of a transparent conductive oxide pattern such as ITO, and is excellent in pattern formability, color unevenness, moisture resistance reliability, and heat discoloration resistance, and therefore is useful as an insulating film or a protective film for a touch panel. Further, the composition is also useful as an overcoat or an insulating film having excellent pattern formability and heat resistance, and is applicable to, for example, formation in the form of a thin film because of realization of a high refractive index, and is also useful as a component of a display device such as a color filter.

Claims

1. A photosensitive resin composition for a touch panel, comprising:

(A-1) an alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or anhydride thereof and (b) a tetracarboxylic acid or acid dianhydride thereof with a reactant of an epoxy compound having two glycidyl ether groups derived from a bisphenol and a monocarboxylic acid having an unsaturated group; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) metal oxide particles of at least one selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium; (E) a surfactant; and (F) a silane compound, and the photosensitive resin composition for a touch screen, wherein:

the component (A-1) is represented by the general formula (V) and is obtained by reacting at a ratio of (a)/(b) of 0.01 to 3.0, has a weight average molecular weight of 2000 to 10000, an acid value of 30 to 200mgKOH/g,

the photosensitive resin composition contains 0.001 to 5 mass% of the component (E), and the photosensitive resin composition contains 0.01 to 20 mass% of the component (F) in a solid content which becomes a solid content after photo-curing,

in the formula, R₃、R₄、R₅And R₆Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R₁Represents a hydrogen atom or a methyl group, A represents a fluorene-9, 9-diyl group, Y represents a tetravalent carboxylic acid residue, and W each independently represents a hydrogen atom or-OC-L- (COOH) s, wherein L represents a divalent or trivalent carboxylic acid residue, and s represents an integer of 1 or 2; in addition, r is an integer of 1 to 20 per molecule, and r represents an average value of 1 to 20.

2. The photosensitive resin composition for a touch panel according to claim 1, wherein: (F) the component is a silane compound with carbamido.

3. The photosensitive resin composition for a touch panel according to claim 1 or 2, wherein: (E) the component (E) is a surfactant having a surface tension of 20 to 28mN/m as measured with respect to a propylene glycol monomethyl ether acetate solution having a concentration of 0.1% by mass of the component (E).

4. The photosensitive resin composition for a touch panel according to claim 1 or 2, wherein: 5 to 100 parts by mass of the component (B) per 100 parts by mass of the component (A-1); 0.1 to 40 parts by mass of the component (C) per 100 parts by mass of the total amount of the component (A-1) and the component (B); the component (D) is 1 to 60 mass% in the solid content.

5. A cured film, characterized in that: the photosensitive resin composition for a touch panel according to any one of claims 1 to 4 is cured.

6. A touch screen, characterized by: has the hardened film of claim 5.