JP6822758B2 - A photosensitive resin composition for a touch panel, a cured film thereof, and a touch panel having the cured film. - Google Patents

Description

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.

Today, the demand for liquid crystal displays is increasing, driven by small and medium-sized displays such as mobile phones, smartphones, and tablet terminals in addition to large displays such as personal computers and televisions. Recently, touch panels have come to be widely used as data input means in display devices such as liquid crystal displays, and among them, capacitive touch panels have come to be used. The capacitance type touch panel has a structure in which mosaic-like electrode patterns formed of a transparent conductive material such as ITO are arranged on both sides of a transparent insulating film. The two-layer electrode patterns arranged on both sides show a shape connected in the x-axis direction and the y-axis direction, respectively, and are connected to an external control circuit via take-out wiring of metal or the like. When a finger touches the screen, a change in capacitance occurs in the electrode pattern in the vicinity, and the control circuit can detect this as coordinate information to identify the position of the finger (see, for example, Patent Document 1).

When a touch panel having such a structure is used for a display device such as a display, the electrode pattern can be seen due to the difference in optical physical characteristics between the portion with the electrode pattern and the portion without the electrode pattern, that is, the so-called "bone visibility" reduces the visibility. was there. In order to reduce the appearance of bone, a transparent conductive material that reduces the film thickness of the electrode pattern or replaces ITO has been proposed (see Patent Document 2). Further, a method of arranging a high refractive index layer for the purpose of reducing the difference in optical physical properties has been proposed, but problems such as lack of patterning property and poor heat resistance remain, and higher performance is achieved. Development of materials is desired (see Patent Documents 3 and 4). Further, recently, after forming a high refractive index layer on the electrode pattern, color unevenness occurs because the height differs between the portion with the electrode pattern and the portion without the electrode pattern. Therefore, it is desired to develop a material for forming a high refractive index layer, which can secure flatness after forming the high refractive index layer even if there are irregularities between the electrode patterns.

Japanese Unexamined Patent Publication No. 2011-186717 Japanese Unexamined Patent Publication No. 2012-209030 WO2013 / 038718 Pamphlet Japanese Unexamined Patent Publication No. 2013-14229

Therefore, an object of the present invention is to provide a photosensitive resin composition for a touch panel capable of suppressing a decrease in visibility due to bone visibility, a cured film using the same, and a touch panel having the cured film. Further, by using a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure, it is an effective technique when there is a demand for excellent patterning property and heat resistance, and a cured film to which this technique is applied. Can also be applied to an overcoat or an insulating film having good heat resistance, so that it can be used as a component of a touch panel or a color filter having good heat resistance. Further, a photosensitive resin composition for a touch panel for forming a high refractive index layer, which has good flatness after forming a high refractive index layer and can reduce the possibility of causing a problem in a process after forming the high refractive index layer. To provide things.

As a result of diligent research to solve the above-mentioned problems, the present inventors have obtained a bone appearance by using a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure and a specific metal oxide or the like. It has been found that it is possible to obtain a photosensitive resin composition that can suppress a decrease in visibility, has excellent patterning properties, and satisfies the requirements for heat resistance. Furthermore, it has been found that a photosensitive resin composition for forming a high refractive index layer having good flatness after forming the high refractive index layer can also be obtained.
That is, the gist of the present invention is as follows.

(1) The present invention relates to (A-1) a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid, and (a) dicarboxylic acid or A tricarboxylic acid or an acid anhydride thereof, (b) an alkali-soluble resin obtained by reacting a tetracarboxylic acid or an acid dianhydride thereof, and (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond. , (C) Photopolymerization initiator, (D) at least one metal oxide particle selected from (D) aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium, (E) surfactant, and (F). A photosensitive resin composition for a touch panel containing a silane compound, the component (E) is contained in the photosensitive resin composition in an amount of 0.001 to 5% by mass, and the component (F) is the photosensitive resin composition. A photosensitive resin composition for a touch panel, which is contained in an amount of 0.01 to 20% by mass in a solid content that becomes a solid content after photocuring.

（但し、Ｒ₁は水素原子またはメチル基を示す。Ｘは単結合又は内部にヘテロ元素を含んでいてもよい炭素数１〜２０の２価の有機基を示し、Ｙは４価のカルボン酸残基を示し、Ｚは水素原子又は下記一般式（II）で表される置換基を示し、Ｇは水素原子または下記一般式（III）で表される置換基を示す。ｎは１〜２０の平均値を示す。）

（但し、Ｒ₁は水素原子又はメチル基を示し、Ｒ₂は炭素数２〜１０の２価の炭化水素基を示し、Ｌは２価又は３価のカルボン酸残基を示す。ｍは０又は１を表す。ｐ及びｑは、それぞれ０又は１又は２であり、ｐ＋ｑは１又は２である。）

（但し、Ｒ₁は水素原子又はメチル基を示し、Ｒ₂は炭素数２〜１０の２価の炭化水素基を示す。ｍは０又は１を表す。） (2) (A-2) Unsaturated group-containing alkali-soluble resin represented by the general formula (I), (B) Photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) Initiation of photopolymerization For touch panels containing agents, (D) at least one metal oxide particle selected from aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium, (E) surfactant, and (F) silane compound. a photosensitive resin composition, (E) component is contained 0.001 to 5 wt% in the photosensitive resin composition, (F) component, the solid component after photocuring of the photosensitive resin composition A photosensitive resin composition for a touch panel, which is contained in an amount of 0.01 to 20% by mass in the solid content.

(However, R ₁ represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside, and Y represents a tetravalent carboxylic acid. Indicates a residue, Z represents a hydrogen atom or a substituent represented by the following general formula (II), G represents a hydrogen atom or a substituent represented by the following general formula (III), and n represents 1 to 20. Shows the average value of.)

(However, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, and m is 0. Or 1; p and q are 0 or 1 or 2, respectively, and p + q is 1 or 2.)

(However, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and m represents 0 or 1.)

(3) The present invention also includes 5 to 100 parts by mass of (B) and (C) with respect to 100 parts by mass of (A-1) and / or (A-2) in the photosensitive resin composition for a touch panel. Is 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of (A-1) and / or (A-2) and (B), and further becomes solid content (solid content by photocuring reaction). The photosensitive resin composition for a touch panel according to (1) or (2), wherein (D) in (containing a monomer component) is 1 to 60% by mass.

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

(5) The present invention is also any of (1) to (3), wherein the component (F) is a silane compound having a functional group of any of an epoxy group, an oxetanyl group, an isocyanate group, and a ureido group. Epoxy resin composition.

(6) The present invention is also 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).

The photosensitive resin composition for a touch panel of the present invention can form a pattern by photolithography, is particularly excellent in development characteristics, and the formed cured film has high transparency and a high refractive index, so that the touch panel is transparent. As the insulating film and the protective film, it is possible to obtain a good cured film that prevents the phenomenon of bone appearance of the ITO wiring pattern and is also excellent in flatness after forming the cured film.

The touch panel of the present invention is obtained by arranging a 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.

The present invention will be described in detail below.

In the photosensitive resin composition for a touch panel of the present invention, (A-1) is a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid. It is an alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof. Preferably, it is an alkali-soluble resin reacted in a range where the molar ratio of (a) / (b) is 0.01 to 10.

Examples of bisphenols used as raw materials for (A-1) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and 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, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxy-3-chlorophenyl) propane Hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9 -Bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9 -Bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene , 9,9-Bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol and the like, and derivatives thereof. Among these, those having a fluorene-9,9-diyl group are particularly preferably used.

Next, the above bisphenols are reacted with epichlorohydrin to obtain an epoxy compound having two glycidyl ether groups. Since this reaction generally involves oligomerization of the diglycidyl ether compound, the epoxy compound of the following general formula (IV) can be obtained.

Here, in the above general formula (I), R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, respectively. A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, Fluoren- Represents a 9,9-diyl group or direct bond. l is an integer of 0 to 10 in each molecule. Preferred R ₃ , R ₄ , R ₅ and R ₆ are hydrogen atoms and preferred A is a fluorene-9,9-diyl group. Further, l is an integer of 1 to 10 in each molecule, and the average value is usually 0 to 10 (not necessarily an integer) because a plurality of values are mixed, but the average value of l is preferable. Is 0 to 3. If the average value of l exceeds the upper limit, the viscosity of the composition becomes too large when an alkali-soluble resin synthesized using the epoxy compound is used to prepare a photosensitive resin composition, and the coating cannot be performed successfully. Or, the alkali solubility cannot be sufficiently imparted, and the alkali developability becomes very poor.

Next, the compound of the general formula (IV) is reacted with acrylic acid or methacrylic acid as an unsaturated group-containing monocarboxylic acid, or both, and the obtained reaction product having a hydroxy group is subjected to (a) dicarboxylic acid or The tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its acid dianhydride are reacted preferably in a range where the molar ratio of (a) / (b) is 0.01 to 10 to obtain the following. An alkali-soluble resin having a structure of an epoxy (meth) acrylate acid adduct represented by the general formula (V) is obtained.

〔式中、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ_１は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、フルオレン−９，９−ジイル基又は直結合を表し、Ｙは４価のカルボン酸残基を表し、Ｗは、それぞれ独立して水素原子又は−ＯＣ−Ｌ−（ＣＯＯＨ）ｓ（但し、Ｌは２価又は３価のカルボン酸残基を表し、ｓは１又は２の整数を表す）を表す。また、ｒは１つ１つの分子において各々１〜２０の整数であり、ｒは１〜２０の平均値を示す。〕

[In the formula, R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₁ is a hydrogen atom or a methyl group. , A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O- , Fluolene-9,9-diyl group or direct bond, Y represents a tetravalent carboxylic acid residue, W represents a hydrogen atom or -OC-L- (COOH) s (where L), respectively. Represents a divalent or trivalent carboxylic acid residue, and s represents an integer of 1 or 2). Further, r is an integer of 1 to 20 in each molecule, and r indicates an average value of 1 to 20. ]

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

The (a) dicarboxylic acid or tricarboxylic acid used in the epoxy (meth) acrylate acid adduct of the general formula (V) according to (A-1) of the present invention or its acid anhydride is a chain hydrocarbon dicarboxylic acid. Alternatively, a tricarboxylic acid or an acid anhydride thereof, an alicyclic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is used. Here, examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralinic acid, malonic acid, and glutaric acid. There are compounds such as succinic acid, tartrate acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and further, a dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein or an acid anhydride thereof may be used. Further, examples of the alicyclic dicarboxylic acid or tricarboxylic acid or its acid anhydride include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid and norbornandicarboxylic acid, and further optionally. It may be a dicarboxylic acid or a tricarboxylic acid into which the substituent of the above is introduced, or an acid anhydride thereof. Further, examples of the aromatic dicarboxylic acid or tricarboxylic acid or its acid anhydride include compounds such as phthalic acid, isophthalic acid and trimellitic acid, and further, a dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein or its acid anhydride. It may be an acid anhydride.

Further, as the (b) tetracarboxylic acid or its acid dianhydride used in the epoxy (meth) acrylate acid adduct of the general formula (V) according to the present invention (A-1), a chain hydrocarbon tetra is used. A carboxylic acid or its acid dianhydride, an alicyclic tetracarboxylic acid or its acid dianhydride, or an aromatic polyvalent carboxylic acid or its acid dianhydride is used. Here, examples of the chain hydrocarbon tetracarboxylic acid or its acid dianhydride include butanetetracarboxylic acid, pentantetracarboxylic acid, hexanetetracarboxylic acid and the like, and further, tetracarboxylic acid having a substituent introduced therein. Alternatively, the acid dianhydride thereof may be used. Examples of the alicyclic tetracarboxylic acid or its acid dianhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptantetracarboxylic acid, norbornanetetracarboxylic acid and the like. Further, a tetracarboxylic acid having a substituent introduced therein or an acid dianhydride thereof may be used. Further, examples of the aromatic tetracarboxylic acid and its acid dianhydride include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid or its acid dianhydride, and further, substitution thereof. It may be a tetracarboxylic acid having an introduced group or an acid dianhydride thereof.

(A) Dicarboxylic acid or tricarboxylic acid or acid anhydride thereof used in the epoxy (meth) acrylate acid adduct of the general formula (V) according to (A-1) of the present invention and (b) tetracarboxylic acid or its own. The molar ratio (a) / (b) with the acid dianhydride is in the range of 0.01 to 10, preferably 0.1 to 3.0. If the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight cannot be obtained, and in the photosensitive resin composition using (A-1), alkali developability, heat resistance, solvent resistance, and pattern shape Etc. are deteriorated, which is not preferable. The smaller the molar ratio (a) / (b), the greater the alkali solubility and the larger the molecular weight.

Further, the epoxy (meth) acrylate adduct of the general formula (V) according to (A-1) of the present invention preferably has a weight average molecular weight (Mw) of 2000 to 10000, preferably 3000 to 7000. It is particularly preferable to be between. If the weight average molecular weight (Mw) is less than 2000, the adhesion of the pattern during development of the photosensitive resin composition using (A-1) cannot be maintained, pattern peeling occurs, and the weight average molecular weight (Mw) ) Exceeds 10,000, the development residue and the residual film of the unexposed portion are likely to remain. Further, it is desirable that the acid value of (A-1) is in the range of 30 to 200 mgKOH / g. If this value is less than 30 mgKOH / g, alkaline development of the photosensitive resin composition using (A-1) cannot be performed well, or special development conditions such as strong alkali are required, and if it exceeds 200 mgKOH / g (A). -1) is not preferable because the alkaline developer permeates the photosensitive resin composition using the same material too quickly and peeling development occurs.

The epoxy (meth) acrylate adduct of the general formula (V) used in the present invention is described in known methods such as JP-A-8-278629 and JP-A-2008-9401 by the above steps. It can be manufactured by the method of. First, as a method of reacting the epoxy compound of the general formula (IV) with the unsaturated group-containing monocarboxylic acid, for example, the epoxy group of the epoxy compound and this molar amount of the unsaturated group-containing monocarboxylic acid are added to the solvent. In the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), there is a method of heating and stirring at 90 to 120 ° C. while blowing air to react. Next, as a method of reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound which is the reaction product, a predetermined amount of the epoxy acrylate compound, the acid dianhydride and the acid monoanhydride is added to the solvent, and a catalyst (odor) is added. There is a method of reacting by heating and stirring at 90 to 130 ° C. in the presence of tetraethylammonium oxide, triphenylphosphine, etc.).

（但し、Ｘは一般式（Ｉ）に示したものと同義である。） (A-2) in the photosensitive resin composition for a touch panel of the present invention is described as an unsaturated group-containing alkali-soluble resin represented by the general formula (I) (hereinafter, referred to as "alkali-soluble resin of the general formula (I)". To do). The method for producing the alkali-soluble resin of the general formula (I) is shown in detail below.
First, an unsaturated group-containing monocarboxylic acid is reacted with an epoxy compound having two epoxycycloalkyl groups in one molecule represented by the general formula (VI), and preferably (meth) acrylic acid is reacted. Obtain an epoxy (meth) acrylate compound. Examples of the unsaturated group-containing monocarboxylic acid compound include compounds obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride, in addition to acrylic acid and methacrylic acid. Be done.

(However, X is synonymous with the one shown in the general formula (I).)

（但し、Ｒ₁、Ｘは一般式（Ｉ）に示したものと同義である。） For the reaction of such an epoxy compound with (meth) acrylic acid, a known method can be used. For example, about 2 mol of (meth) acrylic acid is added to 1 mol of the epoxy compound having two epoxy groups. Do using. The reactants obtained by this reaction are described in, for example, Japanese Patent Application Laid-Open No. 4-355450. The reactant obtained by this reaction is a diol compound containing a polymerizable unsaturated group, and is an epoxy (meth) acrylate compound represented by the following general formula (VII).

(However, R ₁ and X are synonymous with those shown in the general formula (I).)

The X of the epoxy compound having two epoxycycloalkyl groups in the molecule represented by the general formula (VI) is a divalent organic having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside. It is a group. As a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside, a divalent hydrocarbon group and a divalent group having a carboxyl group at one or two ends of the hydrocarbon group Examples thereof include a group, and the hydrocarbon group referred to here may have an ether-bonding oxygen atom or an ester bond inside. Examples of such a divalent hydrocarbon group include a linear hydrocarbon group such as a methylene group, an ethylene group, a propylene group, an isopropylidene group, a sec-butylene group, a methylisobutylene group, a hexylene group, a decylene group and a dodecylene group. Can be mentioned.

（但し、ｇは１〜２０の整数を表し、ｈは２〜２０の整数を表し、ｉは０〜１０の整数を表し、ｊは１〜２０の整数を表し、ｋは０〜１８の整数を表す。） 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 formulas (VIII) to (XIV), and at the same time. Two or more types may be used together. It is preferably an epoxy compound represented by the general formula (XI) or (XII) from the viewpoint of easy availability and physical characteristics of the cured product, and it is preferable that g is 1, h is 5 and i is 1.

(However, 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. Represents.)

Synthesis of epoxy (meth) acrylate compound as represented by the above general formula (VII), subsequent addition reaction of polyvalent carboxylic acid or its anhydride, and polymerizable unsaturated group having reactivity with carboxyl group. In the production of the alkali-soluble resin of the general formula (I), the reaction is usually carried out in a solvent using a catalyst, if necessary, by reacting a monofunctional epoxy compound or the like having the above. Here, the reaction conditions such as the solvent and the catalyst to be used are not particularly limited, but for example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the main component of the reaction solvent, and such a solvent is used. Examples thereof include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether-based or ester-based solvents such as jiglime, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and cyclohexanone. , A ketone solvent such as diisobutylketone is preferable. Further, it is preferable to use a catalyst in the reaction between the carboxyl group and the epoxy group, and the catalyst to be used includes, for example, ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine and tris (2,6-). Known substances such as phosphines such as dimethoxyphenyl) phosphine can be used. These are described in detail in JP-A-9-325494.

（但し、Ｒ₁は水素原子またはメチル基を示す。Ｘは単結合又は内部にヘテロ元素を含んでいてもよい炭素数１〜２０の２価の有機基を示し、Ｙは４価のカルボン酸残基を表し、Ｗは、それぞれ独立して水素原子又は−ＯＣ−Ｌ−（ＣＯＯＨ）ｓ（但し、Ｌは２価又は３価のカルボン酸残基を表し、ｓは１又は２の整数を表す）を表し、ｎは１つ１つの分子において各々１〜２０の整数であり、一般式（XV）のアルカリ可溶性樹脂は、これらの混合物である。つまり、一般式（ＸＶ）におけるｎは１〜２０の平均値を示す。） As the second reaction, the epoxy (meth) acrylate compound (c) obtained by reacting the epoxy compound with the (meth) acrylic acid is reacted with the acid components (a) and (b), and the general formula (XV) is used. A polymerizable unsaturated group-containing alkali-soluble resin represented by (hereinafter, referred to as "alkali-soluble resin of general formula (XV)") can be obtained.

(However, R ₁ represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside, and Y represents a tetravalent carboxylic acid. Represents a residue, W represents a hydrogen atom or -OC-L- (COOH) s (where L represents a divalent or trivalent carboxylic acid residue, and s is an integer of 1 or 2). Represents), where n is an integer of 1 to 20 in each molecule, and the alkali-soluble resin of the general formula (XV) is a mixture of these. That is, n in the general formula (XV) is 1. Shows the average value of ~ 20.)

The acid component used for synthesizing the alkali-soluble resin of the general formula (XV) is a polyvalent acid component capable of reacting with a hydroxyl group in the epoxy (meth) acrylate compound molecule, and is (a) a dicarboxylic acid or It is necessary to use tricarboxylic acid or its acid monoanhydride in combination with (b) tetracarboxylic acid or its acid dianhydride. These (a) dicarboxylic acid or tricarboxylic acid or its acid monoanhydride and (b) tetracarboxylic acid or its acid dianhydride are used in the epoxy (meth) acrylate acid adduct of the general formula (V). A group of compounds similar to those of the above can be mentioned.
The method of reacting the epoxy (meth) acrylate compound (c) with the acid components (a) and (b) is not particularly limited, and is described in, for example, JP-A-9-325494. A known method for reacting an epoxy (meth) acrylate compound with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ° C. can be adopted. Preferably, it is used with an epoxy (meth) acrylate compound (c), a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride (a) thereof, or a tetracarboxylic acid dianhydride (b) so that the end of the compound becomes a carboxyl group. It is desirable to react so that the molar ratio is (c) :( a) :( b) = 1: 0.01 to 1.0: 0.2 to 1.0. Here, a quantitative explanation will be given by taking the case of using (b) acid monoanhydride and (c) acid dianhydride as an example. A diol compound containing a polymerizable unsaturated group (epoxy (meth) acrylate compound) Reaction so that the molar ratio [(c) / [(a) / 2+ (b)]] of the amount of the acid component to (c) [(a) / 2+ (b)] is 0.5 to 1.0. It is desirable to let it. When the molar ratio exceeds 1.0, the content of the diol compound containing an unreacted polymerizable unsaturated group increases, and there is a concern that the stability of the alkali-soluble resin composition over 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 the unreacted acid dianhydride increases to be alkali-soluble. There is concern that the stability of the resin composition may decrease over time. The molar ratio of each component (c), (a) and (b) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the above general formula (XV). ..

（但し、Ｒ₁は水素原子又はメチル基を示し、Ｒ₂は炭素数２〜１０の２価の炭化水素基を示し、ｍは０又は１である。）
上記一般式（ＸＶ）のカルボキシル基に対する上記一般式（ＸVI）で表される不飽和基含有エポキシ化合物のエポキシ基のモル比は上記一般式（Ｉ）で表されるアルカリ可溶性樹脂の光反応の感度（重合性二重結合の量の大小による）や酸価を調整する目的で任意に変更できる。一般式（ＸVI）のモル数は、（ａ）成分のモル数と（ｂ）成分のモル数の２倍の合計モル数に対して、９０％以下であればアルカリ現像性の付与が可能であり、光パターニング性を有する感光性樹脂組成物に用いることができる。また、光反応の感度向上効果を付与したい場合は、１０％以上にすることが必要であるので、１０〜９０％であることが好ましい。さらに、３０〜７０％であることがより好ましい。また、使用する一般式（Ｉ）のアルカリ可溶性樹脂の酸価は、２０〜１８０であることが好く、３０〜１２０であることがより好ましい。 As the third reaction, a 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) to be alkaline-soluble of the general formula (I). Get the resin.

(However, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and 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) is the photoreaction of the alkali-soluble resin represented by the general formula (I). It can be arbitrarily changed for the purpose of adjusting the sensitivity (depending on the amount of polymerizable double bond) and the acid value. If the number of moles of the general formula (XVI) is 90% or less of the total number of moles, which is twice the number of moles of the component (a) and the number of moles of the component (b), alkali developability can be imparted. Yes, it can be used for photosensitive resin compositions having photopatterning properties. Further, when it is desired to impart the effect of improving the sensitivity of the photoreaction, it is necessary to set it to 10% or more, so it is preferably 10 to 90%. Further, it is more preferably 30 to 70%. Further, 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.

Further, the polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin of the above general formula (I) of the present invention measured by gel permeation chromatography (GPC) is usually 1000 to 100,000 and 2000 to 20000. Is preferable. If the weight average molecular weight is less than 1000, the adhesion of the pattern during alkaline development may decrease. If the weight average molecular weight exceeds 100,000, it becomes difficult to obtain a solution viscosity of the photosensitive resin composition suitable for coating, and it takes too much time for alkaline development, which is not preferable.

Examples of the photopolymerizable monomer having at least one ethylenically unsaturated bond (B) in the photosensitive resin composition for a touch panel of the present invention include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). (Meta) acrylic acid esters having a hydroxyl group such as acrylate and 2-ethylhexyl (meth) acrylate, 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, trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erislitol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa. (Meta) acrylates, phosphazene alkylene oxide-modified hexa (meth) acrylates, caprolactone-modified dipentaerythritol hexa (meth) acrylates and other (meth) acrylic acid esters, and aromatics to increase the refractive index of cured products. Examples thereof include those having a plurality of group rings, for example, monomers having a polycyclic aromatic skeleton such as a biphenyl skeleton and a naphthaline skeleton, and monomers containing an element having a large atomic refraction such as S. Specifically, bisphenol A can be mentioned. Diacrylate of ethylene oxide, 2,2'-di (2-acryloxyethoxy) -1,1'-binaphthalene can be mentioned. One or more of these can be used, and it is preferable to include monomers having a plurality of aromatic rings or polycyclic aromatic skeletons and monomers containing elements such as S. Further, as the photopolymerizable monomer having at least one ethylenically unsaturated bond, one having two or more photopolymerizable groups and capable of cross-linking the molecules of the unsaturated group-containing alkali-soluble resin is used. Is preferable. (B) The photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxy group.

Examples of the (C) photopolymerization initiator in the photosensitive resin composition for a touch panel of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, and trichloro. Acetphenones such as acetophenone and p-tert-butyl acetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like. Benzoin ethers, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) )-4,5-Diphenylbimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl- 5-Styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) -1,3,4-Oxaziazole and other halomethyldiazole compounds, 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) ) -1,3,5-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, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Halomethyl-S-triazine compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O) -Benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2- Oxime-O-acetate, 1- (4-methylsulfanylphenyl) butane-1-one Oxime-O-acetate, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ]-, 1- (0-Acetyloxyme), Metanone, (9-Ethyl-6-Nitro-9H-Carbazole-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] -, O-Acetyloxime, Metanone, (2-Methylphenyl) (7-Nitro-9,9-Dipropyl-9H-Fluoren-2-yl)-, Acetyloxime, Etanone, 1-[7-(2-Methyl) Benzoyl) -9,9-dipropyl-9H-fluoren-2-yl]-,1- (O-acetyloxime), etanone, 1- (-9,9-dibutyl-7-nitro-9H-fluoren-2-yl) Il)-, O-acyloxime compounds such as 1-O-acetyloxime, benzyldimethyl ketal, thioxanthone, 2-chlorothioxime, 2,4-diethylthioxime, 2-methylthioxime, 2- Sulfur compounds such as isopropylthioxanson, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumeper oxide and the like. Examples thereof include organic peroxides, thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. Among these, it is preferable to use o-acyloxime compounds from the viewpoint that a highly sensitive photosensitive resin composition can be easily obtained. Among them, the line width is controlled when a transparent film pattern is obtained by photolithography. From the viewpoint of ease, it is particularly preferable to use the compound of the general formula (XVII). Further, two or more kinds of these photopolymerization initiators can be used. The photopolymerization initiator referred to in the present invention is used in the sense of including a sensitizer.

In formula (XVII), R7 is an alkyl group having 1 to 20 carbon atoms (which may be linear or branched, may be substituted with one or more hydroxyl groups, and has one or more in the middle of the alkyl chain. It may have an oxygen atom. It may also have a substituent such as a cycloalkyl group having 5 to 8 carbon atoms or a phenyl group), a cycloalkyl group having 5 to 8 carbon atoms, or a carbon number of carbon atoms. 2 to 20 alkanoyl groups or benzoyl groups (which may be substituted with alkyl or phenyl groups having 1 to 6 carbon atoms), phenyl groups (substituted with alkyl groups, phenyl groups or halogen atoms having 1 to 6 carbon atoms) May be). Further, R8 is an alkanoyl group having 2 to 12 carbon atoms (which may be substituted with one or more halogen atoms or a cyano group), and an alkalinyl having 4 to 6 carbon atoms whose double bond is not conjugated to a carbonyl group. Group, 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 (1 to 6 carbon atoms having 1 or more carbon atoms). It may be substituted with an alkyl group or a halogen atom of). A preferable R7 is an alkyl group having 1 to 20 carbon atoms (it may be linear or branched, and may have a substituent such as a cycloalkyl group having 5 to 8 carbon atoms or a phenyl group). A preferred R8 is an alkanoyl group having 2 to 12 carbon atoms (which may be substituted with one or more halogen atoms or a cyano group) or a benzoyl group (an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group). It may be replaced with).

(D) in the photosensitive resin composition for a touch panel of the present invention is at least one kind of metal oxide particles selected from aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium, but of zirconium or titanium. Oxides can be preferably used, with titanium oxide being particularly preferred. The shape of these metal oxide particles is not particularly limited, and those having an average particle size of 5 to 200 nm by the dynamic scattering method (cumulant method) can be used, and more preferably 10 to 100 nm. If it is less than 5 nm, agglutination is likely to occur and it becomes difficult to disperse uniformly, or when a cured product requires a large amount of dispersant, the desired physical properties cannot be obtained, and curing exceeding 200 nm None of this is good because the haze of the membrane is large.

In the photosensitive resin composition for a touch panel of the present invention, (E) is an interface having a surface tension of 20 to 28 mN / m when measured with a propylene glycol monomethyl ether acetate solution having a concentration of (E) of 0.1% by mass. It is an activator, and examples thereof include a fluorine-based surfactant and a silicone-based surfactant. A surfactant having a surface tension of 20 to 28 mN / m in a 0.1 mass% propylene glycol monomethyl ether acetate solution is preferable because it can ensure flatness after forming a high refractive index layer even if there are irregularities between the electrode patterns. , Fluorine-based surfactants are particularly preferable.

（但し、Ｒ_９は分子内にヘテロ原子を含んでもよい炭素数１〜１０の炭化水素基であり、不飽和結合、エポキシ基（３，４−エポキシシクロヘキシル基のような脂環式エポキシ基を含む）、オキセタニル基、イソシアネート基、アミノ基又はウレイド基を有する反応性基を置換基として有してもよい、Ｒ₁₀はそれぞれ独立に水素原子、炭素数１〜４のアルキル基を示し、Ｒ₁₁はそれぞれ独立に炭素数１〜４のアルキル基を示し、ｔは１〜３である。好ましいＲ₉としては、エポキシ基、オキセタニル基、イソシアネート基又はウレイド基を置換基として有する炭素数１〜１０の炭化水素基であり、好ましいＲ₁₀、Ｒ₁₁としてはメチル基又はエチル基である。） Examples of the (F) silane compound in the photosensitive resin composition for a touch panel of the present invention include a silane compound of the general formula (XVIII), and specific compounds include, for example, 3- (glycidyloxy) propyltri. Examples thereof include methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane and the like. A ureido group-containing silane compound such as 3-ureidopropyltriethoxysilane is preferable because the adhesion between the electrode pattern and the cured film which is a high refractive index layer can be improved.

(However, R ₉ is a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule, and has an unsaturated bond and an epoxy group (an alicyclic epoxy group such as a 3,4-epoxycyclohexyl group). Included), a reactive group having an oxetanyl group, an isocyanate group, an amino group or a ureido group may be used as a substituent, and R ₁₀ independently represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, respectively. ₁₁ each independently represents an alkyl group having 1 to 4 carbon atoms, and t is 1 to 3. Preferred R ₉ has 1 to 1 carbon atoms having an epoxy group, an oxetanyl group, an isocyanate group or a ureido group as a substituent. It is a hydrocarbon group of ₁₀ , and preferred R ₁₀ and R ₁₁ are a methyl group or an ethyl group.)

In the photosensitive resin composition of the present invention, it is preferable to use a solvent in addition to the above (A) to (F) to adjust the viscosity. 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- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, 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, tri Glycol ethers such as ethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethyl lactate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, Examples thereof include esters such as propylene glycol monoethyl ether acetate, and by dissolving and mixing them, a uniform solution-like composition can be obtained.

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 the physical properties of the cured film. Specific compounds include, for example, 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, polyhydric alcohol glycidyl ether, and polyhydric carboxylic acid. Glycidyl ester, polymer containing glycidyl (meth) acrylate as a unit, bis (3,4-epoxycyclohexyl) methane, 2,2'-bis (3,4-epoxycyclohexyl) propane, 3,4-epoxycyclohexane Alicyclic epoxy compounds such as carboxylic acid (3', 4'-epoxycyclohexyl) methyl, 1,2-ethylene-bis (3,4-epoxycyclohexylcarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate , Polyfunctional epoxy compound having a dicyclopentadiene skeleton (for example, HP7200 series manufactured by DIC), 1,2-epoxy-4- (2-oxylanyl) cyclohexane addition of 2,2-bis (hydroxymethyl) -1-butanol Examples thereof include products (for example, "EHPE3150" manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (for example, "NISSO-PB / JP-100" manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton. As these components, a compound having an epoxy equivalent of 90 to 500 g / eq and a number average molecular weight of 100 to 5000 is preferable.

In addition, the photosensitive resin composition of the present invention may contain additives such as a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a leveling agent, and an antifoaming agent, if necessary. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, and the like, and examples of the plasticizer include dibutylphthalate, dioctylphthalate, and phosphorus. Examples thereof include tricresyl acid acid, and examples of the leveling agent and antifoaming agent include silicone-based, fluorine-based, and acrylic-based compounds.

Regarding the preferable composition ratio of each component (A) to (F) in the photosensitive resin composition, (B) is 5 to 100 parts by mass and (C) is (A) with respect to 100 parts by mass of (A). ) And (B) are 0.1 to 40 parts by mass with respect to 100 parts by mass. Further, (D) is 1 to 60% by mass in the solid content of the composition (including the monomer component that becomes a solid content by the photocuring reaction). Further, (E) is 0.001 to 5% by mass, preferably 0.001 to 1.0% by mass in the photosensitive resin composition (including the solvent). If (E) is less than 0.001% by mass, the unevenness between the electrode patterns becomes large, and there is a concern that color unevenness may occur. If (E) exceeds 5% by mass, the cured film may be repelled or uneven. Further, (F) is 0.01 to 20% by mass, preferably 0.01 to 10% by mass in the solid content of the composition (including the monomer component that becomes a solid content by the photocuring reaction). When (F) is less than 0.01% by mass, there is a concern that the adhesiveness may be deteriorated especially under high temperature and high humidity. On the other hand, if (F) exceeds 20% by weight, foreign matter may be generated in the cured film or the stability of the photosensitive resin composition with time may decrease.

The photosensitive resin composition for a touch panel of the present invention contains the above components (A) to (F) as main components. In the photosensitive resin composition solution, the components (A) to (F) are 70% by mass or more in total, preferably 80, in the solid content (including the monomer component that becomes the solid content after photocuring) excluding the solvent. It may contain% by mass, more preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 60 to 90% by mass in the photosensitive resin composition solution.

As a method of using the photosensitive resin composition for a touch panel of the present invention, a transparent conductive metal oxide for wiring formed on a substrate such as glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) A pattern is formed by applying and forming a film on a film, irradiating the coating film with ultraviolet rays through a photomask to cure the exposed part, and further developing to elute the unexposed part using an alkaline aqueous solution. A resist pattern can be formed by a photolithography method such as post-baking to have transparency and to be an insulating film between wires and a protective film for wires and the like.

As a method of applying the photosensitive resin composition solution to the substrate, any method such as a known solution immersion method, a spray method, a roller coater machine, a land coater machine, a slit coater machine, or a spinner machine is adopted. can do. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (prebaking). Pre-baking is performed by heating in an oven, a hot plate, or the like. The heating temperature and heating time in the prebake are appropriately selected according to the solvent used, and are carried out at a temperature of, for example, 60 to 110 ° C. for 1 to 3 minutes. The film thickness of the photosensitive resin composition after prebaking is preferably 0.1 to 5 μm, and if the film thickness is less than 0.1 μm, the adhesion to the substrate during alkaline development in the subsequent step is lowered. On the other hand, if the film thickness exceeds 5 μm, the flatness is lowered, and when the substrate is a transparent film, there is a concern that warpage may occur.

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

Alkaline development after exposure is performed for the purpose of removing the photosensitive resin composition in the unexposed portion, and a desired pattern is formed by this development. Examples of the developing solution suitable for this alkaline 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, and the like, and in particular, sodium carbonate, potassium carbonate, and the like. It is preferable to develop at a temperature of 23 to 27 ° C. using a weak alkaline aqueous solution containing 0.03 to 1% by mass of carbonate, and a commercially available developer or an ultrasonic cleaner is used to precisely obtain a fine image. Can be formed.

After developing in this way, heat treatment (post-baking) is performed at a temperature of 150 to 250 ° C. and conditions of 30 to 120 minutes. This post-baking is performed to obtain the desired physical properties of the cured film.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. Moreover, the evaluation of the resin in the following synthetic examples was carried out as follows unless otherwise specified.

[Solid content concentration]
A glass filter [weight: W ₀ (g)] is impregnated with 1 g of the resin solution obtained in the following synthesis example, weighed [W ₁ (g)], and heated at 160 ° C. for 2 hr, and then weight [W]. ₂ (g)] was calculated from the following equation.
Solid content concentration (% by weight) = 100 x (W _2- W ₀ ) / (W _1- W ₀ )

[Acid value]
The resin solution obtained in the following synthesis example was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator [trade name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.], and the solid content was 1 g. The amount of KOH required per area was taken as the acid value.

[Molecular weight]
Gel Permeation Chromatography (GPC) [HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 ( 1) [manufactured by Tosoh Corporation], temperature: 40 ° C, speed: 0.6 ml / min], measured with standard polystyrene [PS-oligoform kit manufactured by Tosoh Corporation], weight average molecular weight (Mw) Is the value obtained.
[surface tension]
Using an automatic plate method surface tension meter (Model: CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.), the surface tension of a propylene glycol monomethyl ether acetate solution having a surfactant concentration of 0.1% by mass was measured under the conditions of a temperature of 23 ° C. and a humidity of 50%. It was measured.

[Synthesis Example 1]
In a 500 ml four-necked flask with a return condenser, 0.23 mol of bisphenol fluoride type epoxy compound, 0.46 mol of acrylic acid, 161.0 g of propylene glycol monomethyl ether acetate and 0.48 g of tetraethylammonium bromide (TEAB) were charged, and 100 The reaction was carried out by stirring at ~ 105 ° C. under heating for 20 hours. Next, 0.08 mol of 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 0.18 mol of 1,2,3,6-tetrahydrophthalic anhydride were placed in the flask at 120 to 125 ° C. The mixture was stirred under heating for 6 hours to obtain an alkali-soluble resin solution 1 represented by the general formula (V). The solid content concentration of the obtained resin solution was 55.6 wt%, the acid value (in terms of solid content) was 101 mgKOH / g, and the Mw by GPC analysis was 2400.
The bisphenol fluorene type epoxy compound used is a compound of the general formula (IV), where A is a fluorene-9,9-diyl group and R _{3 to} R ₆ are hydrogen atoms. Similar compounds were used in Synthesis Examples 2 and 3.

[Synthesis Example 2]
In a 500 ml four-necked flask with a return condenser, 0.23 mol of bisphenol fluoride type epoxy compound, 0.46 mol of acrylic acid, 161.0 g of propylene glycol monomethyl ether acetate and 0.48 g of tetraethylammonium bromide (TEAB) were charged, and 100 The reaction was carried out by stirring at ~ 105 ° C. under heating for 20 hours. Next, 0.12 mol of 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 0.12 mol of 1,2,3,6-tetrahydrophthalic anhydride were placed in the flask at 120 to 125 ° C. The mixture was stirred under heating for 6 hours to obtain an alkali-soluble resin solution 2 represented by the general formula (V). The solid content concentration of the obtained resin solution was 55.6 wt%, the acid value (in terms of solid content) was 103 mgKOH / g, and the Mw by GPC analysis was 3600.

[Synthesis Example 3]
0.23 mol of bisphenol fluorene type epoxy compound, 0.46 mol of acrylic acid, 156.0 g of propylene glycol monomethyl ether acetate and 0.48 g of tetraethylammonium bromide (TEAB) were charged in a 500 ml four-necked flask with a return condenser, 100. The reaction was carried out by stirring at ~ 105 ° C. under heating for 20 hours. Next, 0.15 mol of 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 0.005 mol of 1,2,3,6-tetrahydrophthalic anhydride were placed in the flask at 120 to 125 ° C. The mixture was stirred under heating for 6 hours to obtain an alkali-soluble resin solution 3 represented by the general formula (V). The solid content concentration of the obtained resin solution was 55.6 wt%, the acid value (in terms of solid content) was 93 mgKOH / g, and the Mw by GPC analysis was 8300.

[Synthesis Example 4]
3,4-Epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate 0.34 mol, acrylic acid 0.68 mol, propylene glycol monomethyl ether acetate 139.0 g and tetraethylammonium bromide (3,4-epoxy) in a 500 ml four-necked flask with a condenser TEAB) 2.15 g was charged and reacted by stirring at 100 to 105 ° C. for 20 hours under heating. Next, 0.12 mol of 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 0.27 mol of 1,2,3,6-tetrahydrophthalic anhydride were placed in a flask and heated at 120 to 125 ° C. Was stirred for 8 hours and reacted. Further, 0.28 mol of glycidyl methacrylate was charged and stirred at 100 to 105 ° C. for 8 hr to obtain an alkali-soluble resin solution 4. The solid content concentration of the obtained resin solution was 57.0 wt%, the acid value (in terms of solid content) was 82 mgKOH / g, and the Mw by GPC analysis was 3500.

[Comparative Synthesis Example 1]
51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, 38.77 g (0.22 mol) of benzyl methacrylate, 5.91 of azobisisobutyronitrile in a 1000 ml four-necked flask with a nitrogen introduction tube and a reflux tube. g and 370 g of diethylene glycol dimethyl ether were charged and polymerized by stirring at 80 to 85 ° C. under a nitrogen stream for 8 hours. Further, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of triphenylphosphine, and 0.055 g of 2,6-di-tert-butyl-p-cresol were placed in the flask, and the mixture was stirred at 80 to 85 ° C. for 16 hours to be alkali-soluble. A resin solution 5 was obtained. The solid content concentration of the obtained resin solution was 32% by mass, the acid value (in terms of solid content) was 110 mgKOH / g, and the Mw by GPC analysis was 18100.

(Preparation of photosensitive resin composition)
The photosensitive resin compositions of Example 8, Reference Examples 1 to 7 and 9 to 11 and Comparative Examples 1 to 7 were prepared by blending according to the compositions shown in Tables 1 and 2. The ingredients used in the formulation are as follows.
-Alkaline-soluble resin solution 1-5: Alkali-soluble resin solution obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Example 1-Photopolymerizable monomer Photopolymerizable monomer 1: Dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [Product name DPHA manufactured by Nippon Kayaku Co., Ltd.]
Photopolymerizable Monomer 2: 2,2'-di (2-Acryloxyethoxy) -1,1-Binaphthalene-Photopolymerization Initiator: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] [BASF product name Irgacure OXE01]
-Metal oxide dispersion: Titanium oxide dispersion of propylene glycol monomethyl ether acetate solvent with titanium oxide concentration of 19.6% by mass and dispersant of 9.3% by mass (average particle size of titanium oxide cumulant method 62 nm)
-Solvent Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA)
Solvent 2: Diethylene glycol methyl ethyl ether / surfactant Surfactant 1: Polyether-modified polydimethylsiloxane [BYK302 manufactured by Big Chemie Japan] diluted 100-fold with PGMEA to obtain a 1% by mass solution (polyether-modified polydimethyl). The surface tension when measured with a PGMEA solution having a siloxane concentration of 0.1% by mass is 25.9 mN / m).
Surfactant 2: A 1% by mass solution obtained by diluting a perfluoroalkyl group-containing oligomer [F-477 manufactured by DIC] 100-fold with PGMEA (PGMEA having a perfluoroalkyl group-containing oligomer concentration of 0.1% by mass). The surface tension when measured with a solution is 27.0 mN / m)
-Silane coupling agent Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane Silane coupling agent 2: 3-ureidopropyltriethoxysilane

The evaluation methods in which various characteristics were evaluated using the photosensitive resin composition solutions of Example 8, Reference Examples 1 to 7 and 9 to 11 and Comparative Examples 1 to 7 are shown below, and the evaluation results thereof are shown in Table 3. And 4.

(Transmittance and refractive index)
The photosensitive resin composition solution is applied and dried on a glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm, which has been degreased and washed, using a spin coater under the condition of a dry film thickness of 1.0 μm, and then photomasked. Without using a mask, a 500 W high-pressure mercury lamp was used to irradiate ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 10 seconds. After the exposure, it was developed at 23 ° C. for 60 seconds at a pressure of 0.1 MPa using a 0.4% aqueous sodium carbonate solution, and then heat-cured at 230 ° C. for 30 minutes using a hot air dryer. The transmittance and the refractive index of the glass substrate on which this cured film was formed were evaluated.
For the transmittance, the light transmittance at 400 nm was measured using a spectrophotometer (device: Nippon Denshoku SD5000). For the refractive index of ◯: 85% or more and ×: less than 85%, the refractive index of a light ray of 633 nm was measured using a prism coupler film thickness / refractometer (Model 2010 / M manufactured by Metricon).

(Developability)
The photosensitive resin composition solution was applied and dried using a spin coater on an ITO film-formed glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm, which had been degreased and washed, under conditions of a dry film thickness of 1.0 μm. After that, a photomask having an L / S (line width / space width) in a predetermined range was brought into close contact with the photomask, and an ultraviolet ray having a wavelength of 365 nm and an illuminance of 10 mW / cm ² was irradiated for 10 seconds using a 500 W high-pressure mercury lamp. After exposure, it was developed at 23 ° C. for 60 seconds at a pressure of 0.1 MPa using a 0.4% aqueous sodium carbonate solution to remove unexposed parts of the coating film, and then using a hot air dryer at 230 ° C. for 30 minutes. It was heat-cured.
The formation of fine lines of the formed resist film pattern was confirmed with a microscope and evaluated as follows.
◯: A pattern having an L / S of 15 μm / 15 μm or more is formed without residue ×: A pattern having an L / S of less than 15 μm / 15 μm is not formed, or the tailing or residue of the pattern is conspicuous.

(Evaluation of bone appearance of ITO pattern)
A polyimide tape having a width of 3 mm was attached in a stripe shape on an ITO-deposited glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm so as to have an interval of 3 mm. Next, after immersing it in a petri dish containing aqua regia for 2 minutes at room temperature, it was washed with pure water to remove the ITO film on the part where the polyimide tape was not attached, and then the polyimide tape was peeled off to form a striped ITO pattern. Was formed. On the glass substrate on which this striped ITO pattern is formed, a photosensitive resin composition solution is applied and dried using a spin coater under the condition that the dry film thickness is 1.0 μm, and then L / in a predetermined range is obtained. A photomask having S (line width / space width) was brought into close contact with the photomask, and an ultraviolet ray having a wavelength of 365 nm and an illuminance of 10 mW / cm ² was irradiated for 10 seconds using a 500 W high-pressure mercury lamp. After exposure, develop with a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa to remove unexposed areas of the coating film, and then use a hot air dryer at 230 ° C. for 30 minutes. The heat curing treatment was performed to form a cured film of the exposed portion. In the glass substrate with ITO stripe pattern on which this cured film is formed, the cured film formed portion and the non-formed portion are visually compared, and the ITO pattern can be confirmed in the non-formed portion, but the ITO pattern can be seen in the formed portion as well (the bone can be seen). It was evaluated whether the ITO pattern was not visible (no bones were visible) at the formation site.
◯: When the ITO pattern is inconspicuous and the bone is not visible due to the cured film ×: When the ITO pattern is conspicuous and the bone is clearly visible even with the cured film

(Color unevenness)
A polyimide tape having a width of 3 mm was attached in a stripe shape on an ITO-deposited glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm so as to have an interval of 3 mm. Next, after immersing it in a petri dish containing aqua regia for 2 minutes at room temperature, it was washed with pure water to remove the ITO film on the part where the polyimide tape was not attached, and then the polyimide tape was peeled off to form a striped ITO pattern. Was formed. On the glass substrate on which this striped ITO pattern was formed, the photosensitive resin composition solution was applied and dried using a spin coater under the condition that the dry film thickness was 1.0 μm, and then the photomask was not used. An ultraviolet ray having a wavelength of 365 nm and an illuminance of 10 mW / cm ² was irradiated for 10 seconds using a 500 W high-pressure mercury lamp. After exposure, develop with a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa to remove unexposed areas of the coating film, and then use a hot air dryer at 230 ° C. for 30 minutes. The heat curing treatment was performed to form a cured film of the exposed portion. In the glass substrate with ITO stripe pattern on which this cured film was formed, color unevenness due to unevenness between ITO patterns was visually evaluated.
⊚: When no color unevenness is observed ○: When color unevenness is observed in an area of 1/4 or less of the glass substrate with ITO stripe pattern △: Color unevenness is observed in an area of 1/3 or less of the glass substrate with ITO stripe pattern ×: When color unevenness is observed on the entire surface of the glass substrate with ITO stripe pattern, or when repellent or unevenness occurs on the cured film.

(Moisture resistance reliability)
The photosensitive resin composition solution is applied and dried on a glass substrate having a thickness of 1.2 mm and a size of 125 mm × 125 mm that has been degreased and washed using a spin coater under the condition of a dry film thickness of 1.0 μm, and then a photomask. Without using a mask, a 500 W high-pressure mercury lamp was used to irradiate ultraviolet rays with a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 10 seconds. After the exposure, it was developed at 23 ° C. for 60 seconds at a pressure of 0.1 MPa using a 0.4% aqueous sodium carbonate solution, and then heat-cured at 230 ° C. for 30 minutes using a hot air dryer. The glass substrate on which this cured film was formed was left to stand for 5 hours under the conditions of a temperature of 121 ° C., a humidity of 100%, and an atmospheric pressure of 2 atm. In addition, use the Super Cutter Guide manufactured by Taiyu Kikai Co., Ltd. to make cuts in the left-standing cured product so that 100 1 mm x 1 mm square squares are formed, and use cellophane tape (made by Nichiban) on the squares. ) Was attached and then peeled off. A tape peeling test was conducted.
⊚: When the cured product in the square is not peeled off at all ○: When less than 1/4 of the cured product in the square is peeled off △: Less than 1/3 of the cured product in the square X: When 1/3 or more is peeled off, or when foreign matter is generated or the stability of the photosensitive resin composition over time deteriorates.

(Heat-resistant discoloration)
After applying and drying the photosensitive resin composition solution on a degreased and washed glass plate with a thickness of 1.2 mm using a spin coater under the condition that the dry film thickness is 1.2 μm, no photomask is used. Then, the entire surface of the white film-forming glass plate similar to the above was irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 10 seconds using a high-pressure mercury lamp of 500 W. After the exposure, the developer was treated with a 0.4% aqueous sodium carbonate solution at 23 ° C. for 60 seconds at a pressure of 0.1 MPa. Then, it was heat-hardened at 230 ° C. for 30 minutes using a hot air dryer. In order to confirm the heat-resistant discoloration, heat treatment was further performed at 230 ° C. for 150 minutes, and the yellowness was measured with a spectrophotometer (device: Nippon Denshoku SD5000).

As is clear from the results of Example 8 and Reference Examples 1 to 7 and 9 to 11, when a cured film is formed on the ITO pattern using the photosensitive resin composition of the present invention, a cured film having a desired pattern is obtained. It was found that a cured film having alkali development patterning property for forming, having no visible bones in the ITO pattern, having excellent color unevenness and moisture resistance reliability, and having excellent heat-resistant discoloration property can be obtained. As in Comparative Example 1, if the specific alkali-soluble resin of the present invention is not used, a cured film having excellent patterning properties and an ITO pattern in which bones are not visible can be obtained by increasing the refractive index, but at 230 ° C. The yellowness after heating for 180 minutes exceeds 1, and only those inferior in heat-resistant discoloration can be obtained. Further, as in Comparative Example 2, if the metal oxide for high refraction is not added, the patterning property and the heat-resistant discoloration property are sufficient, but the refractive index cannot be sufficiently increased, and the bone of the ITO pattern I can't get rid of it. 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, it can be seen that color unevenness and moisture resistance reliability are lowered, respectively.

The photosensitive resin composition of the present invention can suppress a decrease in visibility due to bone visibility of a transparent conductive oxide pattern such as ITO, and is also excellent in patterning property, color unevenness, moisture resistance reliability, and heat discoloration property. It is useful as an insulating film and a protective film. It is also useful as an overcoat or insulating film with good patterning and heat resistance, and can be applied especially when it is desired to form a thin film because it can have a high refractive index, and it is applied to components of display devices such as color filters. It is possible to do.

Claims (8)

(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) Photosensitive resin for touch panel containing at least one metal oxide particle selected from aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium, (E) surfactant, and (F) silane compound. It is a composition, and the component (E) is contained in the photosensitive resin composition in an amount of 0.001 to 5% by mass, and the component (F) becomes a solid content after photocuring of the photosensitive resin composition. A photosensitive resin composition for a touch panel, which is contained in an amount of 0.01 to 20% by mass.

(However, R ₁ represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside, and Y represents a tetravalent carboxylic acid. Indicates a residue, Z represents a hydrogen atom or a substituent represented by the following general formula (II), G represents a hydrogen atom or a substituent represented by the following general formula (III), and n represents 1 to 20. Shows the average value of.)

(However, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, L represents a divalent or trivalent carboxylic acid residue, and m is 0. Or 1; p and q are 0 or 1 or 2, respectively, and p + q is 1 or 2.)

(However, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and m represents 0 or 1.) Further, with respect to (A-1) a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid, (a) a dicarboxylic acid or a tricarboxylic acid or an acid thereof. The photosensitive resin composition for a touch panel according to claim 1, further comprising an anhydride and (b) an alkali-soluble resin obtained by reacting a tetracarboxylic acid or an acid dianhydride thereof. ( B) is 5 to 100 parts by mass with respect to 100 parts by mass of (A-2) or 100 parts by mass of (A-2) and (A-1), and (C) is 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of (A-2) and (B) or 100 parts by mass of the total amount of (A-2), (A-1) and (B) The photosensitive resin composition for a touch panel according to claim 1 or 2, wherein the solid content (D) is 1 to 60% by mass. The components (E) are surfactants having a surface tension of 20 to 28 mN / m as measured by a propylene glycol monomethyl ether acetate solution having a concentration of the component (E) of 0.1% by mass, claims 1 to 3. The photosensitive resin composition according to any one of. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (F) is a silane compound having a functional group of any one of an epoxy group, an oxetanyl group, an isocyanate group, and a ureido group. The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (F) is a silane compound having a ureido group. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6. A touch panel having the cured film according to claim 7.