TWI830897B - Photosensitive resin composition,cuered film thereof,and display device with that film - Google Patents

Abstract

The present invention provides a photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a display device having the cured film. The photosensitive resin composition is suitable for applications including gas-generating devices with low gas generation. Protective film, light-shielding film, tinted film, etc. The photosensitive resin composition of the present invention contains the following components (A) to (D) as essential components: (A) a polymerizable unsaturated group-containing alkali-soluble resin of the general formula (1), (B) having at least three A photopolymerizable monomer with an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a solvent.

Description

Photosensitive resin composition, cured film obtained by curing the photosensitive resin composition, and display device having the cured film

The present invention relates to a photosensitive resin composition containing a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure, a cured film obtained by curing the photosensitive resin composition, and a composition containing the cured film. Ingredients for touch screens and color filters.

Conventionally, a transparent cured film (hereinafter also referred to as "protective film") as a protective layer was formed on the surface of a color filter used to manufacture a color liquid crystal display (LCD). The purpose of forming the protective film of the color filter is to flatten the unevenness between the pixels of the color filter; to improve the durability of the color filter against heat treatment and chemical treatment in subsequent steps; Improve the reliability of color LCD displays, etc. As a protective film for color filters, it is required to be excellent in transparency, chemical resistance, adhesion, hardness, flatness, heat resistance, and electrical reliability.

On the other hand, as a method of forming a protective film, there is a method of forming a protective film on the front surface by thermal curing, and a method of forming a protective film by a photodevelopment method. The formation method of the protective film can be selected according to the characteristics that the protective film should have and whether patterning is required during the design process of the panel design and processing steps of the color filter. Here, as the characteristics of the protective film that are important when formed by a photodevelopment method, on the premise that it can have development characteristics that can form a desired protective film pattern, it must have transparency, chemical resistance, and tightness. Compatibility, hardness and electrical reliability.

For example, as transparency, the protective film is required to have no absorption in the visible light wavelength range so as not to impair the color characteristics of the color filter. As chemical resistance, the protective film is required to have stability against acids, alkalis, solvents, etc. used in subsequent steps. As for the adhesion, when manufacturing a liquid crystal display screen, the substrate is sometimes bonded on the protective film, so it is required that even if the base of the protective film in the said part is a glass substrate or indium tin oxide (ITO) The substrate and molybdenum/aluminum/molybdenum (MAM) substrate will not peel off. As hardness, from the viewpoint of durability of the protective film, high hardness is required. For electrical reliability, it is required that the protective film maintains insulation and that impurities contained in the protective film do not contaminate the liquid crystal.

Among the required characteristics of the protective film, as LCD panels become more functional, wide viewing angles and high-speed response are required, and a display method similar to the In-plane Switching (IPS) mode is gradually being used. , the requirements have become more stringent. In a display mode such as the IPS mode, if gaseous or liquid components or water generated or exuded from the color filter layer enter the liquid crystal layer through the protective layer, the concentration of moisture or ionic impurities in the liquid crystal layer increases, or Formation of bubbles in the liquid crystal layer may lead to poor display. Therefore, it is of course necessary to prevent the impurity components from passing through. Furthermore, gas generated from the protective film in direct contact with the liquid crystal layer is directly related to display defects, so low gas generation is particularly important.

Furthermore, after the protective film is formed, problems arise in the LCD panel manufacturing process such as the photo-alignment treatment of the alignment film of the liquid crystal, or in the reduction of external light in various display devices including organic electroluminescence (EL). impact issues. Therefore, in addition to ensuring transparency (high transmittance) as a protective film, there are cases where the protective film is required to have the ability to absorb short-wavelength ultraviolet light that does not contribute to color display.

[Problem to be solved by the invention] It is desired to have a photosensitive resin composition that can form an appropriate protective film pattern by a photodevelopment method while fully maintaining characteristics such as transparency, chemical resistance, adhesion, and hardness. Sufficiently reduce gas generation that affects electrical reliability. In addition, in color resists for forming red, green, and blue (RGB) pixels, black resists for forming light-shielding films, etc., there is also a demand for a resist that not only has the necessary characteristics but also has low gas generation properties. Also excellent in the case of cured film.

The present invention was made in view of the above problems, and an object thereof is to provide a photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a display device having the cured film. The flexible resin composition can be suitably used for colored films including protective films and light-shielding films that generate less gas. [Technical means to solve problems]

The present inventors conducted research in order to solve the problems in the photosensitive resin composition for light-shielding film applications, and found that a specific coloring material is preferable as a light-shielding component of the photosensitive resin composition for target light-shielding film applications. The present invention was completed.

The photosensitive resin composition of the present invention contains the following components (A) to (D) as essential components: (A) a polymerizable unsaturated group-containing alkali-soluble resin of the general formula (1); (B) having at least three A photopolymerizable monomer with an ethylenically unsaturated bond; (C) a photopolymerization initiator; and (D) a solvent.

[Chemical 1]

(In formula (1), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms, and part of the bonded hydrogen atoms can be an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and l is respectively is independently a number from 0 to 3. G is a substituent represented by the general formula (2) or the general formula (3), and Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or is represented by the general formula (4) The substituent represented by general formula (4), and at least one is a substituent represented by general formula (4). n is a number with an average value of 1 to 20.)

[Chemicalization 2]

[Chemical 3]

(In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group or aryl aryl group having 2 to 20 carbon atoms. Bivalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

[Chemical 4]

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

The cured film of the present invention is formed by curing the photosensitive resin composition.

The display device of the present invention has the cured film. [Effects of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a display device having the cured film. The photosensitive resin composition can be suitably used for gas-containing gases. Protective films, light-shielding films, tinted films, etc. that produce less.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In addition, in the present invention, when the first decimal place is 0 regarding the content of each component, the expression after the decimal point may be omitted.

The polymerizable unsaturated group-containing alkali-soluble resin of the component (A) represented by the general formula (1) of the present invention is obtained by mixing an epoxy compound (a-1) having two glycidyl ether groups with The reaction product of the (meth)acrylic acid derivative reacts with dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), and tetracarboxylic acid or its acid dianhydride (c).

In addition, the polymerizable unsaturated group-containing alkali-soluble resin is characterized in that the epoxy compound used as the raw material is an epoxy compound that can contain several oxyalkylene groups in one molecule. Ar in the general formula (1) is carbon. A compound with an aromatic hydrocarbon group of 6 to 14.

Preferable examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a divalent naphthyl group and a phenylene group in which part of the hydrogen atoms may be substituted with an alkyl group or the like. Here, (A) the polymerizable unsaturated group-containing alkali-soluble resin of the present invention is preferably one in which both Ar bonded to the fluorine group in the general formula (1) are naphthyl groups (having a bis-naphthol fluoride skeleton) or Both are phenylene groups (having a bisphenol fluorine skeleton), and more preferably, the two Ar bonded to the fluorine group are both naphthyl groups. The reason for this is that the gas is generated when a cured film (coating film) hardened by (A) alkali-soluble resin containing a polymerizable unsaturated group in which both Ar bonded to the fluorine group are naphthyl groups. The amount is small. In addition, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and refers to one or both of them.

[Chemistry 5]

(In formula (1), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms, and part of the bonded hydrogen atoms can be an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and l is respectively is independently a number from 0 to 3. G is a substituent represented by the general formula (2) or the general formula (3), and Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or is represented by the general formula (4) The substituent represented by general formula (4), and at least one is a substituent represented by general formula (4). n is a number with an average value of 1 to 20.)

[Chemical 6]

[Chemical 7]

(In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group or aryl aryl group having 2 to 20 carbon atoms. Bivalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

[Chemical 8]

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

A method for producing the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (1) will be described in detail.

First, an epoxy compound (a-1) represented by the general formula (5) and having a bisnaphthol quintilde skeleton or a bisphenol quintildene skeleton which may have several oxyalkylene groups in one molecule (hereinafter also referred to as "Epoxy compound (a-1)") reacts with either or both of the (meth)acrylic acid derivatives represented by the general formula (6) or the general formula (7) to obtain (meth)acrylic acid Epoxy ester.

[Chemical 9]

(In formula (5), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms, and part of the bonded hydrogen atoms can be an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and l is respectively Independently a number from 0 to 3.)

[Chemical 10]

[Chemical 11]

(In formula (6) and formula (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group or aryl aryl group having 2 to 20 carbon atoms. Bivalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

A known method can be used for the reaction between the epoxy compound (a-1) and the (meth)acrylic acid derivative. For example, Japanese Patent Application Laid-Open No. 4-355450 describes that by using about 2 moles of (meth)acrylic acid per 1 mole of an epoxy compound having two epoxy groups, a compound containing Polymerizable unsaturated diol compound. In the present invention, the compound obtained by the reaction is the polymerizable unsaturated group-containing diol (d) represented by the formula (8) (hereinafter, also simply referred to as "the compound represented by the general formula (8)"). Diol (d)").

[Chemical 12]

(In formula (8), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms, and part of the bonded hydrogen atoms can be an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. G is substituted by the general formula (2) or the general formula (3) group, R ₁ is each independently an alkylene group having 2 to 4 carbon atoms, and l is each independently a number from 0 to 3.)

[Chemical 13]

[Chemical 14]

(In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group or aryl aryl group having 2 to 20 carbon atoms. Bivalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

Synthesis of the diol (d) represented by the general formula (8) and subsequent reaction of a polycarboxylic acid or its anhydride to produce a polymerizable unsaturated group-containing base represented by the general formula (1) In the case of soluble resins, a catalyst is usually used in the solvent to carry out the reaction if necessary.

Examples of solvents include: cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; diglyme, ethyl carbitol acetate, butyl carbitol High-boiling ether or ester solvents such as bis alcohol acetate and propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone and diisobutyl ketone. In addition, the reaction conditions of the solvent, catalyst, etc. used are not particularly limited. For example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature is preferably used as the reaction solvent.

In addition, it is preferable to use a catalyst in the reaction between an epoxy group and a carboxyl group or a hydroxyl group. Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride; Phosphines such as phenylphosphine and tris(2,6-dimethoxyphenyl)phosphine, etc.

Next, the diol (d) represented by the general formula (8) obtained by the reaction of the epoxy compound (a-1) and the (meth)acrylic acid derivative, and a dicarboxylic acid or tricarboxylic acid are Carboxylic acid or its acid monoanhydride (b) reacts with tetracarboxylic acid or its acid dianhydride (c) to obtain a carboxylic acid or its acid dianhydride (c) represented by the general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule. Alkali soluble resin.

[Chemical 15]

(In formula (1), Ar is an aromatic hydrocarbon group with 6 to 14 carbon atoms, and part of the bonded hydrogen atoms can be an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and l is respectively is independently a number from 0 to 3. G is a substituent represented by the general formula (2) or the general formula (3), and Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or is represented by the general formula (4) The substituent represented by general formula (4), and at least one is a substituent represented by general formula (4). The average value of n is 1 to 20.)

[Chemical 16]

[Chemical 17]

(In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group or aryl aryl group having 2 to 20 carbon atoms. Bivalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

[Chemical 18]

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

Next, the alkali-soluble resin represented by the general formula (1) and derived from the (meth)acrylic acid derivative represented by the general formula (6) and the general formula (7) and composed of the general formula (2) or The substituent represented by the general formula (3) will be described in detail.

General formula (2), general formula (3), general formula (6) and general formula (7) have a polymerizable unsaturated group and at least one ester bond.

[Chemical 19]

[Chemistry 20]

[Chemistry 21]

[Chemistry 22]

R ₂ shown in the general formula (2), the general formula (3), the general formula (6) and the general formula (7) is a hydrogen atom or a methyl group.

In addition, R ₃ shown in the general formula (2), the general formula (3), the general formula (6) and the general formula (7) is a divalent alkylene group or an alkyl aryl group having 2 to 10 carbon atoms. The alkylene group can be either linear or branched, and can be vinyl (ethylene), ethylidene (ethylidene), vinylene (vinylene), vinylidene (vinylidene), propylene (propylene), triethylene Methyl, propenylene, isopropylene, tetramethyl, etc. In addition, as long as the alkyl aryl group is within the range of carbon number, it can be an unsubstituted aryl group, such as o-phenylene group, m-phenylene group, p-phenylene group, methylphenylene group, ethyl phenylene group. Phenyl, n-propylphenylene, isopropylphenylene, straight-chain or branched butylphenylene, pentylphenylene, etc.

In addition, R ₄ shown in the general formula (2), the general formula (3), the general formula (6) and the general formula (7) is a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. . The saturated and unsaturated aliphatic hydrocarbon groups can be either linear or branched, and can be vinyl, ethylene, vinylene, vinylene, propenyl, trimethyl, propenyl, or isopropylene. base, tetramethyl group, etc. In addition, as long as the aromatic hydrocarbon group is within the range of carbon number, it may be an unsubstituted form, such as o-phenylene group, m-phenylene group, p-phenylene group, methylphenylene group, ethylphenylene group, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, pentylphenylene, etc., and as long as the carbon number does not exceed the range, they can also be substituted by two to four substituents. In addition, the aliphatic hydrocarbon group may also be interrupted by an unsaturated bond, an ether bond, or an ester bond.

In addition, p is a number from 0 to 10. When synthesizing the alkali-soluble resin represented by the general formula (1), the average value of p is preferably a number from 0 to 5, and more preferably the average value of p is a number from 0 to 2. . When the average value of p is within the above range, the distribution can be suppressed from being spread over a wide range, and therefore sufficient curability as a cured film can be imparted without degrading the resin performance.

The acid component used to synthesize the alkali-soluble resin represented by the general formula (1) is a polybasic acid component that can react with the hydroxyl group in the diol (d) molecule represented by the general formula (8), and it is necessary to use two diols in combination. Carboxylic acid or tricarboxylic acid or their acid monoanhydride (b) and tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, the carboxylic acid residue may also contain a bond containing a hetero element such as -O-, -S-, or carbonyl group.

Examples of dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides (b) include: chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or Tricarboxylic acids, or their acid monoanhydrides, etc.

Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid , glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and other acid monoanhydrides, and dicarboxylic or tricarboxylic acids with optional substituents introduced Carboxylic acid monoanhydrides, etc. In addition, examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include: cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norborneol Acid monoanhydrides such as alkanedicarboxylic acids and dicarboxylic acids or tricarboxylic acids having optional substituents introduced therein. Examples of aromatic dicarboxylic acids or acid monoanhydrides of tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid, and trimellitic acid, and dicarboxylic acids or compounds in which an optional substituent is introduced. Acid monoanhydride of tricarboxylic acid.

Among the acid monoanhydrides of dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, and more preferred are Succinic acid, itaconic acid, tetrahydrophthalic acid. Among dicarboxylic acids and tricarboxylic acids, it is preferable to use their acid monoanhydrides. Only one type of the dicarboxylic acid or tricarboxylic acid monoanhydride may be used alone, or two or more types may be used in combination.

Examples of tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or their acid dianhydride.

Examples of chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, chain hydrocarbon tetracarboxylic acids in which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced, etc. . In addition, examples of the alicyclic tetracarboxylic acid include: cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and Alicyclic tetracarboxylic acids having introduced substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups. Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, diphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl tetracarboxylic acid, naphthalene-1 , 4,5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, etc. In addition, trimellitic anhydride aryl esters can also be used. Trimellitic anhydride aryl esters are a group of compounds produced by the method described in WO2010/074065, for example, and are structurally aromatic diols (naphthalenediol, biphenol, terphenyldiol, etc.) An acid dianhydride in the form in which two hydroxyl groups react with the carboxyl groups of two molecules of trimellitic anhydride and undergo ester bonding. Hereinafter, the compound will be described as trimellitic anhydride ester of aromatic diol.

Among the tetracarboxylic acids or their acid dianhydrides, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid are preferred, and biphenyl tetracarboxylic acid and diphenyl ether are more preferred. Tetracarboxylic acid. Moreover, among tetracarboxylic acids or acid dianhydrides thereof, it is preferable to use the acid dianhydrides thereof. Furthermore, trimellitic anhydride ester of naphthalenediol can also be preferably used. In addition, only one type of the tetracarboxylic acid or its acid dianhydride and the trimellitic anhydride ester of the aromatic diol may be used alone, or two or more types may be used in combination.

The reaction between the diol (d) represented by the general formula (8) and the acid component (b) and the acid component (c) is not particularly limited, and a known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting (meth)acrylic acid epoxy ester and tetracarboxylic dianhydride at a reaction temperature of 90°C to 140°C.

Here, in order to make the terminal of the compound a carboxyl group, it is preferable to use a diol (d) represented by the general formula (8), a dicarboxylic acid or a tricarboxylic acid or their acid monoanhydride (b), a tetracarboxylic acid or its The reaction is carried out so that the molar ratio of the acid dianhydride (c) becomes (d): (b): (c) = 1.0: 0.01 to 1.0: 0.2 to 1.0.

For example, when using acid monoanhydride (b) or acid dianhydride (c), it is preferable to use the amount of the acid component [(b)/2+(c)] relative to the polymerizable unsaturated group-containing diol ( The reaction is performed so that the molar ratio of d) [(d)/[(b)/2+(c)]] becomes 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of the unreacted polymerizable unsaturated group-containing diol does not increase, so the stability over time of the alkali-soluble resin composition can be improved. On the other hand, when the molar ratio exceeds 0.5, since the terminal of the alkali-soluble resin represented by formula (2) does not become an acid anhydride, an increase in the content of unreacted acid dianhydride can be suppressed, and therefore the alkali-soluble resin can be improved. Stability of the composition over time. In addition, the molar ratio of each component of (b), (c), and (d) may be arbitrarily set within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (2). change.

In addition, the acid value of the alkali-soluble resin represented by the general formula (1) has a preferable range of 20 mgKOH/g to 180 mgKOH/g, and preferably 40 mgKOH/g or more and 120 mgKOH/g or less. When the acid value is 20 mgKOH/g or more, residues are less likely to remain during alkaline development. When the acid value is 180 mgKOH/g or less, the alkaline developer does not penetrate too quickly, so it can Suppress peeling phenomenon. In addition, the acid value can be determined by titrating with a 1/10N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The alkali-soluble resin represented by the general formula (1) was measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Co., Ltd.) in terms of polystyrene The weight average molecular weight (Mw) is usually 1,000 to 100,000, preferably 2,000 to 20,000, and more preferably 2,000 to 6,000. When the weight average molecular weight is 1,000 or more, the reduction in pattern adhesion during alkaline development can be suppressed. In addition, when the weight average molecular weight (Mw) is less than 100,000, it is easy to adjust to the solution viscosity of the photosensitive resin composition preferred for coating, and alkaline development does not require excessive time.

Next, the photosensitive resin composition using the alkali-soluble resin represented by General Formula (1) of the present invention will be described.

In the photosensitive resin composition of the present invention, the content of component (A) is preferably 10 to 90 mass % with respect to the total mass of solid content. In addition, the content of component (B) is preferably 5 to 200 parts by mass relative to 100 parts by mass of component (A), and the content of component (C) is preferably 5 to 200 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (B). The content of is preferably 0.1 parts by mass to 30 parts by mass.

Examples of the (B) photopolymerizable monomer having at least three ethylenically unsaturated bonds in the photosensitive resin composition of the present invention include: trimethylolpropane tri(meth)acrylate, trimethylolethane Alkane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol Penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, epoxy-modified hexa(meth)acrylate of phosphazene, hexane Lactone-modified dipentaerythritol hexa(meth)acrylate and other (meth)acrylates; dendrimer-type multifunctional acrylates, etc. Only one type of the photopolymerizable monomer may be used alone, or two or more types may be used in combination.

The content of component (B) is preferably 5 to 200 parts by mass based on 100 parts by mass of component (A), more preferably 10 to 80 parts by mass based on 100 parts by mass of component (A), and still more preferably 10 parts by mass to 60 parts by mass. When the content of component (B) is 5 parts by mass or more relative to 100 parts by mass of component (A), the photoreactive functional group occupies a sufficient amount in the resin, and therefore a sufficient crosslinked structure is formed. In addition, since the acid value in the resin component is not too high, the solubility of the exposed part with respect to the alkaline developer is reduced, so that the formed pattern can be prevented from becoming thinner than the target line width, and the pattern can be prevented from being formed. missing. In addition, when the content of the component (B) is 200 parts by mass or less with respect to 100 parts by mass of the component (A), a cured film having sufficient curability can be obtained, so that the edge of the pattern can be made clear.

Examples of (C) photopolymerization initiator in the photosensitive resin composition of the present invention include: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethyl Acetophenones such as aminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone; benzophenone, 2-chlorobenzophenone, p,p'-bisdi Benzophenones such as methylaminobenzophenone; benzoin ethers such as benzoyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2-(o-chlorophenyl)- 4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenyl Biimidazole compounds such as biimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole; 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-oxadiazole 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 Azine, 2-(4-methoxystyrene)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyrene methyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1 , 3,5-triazine and other halomethyl-s-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyl acyl oxime), 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-oxime-O-acetate and other O-carboxylic acid groups Oxime compounds; benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2-methylthioxanthone, 2-iso Sulfur compounds such as propylthioanthrone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone; azobisiso Organic peroxides such as butyronitrile, benzyl peroxide, cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; triethanolamine , triethylamine and other tertiary amines, etc. In addition, only one type of the photopolymerization initiator may be used alone, or two or more types may be used in combination.

Particularly in the case of a photosensitive resin composition containing a coloring material, it is preferable to use O-carboxyloxime compounds (including ketoximes). As a specific compound group, there are O-acyl oxime-based photopolymerization initiators represented by general formula (9) or general formula (10). Among the above compound groups, when using a coloring material with a high pigment concentration or forming a light-shielding film pattern, it is preferable to use an O-carboxyloxime with a molar absorption coefficient at 365 nm of 10000 L/mol･cm or more. It is a photopolymerization initiator. In addition, the "photopolymerization initiator" mentioned in the present invention is used in the sense of including a sensitizer.

[Chemistry 23]

(In formula (9), R ₅ and R ₆ are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an alkyl group having 4 to 12 carbon atoms. Heterocyclic group, R ₇ is an alkyl group with 1 to 15 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an arylalkyl group with 7 to 20 carbon atoms. Here, the alkyl group and the aryl group can be from 1 to 20 carbon atoms. An alkyl group of 10, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen substitution, and the alkylene group may include an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, The alkyl group can be any linear, branched or cyclic alkyl group.)

[Chemistry 24]

(In formula (10), R ₈ and R ₉ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group, cycloalkylalkyl group having 4 to 10 carbon atoms, or Alkylcycloalkyl, or phenyl which may be substituted by an alkyl group having 1 to 6 carbon atoms. R ₁₀ is each independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and the alkyl group A part of the -CH ₂ - group in the group or alkenyl group may be substituted by an -O- group. Furthermore, a part of the hydrogen atoms in the group of R ₈ to R ₁₀ may also be substituted by a halogen atom.)

The content of component (C) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 25 parts by mass relative to 100 parts by mass of the total amount of component (A) and (B). When the content of component (C) is 0.1 parts by mass or more, the photopolymerization speed is moderate, so that the decrease in sensitivity can be suppressed. In addition, when the content of component (C) is 30 parts by mass or less, line widths faithful to the mask can be reproduced, and the edges of the pattern can be made clear.

(D) Examples of the solvent contained in the photosensitive resin composition include: methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol mono Alcohols such as butyl ether, 3-hydroxy-2-butanone, diacetone alcohol; terpenes such as α-terpineol or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-methyl Ketones such as 2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol Alcohol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether Ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate , 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. By dissolving and mixing them, a uniform solution-like composition can be prepared. In order to obtain necessary characteristics such as coatability, the solvents may be used alone or two or more thereof may be used in combination. The amount of the solvent changes depending on the target viscosity, but is preferably 60% by mass to 90% by mass in the photosensitive resin composition solution.

The photosensitive resin composition contains a coloring material as the (E) component. When used as a resist for a light-shielding film, the component (E) is one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials, and is preferably a black organic pigment. and/or mixed color organic pigments. In addition, the average secondary particle diameter of the black organic pigment and/or mixed color organic pigment is preferably 20 nm to 500 nm. The average secondary particle diameter of the black organic pigment and the mixed color organic pigment can be measured by the accumulation method using a particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) using a dynamic light scattering method.

The content of the coloring material as the component (E) can be arbitrarily determined according to the desired shading degree, but is preferably 1 to 80 mass % with respect to the solid content in the photosensitive resin composition. When using organic pigments or carbon-based inorganic In the case of pigments, the content is more preferably 20% by mass to 60% by mass.

Examples of the black organic pigment as the component (E) include perylene black, aniline black, cyanine black, lactamine black, and the like. Examples of mixed-color organic pigments include: selected from azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, and dioxazines Pigments, threne pigments, perylene pigments, perinone pigments, quinoline yellow pigments, diketopyrrolopyrrole pigments, thioindigo pigments and other organic pigments are mixed and analogously blackened. finished paint. As light-shielding materials, carbon black, chromium oxide, iron oxide, titanium black, etc. are included. As the component (E), a pigment suitably surface-treated according to the function of the intended photosensitive resin composition may be used. In addition, only one type of the component (E) may be used alone, or two or more types may be used in combination.

Examples of organic pigments that can be used as the component (E) include pigments with the following numbers in the Color Index (Color Index) names, but are not limited thereto. Pigment red (pigment red) 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment orange (pigment orange) 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment yellow (pigment yellow) 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment green (pigment green) 7, 36, 58, etc. Pigment blue (pigment blue) 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment violet (pigment violet) 19, 23, 37, etc.

In addition, the coloring material as the component (E) is preferably dispersed in the solvent (D) together with the dispersant (F) in advance to prepare a coloring material dispersion, and then blended into the photosensitive resin composition. Here, since the solvent used for dispersion becomes a part of the component (D), any solvent included in the component (D) can be used. Among the components (D), propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butyl acetate, etc. are preferred.

The content of component (E) is preferably 1 to 80 mass%, and more preferably 30 to 60 mass% with respect to the total solid content of the photosensitive resin composition of the present invention. In addition, the said solid content means the component other than (D) component in a photosensitive resin composition. The solid component also includes component (B) that becomes a solid component after photocuring. When the component (E) is 1 mass % or more, it is easy to set the desired light-shielding property. In addition, when the content of component (E) is 80% by mass or less, desired developing characteristics and film-forming ability can be obtained.

The (F) dispersant may be any known compound used for dispersing coloring materials (pigments) (compounds commercially available as dispersants, dispersion wetting agents, dispersion accelerators, etc.), etc., without particular limitation. .

Examples of the dispersant as component (F) include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). Especially in terms of adsorption of coloring materials, the dispersant preferably has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary amino group, a secondary amino group, or a tertiary amino group, and has an amine value of 1 mgKOH/g to 100 mgKOH/g, a cationic polymer dispersant with a number average molecular weight in the range of 1,000 to 100,000. The blending amount of the dispersant is preferably 1% to 35% by mass, and more preferably 2% to 25% by mass relative to the coloring material. In addition, high-viscosity substances such as resins generally have the effect of stabilizing dispersion, and substances that do not have the ability to promote dispersion are not considered dispersants. However, use is not limited to the purpose of stabilizing dispersion.

In addition, when preparing the coloring material dispersion, not only the dispersant (F) but also a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is co-dispersed, thereby making it easy to prepare the coloring material dispersion. A photosensitive resin composition that maintains high exposure sensitivity, has good adhesion during development, and is less likely to cause residue problems. In the coloring material dispersion, the content of component (A) is preferably 2 to 20 mass%, and more preferably 5 to 15 mass%. When the content of component (A) is 2 mass % or more, co-dispersion effects such as improved sensitivity, improved adhesion, and reduced residue can be obtained. In addition, when the component (A) is 20 mass % or less, a cured film (coating film) in which the component (E) is uniformly dispersed can be obtained.

The coloring material dispersion is prepared by co-dispersing the coloring material dispersion with the component (A) (when the component (A) is co-dispersed when preparing the coloring material dispersion), the component (B), the component (C), It can be mixed with the remaining component (E) to prepare a photosensitive resin composition for light-shielding films.

Moreover, the photosensitive resin composition of this invention can use other resin components polymerized or hardened by light or heat together as needed. Examples of other resin components include: epoxy resins such as novolak epoxy resins and bisphenol-type epoxy resins derived from novolaks such as phenol novolac and cresol novolac; and combining the epoxy resin with (methyl ) Alkali-soluble resin (except component (A)) obtained by the reaction of acrylic acid and acid anhydride, copolymers with (meth)acrylic acid and/or (meth)acrylate esters, and carboxyl groups in the copolymer containing Alkali-soluble resin obtained by reacting epoxy (meth)acrylate, etc.

The photosensitive resin composition of the present invention may be blended with additives such as hardeners, hardening accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, defoaming agents, surfactants, and coupling agents as needed. .

Examples of hardeners include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyanodiamine, Lewis acid complex compounds, and the like that contribute to hardening of epoxy resin. Examples of hardening accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organic metal compounds, imidazoles, and the like that help accelerate the hardening of epoxy resins. Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiol, hindered phenol compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of filler materials include: fiberglass, silica, mica, alumina, etc. Examples of defoaming agents or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include: 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 -Ureidopropyltriethoxysilane, etc.

The cured film (coating film) of the present invention can be formed by a photodevelopment method using the photosensitive resin composition of the present invention. The method is as follows: first, apply a photosensitive resin composition solution on the surface of a substrate, dry the solvent (pre-baking), place a photoresist on the coating film and irradiate ultraviolet rays to harden the exposed part, and then use an alkali. The aqueous solution is developed to elute the unexposed portion to form a pattern, and post-baking is performed as post-hardening. Here, examples of the substrate to which the photosensitive resin composition solution is applied include glass, transparent films (for example, polycarbonate, polyethylene terephthalate, polyether ester, etc.).

The substrate may be a transparent substrate or a substrate other than a transparent substrate. Examples of transparent substrates coated with photosensitive resin compositions include not only glass substrates, but also transparent films (for example, polycarbonate, polyethylene terephthalate, polyether terephthalate, etc.) on which ITO is evaporated or patterned Or a transparent electrode substrate such as gold.

As a method for coating the photosensitive resin composition solution on the substrate, not only the well-known solution dipping method and the spray method can be used, but also a roll coater, a land coater machine (land coater machine), and a slit coater can be used. Or the method of rotating the machine, etc. After coating to a desired thickness using the above method, the solvent is dried (prebaked) to form a film. In addition, prebaking is performed by heating using an oven, a hot plate, etc. The heating temperature and heating time in the prebaking can be appropriately selected according to the solvent used. For example, the heating temperature and heating time are performed at a temperature of 60°C to 110°C for 1 minute to 3 minutes.

Exposure after prebaking is performed using an ultraviolet exposure device, and exposure is performed through a photoresist, whereby only the portion of the resist corresponding to the pattern is exposed to light. The exposure device and its exposure irradiation conditions should be appropriately selected and light sources such as ultra-high-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, far ultraviolet lamp, etc. should be used for exposure, thereby photohardening the photosensitive resin composition in the coating film.

As the radiation used for exposure, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. can be used. The wavelength range of the radiation is preferably 250 nm to 450 nm. In addition, as a developer suitable for the alkaline development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. The developer can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. The development temperature is preferably 20°C to 35°C, and a commercially available developing machine or ultrasonic cleaning machine can be used to accurately form a fine image. In addition, after alkaline development, water washing is usually performed. As the development treatment method, spray development method, spray development method, dip development method, puddle (liquid coating) development method, etc. can be applied.

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 the development. Examples of the developer suitable for the alkaline development include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, and the like. In particular, sodium carbonate containing 0.03% to 1% by weight is preferably used. , potassium carbonate and other carbonates are developed at a temperature of 23°C to 27°C, and fine images can be accurately formed using commercially available developing machines or ultrasonic cleaning machines.

After developing in the above manner, heat treatment (post-baking) is performed at 180°C to 250°C for 20 minutes to 100 minutes. However, when the heat resistance of a substrate or the like used for film formation is low, the formulation of the composition can be designed so that post-baking conditions can be set to 80°C to 180°C for 30 minutes to 100 minutes. The post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. Like prebaking, this is performed by heating using an oven, a hot plate, or the like. The patterned resin film of the present invention is formed through each of the above steps using the photodevelopment method. [Example]

Hereinafter, embodiments of the present invention will be described in detail based on Examples and Comparative Examples. However, the present invention is not limited to the Examples and Comparative Examples.

First, description will be given starting with a synthesis example of a polymerizable unsaturated group-containing alkali-soluble resin containing a structure represented by general formula (1). Unless otherwise specified, the evaluation of the resin in the synthesis example is as follows. Proceed normally. Regarding various measuring equipment, when the same model is used, the name of the equipment manufacturer is omitted from the second place onwards. In addition, in Example 1 and Example 2, the glass substrate which carried out the same process was used for the glass substrate used for preparation of the board|substrate with the cured film for measurement.

[Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)], and heated at 160°C for 2 The weight [W ₂ (g)] after 1 hour is calculated using the following equation (1). Solid content concentration (weight%) =100×(W ₂ -W ₀ )/(W ₁ -W ₀ ) (1)

[Epoxy equivalent] After the resin solution was dissolved in dioxane, an acetic acid solution of tetraethylammonium bromide was added, and a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) was used, and a 1/10N-perchloric acid solution was used. Calculate it by titration.

[acid value] The resin solution was dissolved in dioxane and titrated with a 1/10N-KOH aqueous solution using a potentiometric titration device "COM-1600" to obtain the result.

[Molecular weight] Colloidal permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 pieces) + TSKgelSuperH-3000 (1 piece) + TSKgelSuperH- 4000 (1 piece) + TSKgelSuperH-5000 (1 piece) (manufactured by Tosoh Co., Ltd.), temperature: 40°C, speed: 0.6 ml/min) was measured and used as a standard polystyrene (Tosoh (Tosoh) Tosoh Co., Ltd. PS-oligomer set) to calculate the weight average molecular weight (Mw).

In addition, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows. BPFE: Bisphenol-type epoxy resin (Epoxy resin in which Ar is a benzene ring and l is 0 in the general formula (5), and the epoxy equivalent is 256) BNFE: bis-naphthol-type epoxy resin (Epoxy resin in which Ar is a naphthalene ring and l is 0 in the general formula (5), and the epoxy equivalent is 281) HOA-HH: 2-propenyloxyethylhexahydrophthalic acid (Light Acrylate HOA-HH (N), manufactured by Kyoeisha Chemical Co., Ltd.) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride BTDA: benzophenone tetracarboxylic dianhydride BTANE: Trimellitic anhydride ester of naphthalenediol (DHN-D1, manufactured by Honshu Chemical Industry Co., Ltd.) THPA: 1,2,3,6-tetrahydrophthalic anhydride TPP: Triphenylphosphine TBPC: 2,6-di-tert-butyl-p-cresol AA: acrylic MAA: methacrylic acid MMA: methyl methacrylate CHMA: cyclohexyl methacrylate AIBN: Azobisisobutyronitrile GMA: glycidyl methacrylate PGMEA: propylene glycol monomethyl ether acetate

[Synthesis example 1] Put BPFE (46.64 g, 0.09 mol), AA (13.12 g, 0.18 mol), TPP (0.24 g), and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C~ The mixture was stirred at 105° C. for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was added to adjust the solid content to 50 mass%.

Next, BPDA (13.45 g, 0.05 mol) and THPA (6.96 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble solution containing a polymerizable unsaturated group. Resin solution (A)-1. The solid content concentration of the obtained resin solution was 57.3% by mass, the acid value (in terms of solid content) was 96 mgKOH/g, and the Mw analyzed by GPC was 3600.

[Synthesis example 2] Put BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat at 100°C~ The mixture was stirred at 105° C. for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was added to adjust the solid content to 50 mass%.

Next, BPDA (12.49 g, 0.04 mol) and THPA (6.46 g, 0.04 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble solution containing a polymerizable unsaturated group. Resin solution (A)-2. The solid content concentration of the obtained resin solution was 56.9 mass%, the acid value (solid content conversion) was 90 mgKOH/g, and the Mw analyzed by GPC was 4000.

[Synthesis example 3] Put BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat at 100°C~ The mixture was stirred at 105° C. for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was added to adjust the solid content to 50 mass%.

Next, BPDA (8.74 g, 0.03 mol) and THPA (10.34 g, 0.07 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble solution containing a polymerizable unsaturated group. Resin solution (A)-3. The solid content concentration of the obtained resin solution was 56.9 mass%, the acid value (solid content conversion) was 90 mgKOH/g, and the Mw analyzed by GPC was 2600.

[Synthesis Example 4] Put BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat at 100°C~ The mixture was stirred at 105° C. for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was added to adjust the solid content to 50 mass%.

Then, BPDA (16.49 g, 0.06 mol) and THPA (0.26 g, 0.002 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble solution containing a polymerizable unsaturated group. Resin solution (A)-4. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (in terms of solid content) was 83 mgKOH/g, and the Mw analyzed by GPC was 7000.

[Synthesis Example 5] Put BNFE (30.53 g, 0.05 mol), HOA-HH (29.33 g, 0.11 mol), TPP (0.14 g), and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler. The reaction product was obtained by stirring at 105°C to 105°C for 12 hours. Then, PGMEA (20.00 g) was added to adjust the solid content to 50 mass%.

Next, BPDA (8.00 g, 0.03 mol) and THPA (4.14 g, 0.03 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain alkali-soluble polymerizable unsaturated group-containing Resin solution (A)-5. The solid content concentration of the obtained resin solution was 54.6 mass%, the acid value (solid content conversion) was 63 mgKOH/g, and the Mw analyzed by GPC was 5300.

[Synthesis example 6] Put BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat at 100°C~ The mixture was stirred at 105° C. for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was added to adjust the solid content to 50 mass%.

Next, BTDA (13.68 g, 0.04 mol) and THPA (6.46 g, 0.04 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain alkali-soluble polymerizable unsaturated group-containing Resin solution (A)-6. The solid content concentration of the obtained resin solution was 54.6% by mass, the acid value (in terms of solid content) was 92 mgKOH/g, and the Mw analyzed by GPC was 4100.

[Synthesis Example 7] Put BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat at 100°C~ The mixture was stirred at 105° C. for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was added to adjust the solid content to 50 mass%.

Next, BTANE (21.58 g, 0.04 mol) and THPA (6.46 g, 0.04 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 7 hours to obtain alkali-soluble polymerizable unsaturated group-containing Resin Solution (A)-7. The solid content concentration of the obtained resin solution was 54.6 mass%, the acid value (solid content conversion) was 91 mgKOH/g, and the Mw analyzed by GPC was 5000.

[Synthesis example 8] Put MAA (51.65 g, 0.60 mol), MMA (36.04 g, 0.36 mol), CHMA (40.38 g, 0.24 mol), and AIBN (5.91 g), and PGMEA (360 g), and polymerized by stirring at 80°C to 85°C under nitrogen flow for 8 hours. Furthermore, GMA (61.41 g, 0.43 mol), TPP (2.27 g) and TBPC (0.086 g) were put into the flask, and stirred at 80°C to 85°C for 16 hours to obtain an alkali-soluble resin containing a polymerizable unsaturated group. Solution (A)-8. The solid content concentration of the obtained resin solution was 35.7% by mass, the acid value (in terms of solid content) was 50 mgKOH/g, and the Mw analyzed by GPC was 19,600.

(Alkali-soluble resin solution) (A)-1: Alkali-soluble resin solution obtained in Synthesis Example 1 (A)-2: Alkali-soluble resin solution obtained in Synthesis Example 2 (A)-3: Alkali-soluble resin solution obtained in Synthesis Example 3 (A)-4: Alkali-soluble resin solution obtained in Synthesis Example 4 (A)-5: Alkali-soluble resin solution obtained in Synthesis Example 5 (A)-6: Alkali-soluble resin solution obtained in Synthesis Example 6 (A)-7: Alkali-soluble resin solution obtained in Synthesis Example 7 (A)-8: Alkali-soluble resin solution obtained in Synthesis Example 8

(Photopolymerizable monomer) (B): DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

(Photopolymerization initiator) (C): Irgacure OXE-02 (Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-triazol-3-yl]-, 1 -(O-acetyl oxime), manufactured by BASF, "Irgacure" is a registered trademark of this company)

(solvent) (D)-1: Propylene glycol monomethyl ether acetate (D)-2: 3-methoxy-3-methyl-1-butyl acetate

(surfactant) BYK-330 PGMEA solution (solid content 1.0%) (manufactured by BYK-Chemie)

[Example 1] The components (A) to (F) were prepared in the proportions shown in Table 1 to prepare photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2. (D)-1 in the solvent column does not include PGMEA (same as (D)-1) in an unsaturated group-containing resin solution (alkali-soluble resin solution containing a polymerizable unsaturated group), or light-shielding pigment dispersion The amount of solvent in the liquid and the solvent in the surfactant. In addition, all numerical values in Table 1 represent mass %.

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 Alkali soluble resin solution (A)-1 23.8 15.3 (A)-2 29.1 twenty four 15.4 (A)-3 twenty four (A)-4 24.3 (A)-5 25 (A)-6 25 (A)-7 25 (A)-8 38.2 24.6 Photopolymerizable monomer (B) 5.8 10.7 2.9 5.8 10.7 5.8 5.8 5.8 5.8 5.8 5.8 10.7 Photopolymerization initiator (C) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Solvent (D)-1 57.4 61 55 57.2 60.9 57.2 56.9 56.2 56.2 56.2 43 51.7 (D)-2 12 12 12 12 12 12 12 12 12 12 12 12 surfactant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 total 100 100 100 100 100 100 100 100 100 100 100 100

[evaluation] The following evaluation was performed using the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2.

(Preparation of cured film (coating film)) Using a spin coater, the photosensitive resin composition shown in Table 1 was applied to a surface that had been previously irradiated with a low-pressure mercury lamp with a wavelength of 254 nm so that the film thickness after heat curing treatment was 1.5 μm. A 50 mm × 50 mm glass substrate "EAGLE XG" (manufactured by Corning Corporation) (hereinafter referred to as "glass substrate") with an illumination intensity of 1000 mJ/cm ² and its surface cleaned, indium tin The oxide evaporated glass substrate (hereinafter referred to as "ITO substrate") and the molybdenum-aluminum alloy evaporated substrate (hereinafter referred to as "MAM substrate") were prebaked at 90°C for 1 minute using a hot plate to produce Coated board. Then, a high-pressure mercury lamp with a wavelength of 365 nm and an illumination of 30 mW/cm ² was used to irradiate ultraviolet light of 100 mJ/cm ² to perform a photohardening reaction. Then, hardening treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain cured films (coating films) of Examples 1 to 10 and Comparative Examples 1 and 2.

The cured films (coating films) containing the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 obtained above were evaluated for the following items, and the results are shown in Table 2. Their evaluation method is as follows. In addition, regarding high-temperature and high-humidity-resistant adhesion and chemical-resistant adhesion, not only cured films (coating films) on glass substrates were evaluated, but also cured films (coating films) produced on ITO substrates and MAM substrates. Make an evaluation.

(Film thickness measurement) The cured films (coating films) of Examples 1 to 10 and Comparative Examples 1 and 2 were measured using a stylus type step shape measuring device "P-17" (manufactured by KLA-Tencor Co., Ltd.). film thickness.

[High temperature and high humidity resistance adhesion] (evaluation method) The cured film (coating film) produced on the glass substrate, ITO substrate, and MAM substrate was left to stand for 5 hours under the conditions of temperature 121°C, humidity 100%, and air pressure 2 atm. Then, a cross cut peeling test was performed by using a Super Cutter Guide (manufactured by Taiyu Machinery Co., Ltd.) to cut incisions on the substrate to form 100 1 mm×1 mm A square grid, attach cellophane tape (manufactured by Nichiban Co., Ltd.) to the grid and then peel it off.

(Evaluation criteria) ○: None of the cured film (coating film) in the mesh has been peeled off △: Less than 1/3 of the cured film (coating film) in the mesh is peeled off ×: More than 1/3 peeled off

[Chemical Resistant Adhesion] (evaluation method) The cured film (coating film) produced on the glass substrate, ITO substrate, and MAM substrate was immersed in a petri dish containing N-methyl-2-pyrrolidone at 60°C for 2 minutes, and then treated with pure water. Wash and wipe away moisture. Then, a cross-cut peeling test was performed by using a Super Cutter Guide to cut incisions on the substrate to form 100 square grids of 1 mm × 1 mm, and attaching cellophane tape to the grids Peel it off later.

(Evaluation criteria) ○: None of the cured film (coating film) in the grid has been peeled off △: Less than 1/3 of the cured film (coating film) in the mesh is peeled off ×: More than 1/3 peeled off

[Coating film hardness 1] (evaluation method) In accordance with the test method of Japanese Industrial Standards (JIS)-K5600-5-4, a pencil hardness testing machine was used to apply a load of 750 g to the cured film (coating film) produced on the glass substrate. ) is expressed as the highest pencil hardness when no damage occurs. The pencil used is "Mitsubishi Hi-Uni" (manufactured by Mitsubishi Pencil Co., Ltd.). In addition, this evaluation was performed as an index of the resistance of the coating film surface to force (scratches) in the transverse direction.

(Evaluation criteria) ○：3H or more △：2H ×：H or less

[Coating Film Hardness 2] (Evaluation Method) The cured film (coating film) produced on the glass substrate was measured using a microfilm hardness meter "HM2000" (manufactured by Fischer Instruments). A Vickers indenter was used as the indenter, and a load of 5 mN/μm ² was applied at a load speed of 0.25 mN/sec. After holding for 1 second, the load was removed and the Martens hardness was measured (according to the International Organization for Standardization). , ISO)14577). This evaluation was performed as an index of the resistance of the cured film (coating film) surface to force (pressure) in the longitudinal direction. In addition, "Martens hardness" refers to the hardness calculated from the load-penetration depth curve.

(Evaluation criteria) ○: 65 N/mm ² or more △: 60 N/mm ² or more and less than 65 N/mm ² ×: less than 60 N/mm ²

[Transmittance 1] (evaluation method) Using a transmittance meter "SPECTRO PHOTOMETER SD 5000" (manufactured by Nippon Denshoku Industries Co., Ltd.), the cured film produced with a film thickness of 2 μm on the glass substrate "EAGLE XG" (Coating film) for transmittance measurement.

(Evaluation criteria) ○: Transmittance at wavelength 400 nm is over 95% △: The transmittance at a wavelength of 400 nm is more than 90% and less than 95% ×: less than 90%

[Transmittance 2] Using a transmittance meter "SPECTRO PHOTOMETER SD 5000", the transmittance of a cured film (coating film) produced with a film thickness of 3 μm on a glass substrate "EAGLE XG" was measured.

(Evaluation criteria) ○: Transmittance at wavelength 340 nm is less than 20% △: The transmittance at a wavelength of 340 nm is more than 20% and less than 65% ×：More than 65%

[gas generating property] (evaluation method) The cured film (coating film) produced on the glass substrate "EAGLE Differential Thermal Analysis (TG/DTA)) "EXSTAR 6000" (manufactured by Hitachi High-Tech Science Co., Ltd.) measured 10 mg of the powdery cured film (coating film) obtained thermogravimetric loss. The measurement conditions were preprocessing at 120°C for 30 minutes in the atmosphere and then maintaining at 230°C for 3 hours. The gas generating property was evaluated by the weight reduction rate, and the weight reduction rate was calculated based on the weight reduction before and after heating at 230°C.

(Evaluation criteria) ◎: Weight reduction rate is less than 3% ○: Weight reduction rate is 3% or more and less than 7% △: Weight reduction rate is 7% or more and less than 15% ×: Weight reduction rate is more than 15%

[Water absorbency] (evaluation method) The cured film (coating film) produced on the glass substrate "EAGLE XG" is left to stand at a constant temperature and humidity of 40°C and 90% humidity for 24 hours, and then ground with a scraper, etc. , the thermogravimetric loss of 10 mg of the obtained powdery cured film (coating film) was measured using a differential thermal analysis-thermogravimetric measuring device (TG/DTA) "EXSTAR 6000". The measurement conditions were to raise the temperature to 120°C at 10°C/min in a nitrogen atmosphere and maintain the temperature for 1 hour. Water absorbency was evaluated using the weight reduction rate.

(Evaluation criteria) ○: Weight reduction rate is less than 2% △: Weight reduction rate is more than 2% and less than 5% ×: Weight reduction rate is more than 5%

[Development characteristics] (Preparation of evaluation sample) The photosensitive resin composition shown in Table 1 was applied to a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after heat hardening treatment was 1.5 μm. On the EAGLE XG, pre-bake for 1 minute at 90°C using a hot plate. Then, set the photoresist to an exposure gap of 150 μm, and use a high-pressure mercury lamp with a wavelength of 365 nm and an illumination of 30 mW/ ^cm to irradiate ultraviolet light of 100 mJ/ ^cm to perform a photohardening reaction on the photosensitive part.

Next, use 0.05% potassium hydroxide aqueous solution or 0.2% sodium carbonate aqueous solution at 23°C to develop the exposed cured film (coating film) for 60 seconds under a pressure of 0.1 MPa, and then wash it with water to remove the cured film (coating film). The unexposed portion of the film) is removed. Then, heat hardening processing was performed at 230°C for 30 minutes using a hot air dryer to obtain cured films (patterns) of Examples 1 to 10 and Comparative Examples 1 and 2.

(Evaluation methods and evaluation criteria) The formation of fine lines in the obtained pattern was confirmed using an optical microscope and evaluated in the following three stages. ○: A pattern with L/S of 15 μm/15 μm or more was formed without residue. △: A pattern with L/S of 30 μm/30 μm or more was formed without residue. ×: No pattern with L/S less than 50 μm/50 μm is formed, or there are obvious curls or residues of the pattern.

[Table 2] Example Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 High temperature and humidity resistance Glass base board ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 △ △ ITO substrate ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 △ △ MAM substrate ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 × × Chemical resistance and tightness Glass base board ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 ○ △ ITO substrate ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 △ △ MAM substrate ○ ○ ○ ○ △ ○ ○ ○ 〇 〇 × × Film hardness 1 ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 ○ ○ 2 ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 ○ ○ transmittance 1 ○ ○ △ ○ ○ ○ △ ○ △ △ ○ ○ 2 △ 〇 〇 〇 〇 〇 〇 〇 〇 〇 × × Gas generating property ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ × water absorbency ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 △ △ Development characteristics ○ ○ ○ ○ ○ ○ ○ ○ 〇 〇 ○ ○

[Example 2] The components (A) to (F) were prepared in the proportions shown in Table 3 to prepare photosensitive resin compositions containing light-shielding pigment dispersions of Examples 11 to 16 and Comparative Examples 11 to 13. (D)-1 in the solvent column does not include PGMEA (same as (D)-1) in an unsaturated group-containing resin solution (alkali-soluble resin solution containing a polymerizable unsaturated group), or light-shielding pigment dispersion The amount of solvent in the liquid and the solvent in the surfactant. In addition, all numerical values in Table 3 represent mass %.

(Optical pigment dispersion) (E)-1: PGMEA dispersion containing 15.0% by mass of lactam-based black pigment and 4.5% by mass of polymer dispersant (solid content: 19.5%) (E)-2: PGMEA dispersion containing 25.0 mass% of resin-coated carbon-based black pigment and 5.0 mass% of polymer dispersant (30.0% solid content)

[table 3] Example Comparative example 11 12 13 14 15 16 11 12 13 Alkali soluble resin solution (A)-1 14.5 15 23.8 (A)-2 14.6 15.1 twenty four (A)-8 23.3 24.1 38.2 Photopolymerizable monomer (B) 3.6 3.7 5.8 3.6 3.7 5.8 3.6 3.7 5.8 Photopolymerization initiator (C) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Solvent (D)-1 33.6 44.3 57.4 33.5 44.2 57.2 24.8 35.2 43 (D)-2 12 12 12 12 12 12 12 12 12 Opacifying pigment dispersion (E)-1 28.2 28.2 28.2 (E)-2 7.1 twenty four 7.1 twenty four 7.1 twenty four surfactant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 total 100 100 100 100 100 100 100 100 100

[evaluation] The following evaluation was performed using the photosensitive resin compositions of Examples 11 to 16 and Comparative Examples 11 to 13. Table 4 shows their evaluation results.

[Measurement of optical density] Using a spin coater, apply the photosensitive resin composition shown in Table 3 on a 125 mm × 125 mm glass substrate so that the film thickness after heat hardening is 1.1 μm, and pre-bake at 90°C for 1 minute. . Then, heat hardening processing was performed at 230°C for 30 minutes using a hot air dryer to obtain cured films (coating films) of Examples 11 to 16 and Comparative Examples 11 to 13. Next, the optical density (optical density, OD) of the obtained cured film (coating film) was measured using a Macbeth transmission density meter, and the optical density per unit film thickness was used for evaluation.

[Measurement of volume resistivity] (Measurement method) Using a spin coater, each photosensitive resin composition shown in Table 3 was coated on a 100 mm × 100 mm glass substrate with a thickness of 1.2 mm on which Cr was evaporated so that the film thickness after heat hardening treatment was 3.5 μm. The parts other than the electrodes are pre-baked at 90°C for 1 minute. Then, heat hardening processing was performed at 230°C for 30 minutes using a hot air dryer to obtain cured films (coating films) of Examples 11 to 16 and Comparative Examples 11 to 13. Then, an aluminum electrode is formed on the cured film (coating film) to prepare a substrate for volume resistivity measurement. Next, an electrometer "6517A type" (manufactured by Keithley Co., Ltd.) was used to measure the volume resistivity from an applied voltage of 1 V to an applied voltage of 10 V. In addition, the measurement was performed under the condition that the voltage was maintained at each applied voltage for 60 seconds in steps of 1 V.

[Measurement of dielectric constant] (Measurement method) Using a spin coater, each photosensitive resin composition shown in Table 3 was coated on a 100 mm × 100 mm glass substrate with a thickness of 1.2 mm on which Cr was evaporated so that the film thickness after heat hardening treatment was 3.5 μm. The parts other than the electrodes are pre-baked at 90°C for 1 minute. Then, heat hardening processing was performed at 230°C for 30 minutes using a hot air dryer to obtain cured films (coating films) of Examples 11 to 16 and Comparative Examples 11 to 13. Then, an aluminum electrode was formed on the coating film to prepare a substrate for dielectric constant measurement. Next, an electrostatic capacitance was measured from a frequency of 1 Hz to a frequency of 100,000 Hz using an electrometer (electrometer "6517A type"), and the dielectric constant was calculated based on the electrostatic capacitance.

[gas generating property] (evaluation method) Grind the cured film (coating film) produced on the glass substrate "EAGLE "The thermogravimetric loss of 10 mg of the obtained powdery cured film (coating film) was measured. The measurement conditions were preprocessing at 120°C for 30 minutes in the atmosphere and then maintaining at 230°C for 3 hours.

(Evaluation criteria) ◎: Weight reduction rate is less than 3% ○: Weight reduction rate is 3% or more and less than 7% △: Weight reduction rate is 7% or more and less than 10% ×: Weight reduction rate is more than 10%

[Measurement of elastic recovery rate of spacer] (Measurement method) Each photosensitive resin composition shown in Table 3 was applied to 125 mm using a spin coater so that the film thickness after heat hardening treatment was 3.0 μm. On a ×125 mm glass substrate "EAGLE XG", pre-bake at 90°C for 1 minute. Then, it is closely adhered to the photoresist with a dot pattern, and a high-pressure mercury lamp with a wavelength of 365 nm and an illumination of 30 mW/cm ² is used to irradiate ultraviolet rays of 100 mJ/cm ² to perform a photohardening reaction on the photosensitive part.

Next, the exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at 24° C. and a pressure of 0.1 MPa for 60 seconds to remove the unexposed portion of the cured film (coating film). Then, a heat hardening process was performed at 230° C. for 30 minutes using a hot air dryer to obtain cured films (coating films) of Examples 1 to 6 and Comparative Examples 1 to 3. The spacing characteristics of the obtained cured film (coating film) pattern were evaluated using an ultrafine hardness meter "Fischerscope HM2000Xyp" (manufactured by Fischer Instruments). Press into a 100 μm square flat indenter at a loading speed of 5.0 mN/sec. After loading to a load of 50 mN, unload at an unloading speed of 5.0 mN/sec and create a displacement curve.

The elastic recovery rate is calculated based on the following equation (2), assuming that the displacement amount under load of 50 mN is L1 and the displacement amount during unloading is L2. Elastic recovery rate (%) = (L1-L2)/L1×100 (2)

[Development characteristics] (Preparation of evaluation sample) The photosensitive resin composition shown in Table 3 was applied to a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after heat hardening treatment was 1.5 μm. On the EAGLE XG, pre-bake for 1 minute at 90°C using a hot plate. Then, set the photoresist to an exposure gap of 150 μm, and use a high-pressure mercury lamp with a wavelength of 365 nm and an illumination of 30 mW/ ^cm to irradiate ultraviolet light of 100 mJ/ ^cm to perform a photohardening reaction on the photosensitive part.

Next, use 0.05% potassium hydroxide aqueous solution or 0.2% sodium carbonate aqueous solution at 23°C to develop the exposed cured film (coating film) for 60 seconds under a pressure of 0.1 MPa, and then wash it with water to remove the cured film (coating film). The unexposed portion of the film) is removed. Then, a heat hardening process was performed at 230° C. for 30 minutes using a hot air dryer to obtain cured films (patterns) of Examples 11 to 16 and Comparative Examples 11 to 13.

(Evaluation methods and evaluation criteria) The formation of fine lines in the obtained pattern was confirmed using an optical microscope and evaluated in the following three stages. ○: A pattern with L/S of 15 μm/15 μm or more was formed without residue. △: A pattern with L/S of 30 μm/30 μm or more was formed without residue. ×: No pattern with L/S less than 50 μm/50 μm is formed, or there are obvious curls or residues of the pattern.

[Table 4] Example Comparative example 11 12 13 14 15 16 11 12 13 Optical Density (OD) 2.4 2.0 0.0 2.4 2.0 0.0 2.2 2.0 0.0 Volume resistivity [Ω･cm] 1.9E+15 1.3E+15 1.5E+16 1.9E+15 2.3E+15 1.8E+15 6.0E+15 5.7E+15 9.5E+15 Dielectric constant 4.2 14.0 3.8 3.8 12.6 3.4 5.5 18.8 3.9 Gas generation (%) ○ ○ ○ ◎ ◎ ◎ × × △ Elastic recovery rate (%) 77 73 83 78 74 82 75 70 85 Development characteristics ○ ○ ○ ○ ○ ○ ○ ○ ○

The present invention can obtain a photosensitive resin composition that can provide a cured film with high light-shielding properties and insulation properties; excellent adhesion to a substrate; and excellent elastic modulus, deformation amount, and elastic recovery rate.

[Industrial applicability] The cured film of the photosensitive resin composition of the present invention can be extremely effectively used as a component of a color filter including an organic EL element, a quantum dot display, a TFT array, a wavelength conversion element, and the like. In addition, the resin composition having a bis-naphthol-quinone skeleton is useful because it functions as a light transmission control layer that blocks ultraviolet light in a specific range.

without

without

Claims (6)

A photosensitive resin composition containing the following components (A) to (D) as essential components: (A) a polymerizable unsaturated group-containing alkali-soluble resin of the general formula (1); (B) having at least three A photopolymerizable monomer with an ethylenically unsaturated bond; (C) a photopolymerization initiator; and (D) a solvent,

In formula (1), Ar contains a naphthalene skeleton, and part of the bonded hydrogen atoms can be composed of an alkyl group with 1 to 10 carbon atoms, an aryl or arylalkyl group with 6 to 10 carbon atoms, or a ring with 3 to 10 carbon atoms. Alkyl or cycloalkylalkyl, alkoxy group with 1 to 5 carbon atoms, or halogen group substitution; R ₁ is independently an alkylene group with 2 to 4 carbon atoms, and l is independently a number from 0 to 3 ; G is a substituent represented by general formula (2) or general formula (3), Y is a tetravalent carboxylic acid residue; Z is independently a hydrogen atom or a substituent represented by general formula (4) , and more than one is a substituent represented by general formula (4); n is a number with an average value of 1 to 20;

In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkyl aryl group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group having 2 to 20 carbon atoms. Valent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10;

In formula (4), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2, and the content of component (A) is 10 mass% to 90 mass% relative to the total mass of solid components. The content of the component (B) is 5 to 200 parts by mass relative to 100 parts by mass of the component (A), and the content of the component (C) is 5 to 200 parts by mass relative to 100 parts by mass of the total amount of the component (A) and the component (B). The content of the component is 0.1 parts by mass to 30 parts by mass. The photosensitive resin composition according to claim 1, which contains (E) a coloring material. The photosensitive resin composition according to claim 2, wherein the (E) coloring material is one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials. The photosensitive resin composition according to claim 2, wherein the content of the (E) coloring material is 1 to 80 mass % with respect to the total mass of the solid content of the photosensitive resin composition. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 4. A display device having the cured film according to claim 5.