Photosensitive resin composition, cured film, and display device

Abstract

The present invention provides a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a display device having the cured film. The photosensitive resin composition is suitable for use in protective films, light-shielding films, and other colored films that generate little gas. The photosensitive resin composition of the present invention comprises the following components (A) to (D) as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group of the general formula (1), (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) a photopolymerization initiator, and (D) a solvent.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition containing an alkali-soluble resin having a specific structure and containing a polymerizable unsaturated group, a cured film formed by curing the photosensitive resin composition, and a touch screen and a color filter containing the cured film as a constituent component. Background Art

[0002] Traditionally, a transparent hardened film (hereinafter referred to as a "protective film") has been formed as a protective layer on the surface of color filters used in the manufacture of color liquid crystal displays (LCDs). The purpose of forming a color filter protective film is to: flatten the unevenness between the color filter pixels; improve the durability of the color filter against subsequent heat and chemical treatments; and enhance the reliability of the color LCD. Color filter protective films are required to exhibit excellent transparency, chemical resistance, adhesion, hardness, flatness, heat resistance, and electrical reliability.

[0003] On the other hand, as a method for forming a protective film, there are methods of forming a protective film on the front surface by thermal curing, and methods of forming a protective film by photolithography. The method of forming the protective film can be selected during the design of the color filter panel and the design of the processing steps, based on the properties that the protective film should have and whether patterning is required. Here, as the properties of the protective film that should be considered when forming by photolithography, it is necessary to have transparency, chemical resistance, tightness, hardness, and electrical reliability, as long as it has development properties that can form the desired protective film pattern.

[0004] For example, as transparency, the protective film is required to have no absorption in the visible light wavelength range so as not to damage the color characteristics of the color filter. As chemical resistance, the stability of the protective film relative to the acid, alkali and solvent used in the subsequent process is required. As adhesion, when making a liquid crystal display, sometimes a substrate is bonded to the protective film, so that even if the base of the protective film at the position is a glass substrate, indium tin oxide (ITO) substrate and molybdenum / aluminum / molybdenum (MAM) substrate, it is required that no peeling occurs. As hardness, from the perspective of the durability of the protective film, high hardness is required. As electrical reliability, the protective film is required to maintain insulation and impurities contained in the protective film will not contaminate the liquid crystal.

[0005] Among the required properties for the protective film, wide viewing angles and high-speed response are required as LCD panels become more functional, and these requirements are becoming more stringent as display methods such as in-plane switching (IPS) are gradually adopted. In display methods such as IPS, if gaseous or liquid components or water generated or leaked from the color filter layer enter the liquid crystal layer through the protective layer, the concentration of water or ionic impurities in the liquid crystal layer increases, or bubbles form in the liquid crystal layer, resulting in poor display. Therefore, it is necessary to prevent the passage of these impurities. In addition, gas generated from the protective film in direct contact with the liquid crystal layer is directly related to poor display, so special attention should be paid to low gas generation.

[0006] Furthermore, after the protective film is formed, there are also issues with LCD panel manufacturing processes, such as photo-alignment treatment of the liquid crystal alignment film, and the need to reduce the effects of external light on various display devices, including organic electroluminescence (EL). Therefore, while ensuring transparency (high transmittance) as a protective film, there are also requirements for the protective film to absorb short-wavelength ultraviolet light, which does not contribute to color display. Summary of the Invention

[0007] [Problems to be solved by the invention]

[0008] There is a demand for a photosensitive resin composition that can form an appropriate protective film pattern by photolithography, and that can sufficiently reduce gas generation, which affects electrical reliability, while maintaining sufficient properties such as transparency, chemical resistance, adhesion, and hardness. Furthermore, in color resists used to form red, green, and blue (RGB) pixels and black resists used to form light-shielding films, there is also a demand for a cured film that not only excels in the required properties but also exhibits low gas generation.

[0009] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a display device having the cured film. The photosensitive resin composition is suitable for use in a protective film or a colored film including a light-shielding film that generates little gas.

[0010] [Technical means to solve the problem]

[0011] The present inventors have studied to solve the problems in the photosensitive resin composition for light-shielding film applications and have found that a specific coloring material is preferable as a light-shielding component of the photosensitive resin composition for light-shielding film applications, thereby completing the present invention.

[0012] The photosensitive resin composition of the present invention contains the following components (A) to (D) as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group of the general formula (1); (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) a photopolymerization initiator; and (D) a solvent.

[0013] [Chemistry 1]

[0014]

[0015] (In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, 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. R1 is independently an alkylene group having 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), and Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by general formula (4), and one or more substituents represented by general formula (4) may be present. n is a number having an average value of 1 to 20.)

[0016] [Chemistry 2]

[0017]

[0018] [Chemistry 3]

[0019]

[0020] (In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

[0021] [Chemistry 4]

[0022]

[0023] (In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0024] The cured film of the present invention is formed by curing the photosensitive resin composition.

[0025] The display device of the present invention includes the cured film.

[0026] [Effects of the Invention]

[0027] According to the present invention, there are provided a photosensitive resin composition suitable for use in a protective film or a colored film including a light-shielding film with little gas generation, a cured film formed by curing the photosensitive resin composition, and a display device having the cured film. DETAILED DESCRIPTION

[0028] 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, the decimal places may be omitted.

[0029] The polymerizable unsaturated group-containing alkali-soluble resin of component (A) represented by general formula (1) of the present invention is obtained by reacting a reaction product of an epoxy compound (a-1) having two glycidyl ether groups and a (meth)acrylic acid derivative with a dicarboxylic acid or a tricarboxylic acid or a monoanhydride thereof (b), and a tetracarboxylic acid or a dianhydride thereof (c).

[0030] The polymerizable unsaturated group-containing alkali-soluble resin is characterized in that the epoxy compound used as a raw material is a compound which may contain several oxyalkylene groups in one molecule and in which Ar in the general formula (1) is an aromatic hydrocarbon group having 6 to 14 carbon atoms.

[0031] Preferred examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a divalent naphthyl group and a phenylene group in which a part of the hydrogen atoms may be substituted by an alkyl group or the like. Here, the alkali-soluble resin (A) containing a polymerizable unsaturated group of the present invention is preferably a resin in which both Ar bonded to the fluorenyl group in the general formula (1) are naphthyl groups (having a bis-naphthol fluorene skeleton) or both are phenylene groups (having a bis-phenol fluorene skeleton), and more preferably a resin in which both Ar bonded to the fluorenyl group are naphthyl groups. The reason for this is that the amount of gas generated by curing the alkali-soluble resin (A) containing a polymerizable unsaturated group in which both Ar bonded to the fluorenyl group are naphthyl groups is small when heated. In addition, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and refers to one or both of them.

[0032] [Chemistry 5]

[0033]

[0034] (In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, 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. R1 is independently an alkylene group having 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), and Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by general formula (4), and one or more substituents represented by general formula (4) may be present. n is a number having an average value of 1 to 20.)

[0035] [Chemistry 6]

[0036]

[0037] [Chemistry 7]

[0038]

[0039] (In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

[0040] [Chemistry 8]

[0041]

[0042] (In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0043] The method for producing the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (1) will be described in detail.

[0044] First, an epoxy compound (a-1) (hereinafter also referred to as "epoxy compound (a-1)") represented by general formula (5) and having a bis-naphthol fluorene skeleton or a bis-phenol fluorene skeleton and which may have several oxyalkylene groups in one molecule is reacted with either or both of the (meth)acrylic acid derivatives represented by general formula (6) or general formula (7) to obtain (meth)acrylate epoxy ester.

[0045] [Chemistry 9]

[0046]

[0047] (In formula (5), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, 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. R1 is independently an alkylene group having 2 to 4 carbon atoms, and l is independently a number from 0 to 3.)

[0048] [Chemistry 10]

[0049]

[0050] [Chemistry 11]

[0051]

[0052] (In formula (6) and formula (7), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

[0053] The reaction between the epoxy compound (a-1) and the (meth)acrylic acid derivative can be carried out using a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 describes that a diol compound containing a polymerizable unsaturated group can be obtained by using approximately 2 moles of (meth)acrylic acid per 1 mole of an epoxy compound having two epoxy groups. In the present invention, the compound obtained by this reaction is a diol (d) containing a polymerizable unsaturated group represented by formula (8) (hereinafter also referred to as "diol (d) represented by general formula (8)").

[0054] [Chemistry 12]

[0055]

[0056] (In formula (8), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, 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 a substituent represented by general formula (2) or general formula (3), R1 is independently an alkylene group having 2 to 4 carbon atoms, and l is independently a number from 0 to 3.)

[0057] [Chemistry 13]

[0058]

[0059] [Chemistry 14]

[0060]

[0061] (In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

[0062] When synthesizing the diol (d) represented by the general formula (8) and subsequently reacting the polycarboxylic acid or its anhydride to produce the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (1), the reaction is usually carried out in a solvent using a catalyst as needed.

[0063] Examples of solvents include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling-point ether-based or ester-based solvents such as diethylene glycol dimethyl ether (diglyme), ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone-based solvents such as cyclohexanone and diisobutyl ketone. The reaction conditions regarding the solvent, catalyst, and the like 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.

[0064] In the reaction between the epoxy group and the carboxyl group or the hydroxyl group, a catalyst is preferably used. Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride; and phosphines such as triphenylphosphine and tri(2,6-dimethoxyphenyl)phosphine.

[0065] 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, the dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b), and the tetracarboxylic acid or their dianhydrides (c) are reacted to obtain an alkali-soluble resin represented by the general formula (1) having a carboxyl group and a polymerizable unsaturated group in one molecule.

[0066] [Chemistry 15]

[0067]

[0068] (In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, 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. R1 is independently an alkylene group having 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), and Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by general formula (4), and one or more substituents represented by general formula (4) are present. The average value of n is 1 to 20.)

[0069] [Chemistry 16]

[0070]

[0071] [Chemistry 17]

[0072]

[0073] (In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

[0074] [Chemistry 18]

[0075]

[0076] (In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0077] Next, the substituent represented by the general formula (2) or (3) derived from the (meth)acrylic acid derivative represented by the general formula (6) or (7) constituting the alkali-soluble resin represented by the general formula (1) will be described in detail.

[0078] General formula (2), general formula (3), general formula (6) and general formula (7) have a polymerizable unsaturated group and at least one ester bond.

[0079] [Chemistry 19]

[0080]

[0081] [Chemistry 20]

[0082]

[0083] [Chemistry 21]

[0084]

[0085] [Chemistry 22]

[0086]

[0087] R2 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.

[0088] In addition, R3 shown in general formula (2), general formula (3), general formula (6) and general formula (7) is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms. The alkylene group may be either linear or branched, and may be ethylene, ethylidene, vinylene, vinylidene, propylene, trimethylene, propenylene, isopropylidene, tetramethylene, etc. In addition, the alkylarylene group may be an unsubstituted arylene group as long as the carbon number is within the range, and may be, for example, o-phenylene, m-phenylene, p-phenylene, tolylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, pentylphenylene, etc.

[0089] In addition, R4 shown in general formula (2), general formula (3), general formula (6) and general formula (7) is a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 2 to 20 carbon atoms. The saturated and unsaturated aliphatic hydrocarbon group may be either linear or branched, and may be vinyl, ethylene, vinylene, vinylene, propenyl, trimethylene, propenylene, isopropylidene, tetramethylene, etc. In addition, the aromatic hydrocarbon group may be unsubstituted as long as the carbon number is within the range, such as o-phenylene, m-phenylene, p-phenylene, tolylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, pentylphenylene, etc., and may be substituted with two to four substituents as long as the carbon number is within the range. In addition, the aliphatic hydrocarbon group may be interrupted by an unsaturated bond, an ether bond, or an ester bond.

[0090] Furthermore, 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 a number from 0 to 2. When the average value of p is within the above range, the distribution can be suppressed from being wide, and thus sufficient curability as a cured film can be imparted without degrading the performance of the resin.

[0091] The acid component used to synthesize the alkali-soluble resin represented by general formula (1) is a polyacid component that reacts with the hydroxyl groups in the diol (d) molecule represented by general formula (8), and it is necessary to use a dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b) and a tetracarboxylic acid or their dianhydrides (c) in combination. The carboxylic acid residue of the acid component can be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, the carboxylic acid residue can also contain a bond containing a heteroelement such as -O-, -S-, or a carbonyl group.

[0092] Examples of the dicarboxylic acid or tricarboxylic acid or their 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 monoanhydrides.

[0093] Examples of monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include monoanhydrides of 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, and diglycolic acid, as well as monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituent. Examples of monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid, as well as monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituent. Examples of monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, and trimellitic acid, as well as monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituent.

[0094] Among the monoanhydrides of dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred. Furthermore, among the dicarboxylic acids or tricarboxylic acids, their monoanhydrides are preferred. The monoanhydrides of the dicarboxylic acids or tricarboxylic acids may be used alone or in combination of two or more.

[0095] Moreover, examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, or acid dianhydrides thereof.

[0096] Examples of chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups have been introduced. Examples of alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids into which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups have been introduced. Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid. Bis-trimellitic anhydride aryl esters may also be used. Bis-trimellitic anhydride aryl esters are a group of compounds produced, for example, by the method described in WO2010 / 074065. Structurally, they are dianhydrides formed by reacting two hydroxyl groups of an aromatic diol (such as naphthalene diol, biphenol, or terphenyl diol) with the carboxyl groups of two molecules of trimellitic anhydride to form an ester bond. Hereinafter, these compounds are referred to as bis-trimellitic anhydride esters of aromatic diols.

[0097] Among tetracarboxylic acids or their dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferred, with biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid being more preferred. Furthermore, among tetracarboxylic acids or their dianhydrides, their dianhydrides are preferred. Furthermore, bis-trimellitic anhydride esters of naphthalene diol are also preferably used. Furthermore, the tetracarboxylic acids or their dianhydrides and bis-trimellitic anhydride esters of aromatic diols may be used alone or in combination of two or more.

[0098] The reaction of the diol (d) represented by the general formula (8) with the acid component (b) and the acid component (c) is not particularly limited, and a known method can be employed. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method in which epoxy (meth)acrylate and tetracarboxylic dianhydride are reacted at a reaction temperature of 90°C to 140°C.

[0099] Here, in order to make the terminal of the compound a carboxyl group, it is preferred to react so that the molar ratio of the diol (d) represented by the general formula (8), the dicarboxylic acid or tricarboxylic acid or their monoanhydride (b), and the tetracarboxylic acid or their dianhydride (c) becomes (d): (b): (c) = 1.0:0.01 to 1.0:0.2 to 1.0.

[0100] For example, when using an acid monoanhydride (b) or an acid dianhydride (c), it is preferred to react so that the amount of the acid component [(b) / 2+(c)] relative to the molar ratio of the diol (d) containing a polymerizable unsaturated group [(d) / [(b) / 2+(c)]] is 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of the unreacted diol containing a polymerizable unsaturated group does not increase, thereby improving the temporal stability of the alkali-soluble resin composition. 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, the increase in the content of the unreacted acid dianhydride can be suppressed, thereby improving the temporal stability of the alkali-soluble resin composition. In addition, the molar ratio of each component of (b), (c) and (d) 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 general formula (2).

[0101] The acid value of the alkali-soluble resin represented by the general formula (1) preferably ranges from 20 mgKOH / g to 180 mgKOH / g, preferably from 40 mgKOH / g to 120 mgKOH / g. When the acid value is 20 mgKOH / g or more, residue is less likely to remain during alkaline development, and when the acid value is 180 mgKOH / g or less, the penetration of the alkaline developer does not become too rapid, thereby suppressing peeling. The acid value can be determined by titrating with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0102] The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Co., Ltd.) 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 decrease 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 a solution viscosity of the photosensitive resin composition preferred for coating, and alkaline development does not require excessive time.

[0103] Next, the photosensitive resin composition using the alkali-soluble resin represented by the general formula (1) of the present invention will be described.

[0104] In the photosensitive resin composition of the present invention, the content of component (A) is preferably 10% to 90% by mass relative to the total mass of the solid content. Furthermore, 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 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of components (A) and (B).

[0105] Examples of the (B) photopolymerizable monomer having at least three ethylenically unsaturated bonds in the photosensitive resin composition of the present invention include (meth)acrylates such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene alkylene oxide-modified hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; and dendrimer-type multifunctional acrylates. These photopolymerizable monomers may be used alone or in combination of two or more.

[0106] The content of the (B) component is preferably 5 to 200 parts by mass relative to 100 parts by mass of the (A) component, more preferably 10 to 80 parts by mass relative to 100 parts by mass of the (A) component, and further preferably 10 to 60 parts by mass. When the content of the (B) component is 5 parts by mass or more relative to 100 parts by mass of the (A) component, the amount of the photoreactive functional group in the resin is sufficient, so that a sufficient cross-linked structure is formed. In addition, since the acid value in the resin component is not too high, the solubility of the exposed portion in the alkaline developer is reduced, so that the formed pattern can be suppressed from becoming thinner than the target line width, and the loss of the pattern can be suppressed. In addition, when the content of the (B) component is 200 parts by mass or less relative to 100 parts by mass of the (A) component, a cured film with sufficient curability can be obtained, so that the edge of the pattern can be made clear.

[0107] Examples of the (C) photopolymerization initiator in the photosensitive resin composition of the present invention include: acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-di Biimidazole compounds such as phenylbiimidazole and 2,4,5-triarylbiimidazole; halogenated methyldiazole compounds such as 2-trichloromethyl-5-phenylvinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole and 2-trichloromethyl-5-(p-methoxyphenylvinyl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-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-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiophenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and other halomethyl-s-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoyl O-acyl oxime compounds such as esters, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O-acetate, and 1-(4-methylthiophenyl)butane-1-one-oxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. Furthermore, the photopolymerization initiators may be used alone or in combination of two or more.

[0108] In particular, when a photosensitive resin composition includes a coloring material, it is preferred to use O-acyl oxime compounds (including ketoximes). Specific compound groups include O-acyl oxime photopolymerization initiators represented by general formula (9) or general formula (10). Among these compound groups, when using a coloring material with a high pigment concentration or when forming a light-shielding film pattern, it is preferred to use an O-acyl oxime photopolymerization initiator having a molar absorption coefficient of 10,000 L / mol·cm or more at 365 nm. Furthermore, the term "photopolymerization initiator" as used herein includes a sensitizer.

[0109] [Chemistry 23]

[0110]

[0111] (In formula (9), R5 and R6 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 a heterocyclic group having 4 to 12 carbon atoms, and R7 is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, the alkyl group may be any of linear, branched, or cyclic.)

[0112] [Chemistry 24]

[0113]

[0114] (In formula (10), R8 and R9 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group, cycloalkylalkyl group or alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms. 10 Each of R8 to R10 is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, wherein a portion of the -CH2- group in the alkyl or alkenyl group may be substituted with an -O- group. 10 Some of the hydrogen atoms in the group may be substituted by halogen atoms.)

[0115] The content of component (C) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, relative to 100 parts by mass of the total amount of component (A) and component (B). When the content of component (C) is 0.1 parts by mass or more, a moderate photopolymerization speed is achieved, thereby suppressing a decrease in sensitivity. In addition, when the content of component (C) is 30 parts by mass or less, a line width faithful to the mask can be reproduced, and the pattern edge can be made clear.

[0116] (D) Examples of the solvent contained in the photosensitive resin composition include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α-terpineol and β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, and diethylene glycol ethyl Glycol ethers such as methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as 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, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing these solvents, a uniform solution-like composition can be prepared. To achieve necessary properties such as coatability, these solvents can be used alone or in combination of two or more. The amount of solvent varies depending on the target viscosity, but is preferably 60% to 90% by mass of the photosensitive resin composition solution.

[0117] The photosensitive resin composition contains a coloring material as the (E) component. When used as a resist for a light-shielding film, the (E) component is one or more light-shielding components selected from the group consisting of black organic pigments, mixed color organic pigments, and light-shielding materials, preferably black organic pigments and / or mixed color organic pigments. In addition, the average secondary particle size of the black organic pigment and / or mixed color organic pigment is preferably 20 nm to 500 nm. The average secondary particle size of the black organic pigment and the mixed color organic pigment can be measured using a particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) using a dynamic light scattering method and using a cumulative method.

[0118] The content of the coloring material as the component (E) can be arbitrarily determined depending on the desired light-shielding degree, and is preferably 1 to 80% by mass relative to the solid content in the photosensitive resin composition. When an organic pigment or a carbon-based inorganic pigment is used, it is more preferably 20 to 60% by mass.

[0119] Examples of black organic pigments as component (E) include: perylene black, aniline black, cyanine black, lactam black, etc. Examples of mixed color organic pigments include: pigments obtained by mixing at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolinline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments and performing simulated blackening. As light-shielding materials, carbon black, chromium oxide, iron oxide, titanium black, etc. can be included. The component (E) can also use a pigment that has been appropriately surface-treated according to the function of the target photosensitive resin composition. In addition, the component (E) can be used alone or in combination of two or more.

[0120] Examples of the organic pigment that can be used as the component (E) include the pigments numbered below in the Color Index, but are not limited thereto.

[0121] 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.

[0122] Pigment orange: 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

[0123] 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.

[0124] Pigment green 7, 36, 58, etc.

[0125] Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.

[0126] Pigment violet 19, 23, 37, etc.

[0127] The coloring material (component (E)) is preferably pre-dispersed in the solvent (D) along with the dispersant (F) to form a coloring material dispersion, which is then blended into the photosensitive resin composition. The solvent used for dispersion will become part of component (D), so any solvent included in component (D) can be used. Preferred examples of component (D) include propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methoxy-3-methyl-1-butyl acetate.

[0128] The content of component (E) is preferably 1% to 80% by mass, more preferably 30% to 60% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. In addition, the solid content refers to the components other than component (D) in the photosensitive resin composition. The solid content also includes component (B) that becomes a solid component after photocuring. When component (E) is 1% by mass or more, it is easy to set the desired light-shielding property. In addition, when component (E) is 80% by mass or less, the desired development characteristics and film-forming ability can be obtained.

[0129] The dispersant (F) can be used without particular limitation, and any known compound used for dispersing a coloring material (pigment) (compounds commercially available under names such as dispersants, dispersing wetting agents, and dispersion accelerators) can be used.

[0130] Examples of dispersants as component (F) include: cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersing aids). In particular, with respect to adsorption of coloring materials, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrolyl group, a pyridyl group, a primary amino group, a secondary amino group, or a tertiary amino group, and an amine value of 1 mgKOH / g to 100 mgKOH / g and a number average molecular weight of 1,000 to 100,000. The amount of the dispersant to be blended is preferably 1% to 35% by mass, 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, there is no restriction on use for the purpose of stabilizing dispersion.

[0131] In addition, when preparing the coloring material dispersion, not only the (F) dispersant is dispersed, but also a portion of the alkali-soluble resin containing a polymerizable unsaturated group of the (A) component is co-dispersed, thereby making it easy to maintain the exposure sensitivity at a high sensitivity, good adhesion during development, and not prone to the problem of residue. In the coloring material dispersion, the content of the (A) component is preferably 2% to 20% by mass, more preferably 5% to 15% by mass. When the (A) component is 2% by mass or more, the effects of co-dispersion such as increased sensitivity, increased adhesion, and reduced residue can be obtained. In addition, when the (A) component is 20% by mass or less, a cured film (coating film) uniformly dispersed with the (E) component can be obtained.

[0132] The coloring material dispersion can be mixed with component (A) (if component (A) is co-dispersed during the preparation of the coloring material dispersion, the remaining component (A)), component (B), component (C), and the remaining component (E) to prepare a photosensitive resin composition for a light-shielding film.

[0133] Furthermore, the photosensitive resin composition of the present invention may optionally contain other resin components that polymerize or cure by light or heat. Examples of other resin components include epoxy resins such as novolac epoxy resins derived from novolacs such as phenol novolac and cresol novolac, and bisphenol-type epoxy resins; alkali-soluble resins (excluding component (A)) obtained by reacting such epoxy resins with (meth)acrylic acid and an acid anhydride; copolymers with (meth)acrylic acid and / or (meth)acrylates; and alkali-soluble resins obtained by reacting carboxyl groups in such copolymers with epoxy-containing (meth)acrylates.

[0134] The photosensitive resin composition of the present invention may optionally contain additives such as a hardener, a hardening accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a surfactant, and a coupling agent.

[0135] Examples of hardeners include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, and Lewis acid complex compounds that help harden epoxy resins. Examples of hardening accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, and imidazoles that help accelerate the hardening of epoxy resins. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoamers or leveling agents include silicone, fluorine, and acrylic compounds. Examples of surfactants include fluorine-based surfactants and silicone surfactants. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

[0136] The cured film (coating) of the present invention can be formed by photolithography using the photosensitive resin composition of the present invention. The method involves first applying a photosensitive resin composition solution to a substrate surface, drying the solvent (pre-baking), placing a photomask on the coating, and irradiating the coating with ultraviolet light to cure the exposed areas. Development is then performed using an alkaline aqueous solution to remove the unexposed areas to form a pattern, followed by post-baking for post-curing. Examples of substrates to which the photosensitive resin composition solution is applied include glass and transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.).

[0137] The substrate may be a transparent substrate or a substrate other than a transparent substrate. Examples of transparent substrates for coating the photosensitive resin composition include not only glass substrates but also substrates having transparent electrodes such as ITO or gold deposited or patterned on transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.).

[0138] As a method for coating the photosensitive resin composition solution on the substrate, not only the well-known solution dipping method and spraying method can be used, but also a method using a roll coater, a disc coater (Land coater machine), a slit coater or a rotary machine can be adopted. After coating to a desired thickness using the method, the solvent is dried (pre-baked) to form a film. In addition, pre-baking is carried out by heating using an oven, a hot plate, etc. The heating temperature and heating time in pre-baking can be appropriately selected according to the solvent used, for example, at a temperature of 60°C to 110°C for 1 minute to 3 minutes.

[0139] Exposure after pre-baking is performed using an ultraviolet exposure device through a photomask, thereby sensitizing only the portion of the resist corresponding to the pattern. By appropriately selecting the exposure device and its exposure conditions, and using a light source such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or an extreme ultraviolet lamp, exposure cures the photosensitive resin composition in the coating film.

[0140] As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. can be used, and the wavelength range of the radiation is preferably 250nm to 450nm. 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 as needed. The development temperature is preferably 20°C to 35°C, and a commercially available developer or ultrasonic cleaning machine can be used to accurately form a fine image. In addition, after the alkaline development, water washing is usually performed. As the development treatment method, a spray development method, a spray development method, an immersion (dip) development method, a puddle (liquid covering) development method, etc. can be applied.

[0141] Alkaline development after exposure is performed to remove unexposed portions of the photosensitive resin composition, forming the desired pattern. Suitable developing solutions for alkaline development include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, and the like. In particular, weakly alkaline aqueous solutions containing 0.03% to 1% by weight of carbonates such as sodium carbonate and potassium carbonate are preferably used for development at a temperature of 23°C to 27°C. This allows for precise formation of fine images using commercially available developers or ultrasonic cleaners.

[0142] After development is performed in the above manner, heat treatment (post-baking) is performed at 180°C to 250°C for 20 minutes to 100 minutes. Among them, when the heat resistance of the substrate used for film formation is low, the formulation of the composition can also be designed in a manner that can be set to a post-baking condition of 80°C to 180°C for 30 minutes to 100 minutes. The post-baking is carried out for the purpose of improving the adhesion between the patterned coating film and the substrate. It is carried out by heating using an oven, a hot plate, etc. in the same way as pre-baking. The patterned resin film of the present invention is formed through the above-mentioned steps using photolithography.

[0143] [Example]

[0144] Hereinafter, the embodiment of the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[0145] First, we will describe the synthesis example of an alkali-soluble resin containing a polymerizable unsaturated group and having a structure represented by general formula (1). Unless otherwise specified, the resin in this synthesis example was evaluated as follows. Regarding various measuring instruments, if the same model was used, the manufacturer's name will be omitted from the second reference. Furthermore, in Examples 1 and 2, the glass substrates used in the preparation of the substrates with the cured film for measurement were all treated identically.

[0146] [Solid content concentration]

[0147] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)]. The weight after heating at 160°C for 2 hours [W2 (g)] was used to determine the molecular weight using the following formula (1).

[0148] Solid content concentration (weight %) = 100 × (W2-W0) / (W1-W0) (1)

[0149] [Epoxy equivalent]

[0150] After dissolving the resin solution in dioxane, a tetraethylammonium bromide solution in acetic acid was added and titrated with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the concentration.

[0151] [Acid value]

[0152] The resin solution was dissolved in dioxane and titrated with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" to determine the molecular weight.

[0153] [Molecular weight]

[0154] The measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuperH-2000 (2 columns) + TSKgelSuperH-3000 (1 column) + TSKgelSuperH-4000 (1 column) + TSKgelSuperH-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, flow rate: 0.6 ml / min), and the weight average molecular weight (Mw) was determined as a converted value using standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer set).

[0155] In addition, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

[0156] BPFE: Bisphenol fluorene epoxy resin

[0157] (Epoxy resin wherein Ar is a benzene ring and l is 0, epoxy equivalent weight 256)

[0158] BNFE: Bisnaphthol fluorene epoxy resin

[0159] (Epoxy resin wherein Ar is a naphthalene ring and l is 0 in the general formula (5), epoxy equivalent weight 281)

[0160] HOA-HH: 2-Acryloyloxyethylhexahydrophthalic acid

[0161] (Light Acrylate HOA-HH(N), manufactured by Kyoeisha Chemical Co., Ltd.)

[0162] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0163] BTDA: Benzophenone tetracarboxylic dianhydride

[0164] BTANE: bis(trimellitic anhydride) ester of naphthalene diol (DHN-D1, manufactured by Honshu Chemical Industry Co., Ltd.)

[0165] THPA: 1,2,3,6-tetrahydrophthalic anhydride

[0166] TPP: triphenylphosphine

[0167] TBPC: 2,6-di-tert-butyl-p-cresol

[0168] AA: Acrylic acid

[0169] MAA: Methacrylic acid

[0170] MMA: Methyl Methacrylate

[0171] CHMA: Cyclohexyl methacrylate

[0172] AIBN: Azobisisobutyronitrile

[0173] GMA: Glycidyl methacrylate

[0174] PGMEA: Propylene glycol monomethyl ether acetate

[0175] [Synthesis example 1]

[0176] BPFE (46.64 g, 0.09 mol), AA (13.12 g, 0.18 mol), TPP (0.24 g), and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. PGMEA (20.00 g) was then added to adjust the solid content to 50% by mass.

[0177] Subsequently, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-1. The obtained resin solution had a solid content concentration of 57.3% by mass, an acid value (based on solid content) of 96 mgKOH / g, and an Mw of 3600 as determined by GPC analysis.

[0178] [Synthesis example 2]

[0179] BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. PGMEA (20.00 g) was then added to adjust the solid content to 50% by mass.

[0180] Subsequently, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-2. The obtained resin solution had a solids concentration of 56.9% by mass, an acid value (based on solids) of 90 mgKOH / g, and an Mw of 4000 as determined by GPC analysis.

[0181] [Synthesis example 3]

[0182] BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. PGMEA (20.00 g) was then added to adjust the solid content to 50% by mass.

[0183] Subsequently, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-3. The obtained resin solution had a solid content concentration of 56.9% by mass, an acid value (based on solid content) of 90 mgKOH / g, and an Mw of 2600 as determined by GPC analysis.

[0184] [Synthesis Example 4]

[0185] BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. PGMEA (20.00 g) was then added to adjust the solid content to 50% by mass.

[0186] Subsequently, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-4. The obtained resin solution had a solid content concentration of 56.1% by mass, an acid value (based on solid content) of 83 mgKOH / g, and an Mw of 7000 as determined by GPC analysis.

[0187] [Synthesis example 5]

[0188] In a 250 mL four-necked flask equipped with a reflux cooler, BNFE (30.53 g, 0.05 mol), HOA-HH (29.33 g, 0.11 mol), TPP (0.14 g), and PGMEA (40.00 g) were placed and stirred at 100° C. to 105° C. for 12 hours to obtain a reaction product. PGMEA (20.00 g) was then added to adjust the solid content to 50% by mass.

[0189] Subsequently, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-5. The obtained resin solution had a solid content concentration of 54.6% by mass, an acid value (based on solid content) of 63 mgKOH / g, and an Mw of 5300 as determined by GPC analysis.

[0190] [Synthesis example 6]

[0191] BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. PGMEA (20.00 g) was then added to adjust the solid content to 50% by mass.

[0192] Subsequently, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-6. The obtained resin solution had a solid content concentration of 54.6% by mass, an acid value (based on solid content) of 92 mgKOH / g, and an Mw of 4100 as determined by GPC analysis.

[0193] [Synthesis Example 7]

[0194] BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. PGMEA (20.00 g) was then added to adjust the solid content to 50% by mass.

[0195] Subsequently, 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-7. The obtained resin solution had a solid content concentration of 54.6% by mass, an acid value (based on solid content) of 91 mgKOH / g, and an Mw of 5000 as determined by GPC analysis.

[0196] [Synthesis example 8]

[0197] MAA (51.65 g, 0.60 mol), MMA (36.04 g, 0.36 mol), CHMA (40.38 g, 0.24 mol), AIBN (5.91 g), and PGMEA (360 g) were placed in a 1000 ml four-necked flask equipped with a nitrogen inlet and reflux line, and polymerization was carried out by stirring at 80°C to 85°C for 8 hours under a nitrogen flow. Furthermore, GMA (61.41 g, 0.43 mol), TPP (2.27 g), and TBPC (0.086 g) were placed in the flask and stirred at 80°C to 85°C for 16 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-8. The resulting resin solution had a solids concentration of 35.7% by mass, an acid value (based on solids) of 50 mgKOH / g, and an Mw of 19,600 as determined by GPC analysis.

[0198] (Alkali-soluble resin solution)

[0199] (A)-1: Alkali-soluble resin solution obtained in Synthesis Example 1

[0200] (A)-2: Alkali-soluble resin solution obtained in Synthesis Example 2

[0201] (A)-3: Alkali-soluble resin solution obtained in Synthesis Example 3

[0202] (A)-4: Alkali-soluble resin solution obtained in Synthesis Example 4

[0203] (A)-5: Alkali-soluble resin solution obtained in Synthesis Example 5

[0204] (A)-6: Alkali-soluble resin solution obtained in Synthesis Example 6

[0205] (A)-7: Alkali-soluble resin solution obtained in Synthesis Example 7

[0206] (A)-8: Alkali-soluble resin solution obtained in Synthesis Example 8

[0207] (Photopolymerizable monomer)

[0208] (B): DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

[0209] (Photopolymerization initiator)

[0210] (C): Irgacure OXE-02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), manufactured by BASF. “Irgacure” is a registered trademark of BASF.

[0211] (Solvent)

[0212] (D)-1: Propylene glycol monomethyl ether acetate

[0213] (D)-2: 3-Methoxy-3-methyl-1-butyl acetate

[0214] (Surfactant)

[0215] BYK-330 PGMEA solution (solid content 1.0%) (manufactured by BYK-Chemie)

[0216] [Example 1]

[0217] The components (A) to (F) were blended in the proportions shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2. (D)-1 in the solvent column represents the amount of PGMEA (same as (D)-1) in the unsaturated group-free resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution), the solvent in the light-shielding pigment dispersion, and the solvent in the surfactant. All values ​​in Table 1 are expressed in mass %.

[0218]

[0219] [evaluate]

[0220] The following evaluations were performed using the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2.

[0221] (Production of hardened film (coating film))

[0222] The photosensitive resin composition shown in Table 1 was applied using a spin coater to a substrate previously irradiated with a low-pressure mercury lamp at a wavelength of 254 nm and an illumination intensity of 1000 mJ / cm2 so that the film thickness after heat curing was 1.5 μm. 2The coated plates were prepared by pre-baking on a 50 mm x 50 mm glass substrate "EAGLE XG" (manufactured by Corning) (hereinafter referred to as "glass substrate"), an indium tin oxide vapor-deposited glass substrate (hereinafter referred to as "ITO substrate"), and a molybdenum-aluminum alloy vapor-deposited substrate (hereinafter referred to as "MAM substrate") at 90°C for 1 minute using a hot plate. Subsequently, the coated plates were prepared by irradiating with an illuminance of 30 mW / cm at a wavelength of 365 nm. 2 High-pressure mercury lamp irradiation 100mJ / cm 2 Then, the films were cured at 230° C. for 30 minutes using a hot air dryer to obtain the cured films (coating films) of Examples 1 to 10 and Comparative Examples 1 and 2.

[0223] The cured films (coatings) comprising the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 obtained above were evaluated for the following parameters, and the results are shown in Table 2. These evaluations were performed as follows. Furthermore, high-temperature and high-humidity adhesion and chemical resistance were evaluated not only for the cured films (coatings) formed on glass substrates but also for the cured films (coatings) formed on ITO substrates and MAM substrates.

[0224] (Film thickness measurement)

[0225] The film thicknesses of the cured films (coating films) of Examples 1 to 10 and Comparative Examples 1 and 2 were measured using a stylus-type step profile measuring apparatus “P-17” (manufactured by KLA-Tencor Corporation).

[0226] [High temperature and high humidity resistance]

[0227] (Evaluation method)

[0228] Cured films (coatings) formed on glass, ITO, and MAM substrates were left to stand for 5 hours at 121°C, 100% humidity, and 2 atm. A cross-cut peeling test was then conducted. A Super Cutter Guide (manufactured by Taiyou Machinery Co., Ltd.) was used to cut into the substrates to form a grid of 100 1 mm x 1 mm squares. Cellophane tape (manufactured by Nichiban Co., Ltd.) was then attached to the grid and peeled off.

[0229] (Evaluation Criteria)

[0230] ○: The cured film (coating film) in the grid is not peeled off at all

[0231] △: Less than 1 / 3 of the cured film (coating film) in the grid peeled off

[0232] ×: Peeling occurred in more than 1 / 3 of the samples

[0233] [Chemical resistance and adhesion]

[0234] (Evaluation method)

[0235] Cured films (coatings) produced on glass, ITO, and MAM substrates were immersed in a petri dish containing N-methyl-2-pyrrolidone at 60°C for 2 minutes, then rinsed with pure water and the moisture wiped off. A cross-cut peel test was then conducted. A Super Cutter Guide was used to cut the substrates to form a grid of 100 1 mm x 1 mm squares. Cellophane tape was applied to the grid and then peeled off.

[0236] (Evaluation Criteria)

[0237] ○: The cured film (coating film) in the grid is not peeled off at all

[0238] △: Less than 1 / 3 of the cured film (coating film) in the grid peeled off

[0239] ×: Peeling occurred in more than 1 / 3 of the samples

[0240] [Coating hardness 1]

[0241] (Evaluation method)

[0242] According to the test method of Japanese Industrial Standards (JIS) K5600-5-4, a pencil hardness tester was used to apply a load of 750g to the cured film (coating) produced on a glass substrate. The maximum pencil hardness when no damage occurred in the cured film (coating) was measured. The pencil used was "Mitsubishi HI-Uni" (manufactured by Mitsubishi Pencil Co., Ltd.). This evaluation was conducted as an indicator of the coating surface's resistance to lateral forces (scratches).

[0243] (Evaluation Criteria)

[0244] ○: 3 hours or more

[0245] △: 2H

[0246] ×: H or less

[0247] [Coating hardness 2]

[0248] (Evaluation method)

[0249] The hardness of the cured film (coating film) formed on the glass substrate was measured using a micro film hardness tester "HM2000" (manufactured by Fischer Instruments). A Vickers indenter was used, and a load of 5 mN / μm was applied at a load speed of 0.25 mN / sec. 2 A load of 1000 is applied, held for 1 second, and then the load is removed to measure the Martens hardness (according to ISO 14577). This evaluation is performed as an indicator of the resistance of the hardened film (coating) surface to longitudinal forces (indentation). "Martens hardness" refers to the hardness calculated from the load-penetration depth curve.

[0250] (Evaluation Criteria)

[0251] ○: 65N / mm 2 above

[0252] △: 60N / mm 2 Above and less than 65N / mm 2

[0253] ×: less than 60N / mm 2

[0254] [Transmittance 1]

[0255] (Evaluation method)

[0256] The transmittance of a cured film (coating film) having a film thickness of 2 μm and formed on an “EAGLE XG” glass substrate was measured using a transmittance meter “Spectrophotometer SD 5000” (manufactured by Nippon Denshoku Industries, Ltd.).

[0257] (Evaluation Criteria)

[0258] ○: Transmittance at a wavelength of 400 nm is 95% or more

[0259] △: Transmittance at a wavelength of 400 nm is 90% or more and less than 95%

[0260] ×: less than 90%

[0261] [Transmittance 2]

[0262] The transmittance of a cured film (coating film) produced on an "EAGLE XG" glass substrate in a film thickness of 3 μm was measured using a transmittance meter "Spectrophotometer (SPECTRO PHOTOMETER) SD 5000".

[0263] (Evaluation Criteria)

[0264] ○: Transmittance at a wavelength of 340nm is less than 20%

[0265] △: Transmittance at a wavelength of 340 nm is 20% or more and less than 65%

[0266] ×: 65% or more

[0267] [Gas generation]

[0268] (Evaluation method)

[0269] A cured film (coating) formed on an "EAGLE XG" glass substrate was ground using a scraper or other device. The thermogravimetric loss of 10 mg of the resulting powdered cured film (coating) was measured using an EXSTAR 6000 differential thermal analysis (TG / DTA) instrument (manufactured by Hitachi High-Tech Science Co., Ltd.). The measurement conditions were pre-treatment at 120°C for 30 minutes in atmospheric air, followed by holding at 230°C for 3 hours. Gas generation was evaluated using the weight loss rate, calculated from the weight loss before and after heating at 230°C.

[0270] (Evaluation Criteria)

[0271] ◎: Weight reduction rate is less than 3%

[0272] ○: Weight reduction rate is 3% or more and less than 7%

[0273] △: Weight reduction rate is 7% or more and less than 15%

[0274] ×: Weight reduction rate is 15% or more

[0275] [Water absorption]

[0276] (Evaluation method)

[0277] A cured film (coating) formed on an EAGLE XG glass substrate was allowed to stand for 24 hours at a constant temperature and humidity of 40°C and 90% humidity. The film was then ground with a scraper or other tool. The thermogravimetric loss of 10 mg of the resulting powdered cured film (coating) was measured using an EXSTAR 6000 differential thermal analysis / thermogravimetric analyzer (TG / DTA). The measurement conditions were a nitrogen atmosphere, with the temperature increased at 10°C / min to 120°C and held for 1 hour. Water absorption was evaluated by weight loss.

[0278] (Evaluation Criteria)

[0279] ○: Weight reduction rate is less than 2%

[0280] △: Weight reduction rate is 2% or more and less than 5%

[0281] ×: Weight reduction rate is 5% or more

[0282] [Development Characteristics]

[0283] (Preparation of Evaluation Samples)

[0284] The photosensitive resin composition shown in Table 1 was applied to a 125 mm x 125 mm glass substrate "EAGLE XG" using a spin coater to a film thickness of 1.5 μm after heat curing. The film was pre-baked at 90°C for 1 minute using a hot plate. A photomask was then set with an exposure gap of 150 μm and an illumination of 30 mW / cm2 at a wavelength of 365 nm was used. 2 High-pressure mercury lamp irradiation 100mJ / cm 2 The ultraviolet rays cause the photosensitive part to undergo a light hardening reaction.

[0285] The exposed cured film (coating film) was then developed using a 0.05% potassium hydroxide aqueous solution or a 0.2% sodium carbonate aqueous solution at 23°C under a pressure of 0.1 MPa for 60 seconds, and then washed with water to remove the unexposed portion of the cured film (coating film). The cured film (coating film) was then heat-cured at 230°C for 30 minutes using a hot air dryer to obtain the cured films (patterns) of Examples 1 to 10 and Comparative Examples 1 and 2.

[0286] (Evaluation Method and Evaluation Criteria)

[0287] The formation of thin lines in the obtained pattern was confirmed using an optical microscope and evaluated in the following three stages.

[0288] ○: A pattern with an L / S of 15 μm / 15 μm or more was formed without residue

[0289] △: A pattern with an L / S of 30 μm / 30 μm or more was formed without residue.

[0290] ×: A pattern with an L / S of less than 50 μm / 50 μm was not formed, or curling or residue of the pattern was clearly present.

[0291]

[0292] [Example 2]

[0293] The components (A) to (F) were blended 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 represents the amount of PGMEA (same as (D)-1) in the unsaturated group-free resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution), the solvent in the light-shielding pigment dispersion, and the solvent in the surfactant. All values ​​in Table 3 are expressed in mass %.

[0294] (Light-shielding pigment dispersion)

[0295] (E)-1: PGMEA dispersion containing 15.0% by mass of a lactam-based black pigment and 4.5% by mass of a polymer dispersant (solid content 19.5%)

[0296] (E)-2: PGMEA dispersion containing 25.0% by mass of a resin-coated carbon black pigment and 5.0% by mass of a polymer dispersant (solid content 30.0%)

[0297]

[0298] [evaluate]

[0299] The following evaluations were performed using the photosensitive resin compositions of Examples 11 to 16 and Comparative Examples 11 to 13. Table 4 shows the evaluation results.

[0300] [Measurement of optical density]

[0301] The photosensitive resin compositions shown in Table 3 were applied to a 125 mm x 125 mm glass substrate using a spin coater to a film thickness of 1.1 μm after heat curing. The films were pre-baked at 90°C for 1 minute. Subsequently, the compositions were heat cured at 230°C for 30 minutes using a hot air dryer to obtain the cured films (coatings) of Examples 11 to 16 and Comparative Examples 11 to 13. The optical density (OD) of the resulting cured films (coatings) was measured using a Macbeth transmission densitometer, and evaluation was performed using the optical density per unit film thickness.

[0302] [Measurement of volume resistivity]

[0303] (Measurement method)

[0304] Using a spin coater, each photosensitive resin composition shown in Table 3 was applied to a 100 mm × 100 mm glass substrate with a thickness of 1.2 mm and deposited with Cr, excluding the electrodes, in such a manner that the film thickness after heat curing was 3.5 μm. The film was pre-baked at 90°C for 1 minute. Subsequently, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer to obtain the cured films (coatings) of Examples 11 to 16 and Comparative Examples 11 to 13. Subsequently, an aluminum electrode was formed on the cured film (coating) to prepare a substrate for volume resistivity measurement. Next, using an electrometer (electrometer "Model 6517A" (manufactured by Keithley), the volume resistivity was measured from an applied voltage of 1 V to an applied voltage of 10 V. Furthermore, the measurement was performed under the condition of maintaining the voltage for 60 seconds at each applied voltage in 1 V steps.

[0305] [Determination of dielectric constant]

[0306] (Measurement method)

[0307] Using a spin coater, the photosensitive resin compositions shown in Table 3 were applied to a 100 mm × 100 mm glass substrate with a thickness of 1.2 mm and Cr vapor-deposited thereon, excluding the electrodes, in such a manner that the film thickness after heat curing was 3.5 μm, and pre-baked at 90°C for 1 minute. Subsequently, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer to obtain the cured films (coatings) of Examples 11 to 16 and Comparative Examples 11 to 13. Subsequently, an aluminum electrode was formed on the coating to prepare a substrate for dielectric constant measurement. Next, an electrometer (electrometer type 6517A) was used to measure the electrostatic capacitance at frequencies from 1 Hz to 100,000 Hz, and the dielectric constant was calculated based on the electrostatic capacitance.

[0308] [Gas generation]

[0309] (Evaluation method)

[0310] A cured film (coating) formed on an EAGLE XG glass substrate was ground with a blade, and the thermogravimetric loss of 10 mg of the resulting powdered cured film (coating) was measured using an EXSTAR 6000 differential thermal analysis / thermogravimetric analyzer (TG / DTA). The measurement conditions were: a 30-minute pretreatment at 120°C in air, followed by a 3-hour holding period at 230°C.

[0311] (Evaluation Criteria)

[0312] ◎: Weight reduction rate is less than 3%

[0313] ○: Weight reduction rate is 3% or more and less than 7%

[0314] △: Weight reduction rate is 7% or more and less than 10%

[0315] ×: Weight reduction rate is 10% or more

[0316] [Measurement of elastic recovery rate of spacer]

[0317] (Measurement method)

[0318] The photosensitive resin compositions shown in Table 3 were applied to a 125 mm × 125 mm glass substrate "EAGLE XG" using a spin coater to a film thickness of 3.0 μm after heat curing, and pre-baked at 90°C for 1 minute. The substrate was then placed in close contact with a photomask having a dot pattern and illuminated with a wavelength of 365 nm and an intensity of 30 mW / cm 2 High-pressure mercury lamp irradiation 100mJ / cm 2 The ultraviolet rays cause the photosensitive part to undergo a light hardening reaction.

[0319] 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). Subsequently, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer to obtain the cured films (coatings) of Examples 1 to 6 and Comparative Examples 1 to 3. The spacing characteristics of the obtained cured film (coating) pattern were evaluated using an ultra-micro hardness tester "Fischerscope HM2000Xyp" (manufactured by Fischer Instruments). A 100μm square flat indenter was pressed in at a load rate of 5.0mN / second. After the load reached 50mN, the load was unloaded at a rate of 5.0mN / second, and a displacement curve was prepared.

[0320] The elastic recovery rate was calculated according to the following formula (2), where the displacement amount under a load of 50 mN during loading was defined as L1 and the displacement amount during unloading was defined as L2.

[0321] Elastic recovery rate (%) = (L1-L2) / L1×100(2)

[0322] [Development Characteristics]

[0323] (Preparation of Evaluation Samples)

[0324] The photosensitive resin composition shown in Table 3 was applied to a 125 mm x 125 mm glass substrate "EAGLE XG" using a spin coater to a film thickness of 1.5 μm after heat curing. The film was pre-baked at 90°C for 1 minute using a hot plate. A photomask was then set with an exposure gap of 150 μm and an illumination of 30 mW / cm2 at a wavelength of 365 nm was used. 2 High-pressure mercury lamp irradiation 100mJ / cm 2 The ultraviolet rays cause the photosensitive part to undergo a light hardening reaction.

[0325] The exposed cured film (coating film) was then developed using a 0.05% potassium hydroxide aqueous solution or a 0.2% sodium carbonate aqueous solution at 23°C under a pressure of 0.1 MPa for 60 seconds, and then washed with water to remove the unexposed portion of the cured film (coating film). The cured film (coating film) was then heat-cured at 230°C for 30 minutes using a hot air dryer to obtain the cured films (patterns) of Examples 11 to 16 and Comparative Examples 11 to 13.

[0326] (Evaluation Method and Evaluation Criteria)

[0327] The formation of thin lines in the obtained pattern was confirmed using an optical microscope and evaluated in the following three stages.

[0328] ○: A pattern with an L / S of 15 μm / 15 μm or more was formed without residue

[0329] △: A pattern with an L / S of 30 μm / 30 μm or more was formed without residue.

[0330] ×: A pattern with an L / S of less than 50 μm / 50 μm was not formed, or curling or residue of the pattern was clearly present.

[0331]

[0332] The present invention can provide a photosensitive resin composition capable of providing a cured film having high light-shielding and insulating properties, excellent adhesion to a substrate, and excellent elastic modulus, deformation amount, and elastic recovery rate.

[0333] [Industrial Applicability]

[0334] The cured film of the photosensitive resin composition of the present invention can be extremely effectively used as a component of color filters including organic EL devices, quantum dot displays, TFT arrays, and wavelength conversion devices. Furthermore, resin compositions having a bis-naphthol fluorene skeleton are useful because they function as a light transmission control layer that blocks ultraviolet light within a specific range.

Claims

1. A photosensitive resin composition comprising the following components (A) to (D) as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group of the general formula (1); (B) (meth)acrylates selected from the group consisting of trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene alkylene oxide-modified hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; (C) a photopolymerization initiator; and (D) solvent, In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, 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; R1 is independently an alkylene group having 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), and Y is a tetravalent carboxylic acid residue; Z is independently a hydrogen atom or a substituent represented by general formula (4), and one or more substituents represented by general formula (4); and n is a number having an average value of 1 to 20; In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10; In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2. 2 . The photosensitive resin composition according to claim 1 , comprising (E) a coloring material.

3. 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.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein The component (A) is a compound wherein Ar in the general formula (1) contains a naphthalene skeleton.

5. The photosensitive resin composition according to claim 1, wherein The content of the component (A) is 10% to 90% by mass relative to the total mass of the solid content, 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 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B).

6. The photosensitive resin composition according to claim 2, wherein The content of the (E) coloring material is 1% by mass to 80% by mass relative to the total mass of the solid content of the photosensitive resin composition. 7 . A cured film formed by curing the photosensitive resin composition according to claim 1 . A display device comprising the cured film according to claim 7 .

Images