CN111812942A - Photosensitive resin composition, cured film, and display device - Google Patents

Abstract

The invention provides a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a display device having the cured film, wherein the photosensitive resin composition is suitable for a protection film with less gas generation, a coloring film of a shading film and the like. 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 represented by the general formula (1), (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) a photopolymerization initiator, and (D) a solvent.

Description

Photosensitive resin composition, cured film, and display device

technical field

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 cured film containing the cured film as a constituent touch screen and color filter.

Background technique

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

On the other hand, as a method of forming a protective film, there are a method of forming a protective film on the front surface by thermal curing, and a method of forming a protective film by a photolithography method. The method for forming the protective film can be selected according to the characteristics that the protective film should have and whether patterning is required during the panel design of the color filter and the design of the manufacturing process. Here, as properties of the protective film to be considered important when it is formed by photolithography, it is premised that it can have development properties capable of forming a desired pattern of the protective film, and it is necessary to have transparency, chemical resistance, density fit, hardness and electrical reliability.

For example, as transparency, the protective film is required to have no absorption in the wavelength range of visible light so as not to impair the color characteristics of the color filter. As chemical resistance, the stability of the protective film with respect to acids, alkalis, solvents, etc. used in subsequent steps is required. As for the adhesion, when a liquid crystal display panel is produced, the substrates are sometimes bonded on the protective film, so that the base of the protective film at the part is required to be a glass substrate, an indium tin oxide (ITO) substrate, and a glass substrate. Molybdenum/aluminum/molybdenum (molybdenum/aluminum/molybdenum, MAM) substrates and the like also do not peel off. As the hardness, high hardness is required from the viewpoint of the durability of the protective film. As electrical reliability, it is required that the protective film maintains insulating properties and that impurities and the like contained in the protective film do not contaminate the liquid crystal.

Among the characteristics required for the protective film, a wide viewing angle and high-speed response are required along with the high functionalization of the LCD panel, and a display method similar to an in-plane switching (IPS) mode is gradually used. , the requirements have become more stringent. In a display method such as the IPS mode, if gaseous or liquid components or water generated or exuded from the color filter layer enters the liquid crystal layer through the protective layer, the concentration of moisture or ionic impurities in the liquid crystal layer increases, or The formation of air bubbles in the liquid crystal layer can lead to poor display. Therefore, it is of course necessary to prevent the passage of the impurity components, and since gas generated from the protective film in direct contact with the liquid crystal layer is directly related to display failure, special attention is paid to low gas generation properties.

Furthermore, after the formation of the protective film, problems in the LCD panel manufacturing process such as photo-alignment treatment of the alignment film of the liquid crystal, and reduction of external light including various display devices such as organic electroluminescence (EL) have occurred. issue of influence. Therefore, in addition to securing transparency (high transmittance) as a protective film, there is a case where the protective film is required to have the ability to absorb short-wavelength ultraviolet light that does not contribute to color display.

SUMMARY OF THE INVENTION

[Problems to be Solved by Invention]

A photosensitive resin composition that can form an appropriate protective film pattern by photolithography and can fully maintain the characteristics of transparency, chemical resistance, adhesion, hardness, etc. of the protective film pattern is desired to sufficiently reduce the gas generation that affects electrical reliability. In addition, in color resists for forming red-green-blue (RGB) pixels, black resists for forming light-shielding films, and the like, there has been a demand for not only excellent properties but also low gas generation properties. Also excellent in the case of cured films.

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 The photosensitive resin composition can be suitably used for a protective film with little gas generation, a colored film containing a light-shielding film, and the like.

[Technical means to solve the problem]

The inventors of the present invention conducted studies to solve the problems in the photosensitive resin composition for the light-shielding film application, and as a result, found that a specific coloring material is preferable as a light-shielding component of the photosensitive resin composition for the light-shielding film application. The present invention has been 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 having an ethylenically unsaturated bond; (C) a photopolymerization initiator; and (D) a solvent.

[hua 1]

(In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms to which it is bonded may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl group or a cycloalkylalkyl group with a carbon number of 3 to 10, an alkoxy group with a carbon number of 1 to 5, or a halogen group. R ₁ is independently an alkylene group with a carbon number of 2 to 4, and l is respectively It is a number from 0 to 3 independently. 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 independently a hydrogen atom or is represented by the general formula The substituent represented by (4), and one or more of the substituents represented by the general formula (4). n is a number having an average value of 1 to 20.)

[hua 2]

[hua 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 an alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a carbon number of 2 to 20 The divalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

[hua 4]

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

The cured film of this invention hardens the said photosensitive resin composition.

The display device of this invention has the said cured film.

[Effect of invention]

According to the present invention, there can be provided a photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a display device having the cured film, which can be suitably used for containing A protective film with little gas generation, a colored film of a light-shielding film, and the like.

Detailed ways

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In addition, in this invention, regarding the content of each component, when the 1st decimal place is 0, the expression after a decimal point may be abbreviate|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 reactant 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 a raw material may contain several oxyalkylene groups in one molecule, and Ar in the general formula (1) is A compound of an aromatic hydrocarbon group having 6 to 14 carbon atoms.

Preferable 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 hydrogen atoms may be substituted with an alkyl group or the like. Here, the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention preferably has both of the two Ars bonded to the fluorene group in the general formula (1) that are naphthyl groups (having a bisnaphthol fluorene skeleton) or Both are phenylene groups (having a bisphenolfluorene skeleton), and it is more preferable that both of the two Ars bonded to the fluorenyl group are naphthyl groups. The reason for this is the gas generated when the cured film (coating film) of the (A) polymerizable unsaturated group-containing alkali-soluble resin in which both Ars bonded to the fluorene group are naphthyl groups is heated is heated. amount is small. In addition, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and means one or both of them.

[hua 5]

(In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms to which it is bonded may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl group or a cycloalkylalkyl group with a carbon number of 3 to 10, an alkoxy group with a carbon number of 1 to 5, or a halogen group. R ₁ is independently an alkylene group with a carbon number of 2 to 4, and l is respectively It is a number from 0 to 3 independently. 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 independently a hydrogen atom or is represented by the general formula The substituent represented by (4), and one or more of the substituents represented by the general formula (4). n is a number having an average value of 1 to 20.)

[hua 6]

[hua 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 an alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a carbon number of 2 to 20 The divalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

[hua 8]

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

The manufacturing method of the polymerizable unsaturated group containing alkali-soluble resin represented by General formula (1) is demonstrated in detail.

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

[Chemical 9]

(In formula (5), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms to which it is bonded may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl group or a cycloalkylalkyl group with a carbon number of 3 to 10, an alkoxy group with a carbon number of 1 to 5, or a halogen group. R ₁ is independently an alkylene group with a carbon number of 2 to 4, 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 an alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a carbon number of 2 to 20 The divalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

A well-known method can be used for the reaction of the said epoxy compound (a-1) and the said (meth)acrylic acid derivative. For example, Japanese Patent Laid-Open No. 4-355450 describes that by using about 2 mol of (meth)acrylic acid with respect to 1 mol of an epoxy compound having two epoxy groups, it is possible to obtain a polymerizable Unsaturated diol compounds. In the present invention, the compound obtained by the reaction is a polymerizable unsaturated group-containing diol (d) represented by the formula (8) (hereinafter, also simply referred to as "represented by the general formula (8)" diol (d)").

[Chemical 12]

(In formula (8), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms to which it is bonded may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group. , substituted with a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. G is a substitution represented 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 of 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 an alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a carbon number of 2 to 20 The divalent saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.)

The polymerizable unsaturated group-containing base represented by the general formula (1) is produced by the synthesis of the diol (d) represented by the general formula (8) and subsequent reaction of a polyvalent carboxylic acid or an acid anhydride thereof In the case of a soluble resin, the reaction is usually carried out using a catalyst in a solvent as necessary.

Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; diethylene glycol dimethyl ether (diglyme), ethyl carbitol acetate, butyl card High-boiling ether-based or ester-based solvents such as bisphenol acetate and propylene glycol monomethyl ether acetate; ketone-based solvents such as cyclohexanone and diisobutyl ketone, etc. In addition, the reaction conditions of the solvent, catalyst, etc. to be used are not particularly limited. For example, a solvent having no hydroxyl group and a boiling point higher than the reaction temperature is preferably used as the reaction solvent.

In addition, a catalyst is preferably used in the reaction between an epoxy group and a carboxyl group or a hydroxyl group, and ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride are described in Japanese Patent Laid-Open No. 9-325494; 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 allowed to Carboxylic acid or its acid monoanhydride (b), and tetracarboxylic acid or its acid dianhydride (c) are reacted to obtain a compound having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (1). Alkali-soluble resin.

[Chemical 15]

(In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms to which it is bonded may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group. , substituted by a cycloalkyl group or a cycloalkylalkyl group with a carbon number of 3 to 10, an alkoxy group with a carbon number of 1 to 5, or a halogen group. R ₁ is independently an alkylene group with a carbon number of 2 to 4, and l is respectively It is a number from 0 to 3 independently. 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 independently a hydrogen atom or is represented by the general formula The substituent represented by (4), and one or more of the substituents represented by the 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 an alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a carbon number of 2 to 20 The divalent 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, with respect to the (meth)acrylic acid derivatives represented by the general formula (6) and the general formula (7), which constitute the alkali-soluble resin represented by the general formula (1), the (meth)acrylic acid derivatives represented by 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 or more ester bonds.

[Chemical 19]

[hua 20]

[Chemical 21]

[Chemical 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 alkylarylene group having 2 to 10 carbon atoms. The alkylene group can be any one of straight chain or branched, and is vinyl (ethylene), ethylene (ethylidene), vinylene (vinylene), vinylidene (vinylidene), propylene group (propylene), Sanya Methyl, propenylene, isopropylidene, tetramethylene, etc. In addition, the alkylarylene group may be an unsubstituted arylene group as long as it is within the range of carbon number, for example, o-phenylene, m-phenylene, p-phenylene, tolylene, ethyl phenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, pentylphenylene, and the like.

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 an aromatic hydrocarbon group having 2 to 20 carbon atoms. . The saturated and unsaturated aliphatic hydrocarbon groups can be either straight chain or branched, and are vinyl, ethylene, vinylene, vinylidene, propenyl, trimethylene, propenylene, isopropylene base, tetramethylene, etc. In addition, as long as the aromatic hydrocarbon group is within the range of carbon number, it may be an unsubstituted body, for example, o-phenylene, m-phenylene, p-phenylene, tolylene, ethylphenylene , n-propylphenylene, isopropylphenylene, straight-chain or branched butylphenylene, pentylphenylene, etc., and as long as it does not exceed the range of carbon number, it can also pass through two to four Substituents are substituted. In addition, the aliphatic hydrocarbon group may be interrupted by an unsaturated bond, an ether bond, or an ester bond.

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

The acid component for synthesizing the alkali-soluble resin represented by the general formula (1) is a polybasic acid component that can react with the hydroxyl group in the molecule of the diol (d) represented by the general formula (8), and it is necessary to use two 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 contain a bond containing hetero elements such as -O-, -S-, and carbonyl.

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, and the like.

Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, Acid monoanhydrides such as glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and dicarboxylic or tricarboxylic acids into which optional substituents are introduced Acid monoanhydrides, etc. In addition, examples of the acid monoanhydride of alicyclic dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane An acid monoanhydride such as an alkanedicarboxylic acid, an acid monoanhydride of a dicarboxylic acid or tricarboxylic acid into which an optional substituent is introduced, and the like. In addition, examples of the acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, and dicarboxylic acids into which arbitrary substituents are introduced, or Acid monoanhydrides of tricarboxylic acids.

Among the acid monoanhydrides of dicarboxylic acid or tricarboxylic acid, 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. Moreover, among dicarboxylic acid or tricarboxylic acid, the acid monoanhydride using these is preferable. Only one of these acid monoanhydrides of the dicarboxylic acid or tricarboxylic acid may be used alone, or two or more of them may be used in combination.

In addition, examples of the tetracarboxylic acid or its acid dianhydride (c) include a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or their acid dianhydrides and the like.

Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acid into which substituents such as alicyclic hydrocarbon group and unsaturated hydrocarbon group are introduced. . In addition, examples of the alicyclic tetracarboxylic acid include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and Alicyclic tetracarboxylic acid etc. into which substituents, such as a chain hydrocarbon group and an unsaturated hydrocarbon group, were introduce|transduced. In addition, examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, and naphthalene-1 , 4,5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, etc. In addition, bis-trimellitic anhydride aryl esters can also be used. Bis trimellitic anhydride aryl esters are, for example, a group of compounds produced by the method described in WO2010/074065, and are structurally aromatic diols (naphthalene diol, biphenol, terphenyl diol, etc.) An acid dianhydride in a form in which two hydroxyl groups react with carboxyl groups of two molecules of trimellitic acid anhydride and are ester-bonded. Hereinafter, the compound is described as bis-trimellitic acid 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 acid or its acid dianhydride, its acid dianhydride is used preferably. Furthermore, the bis-trimellitic acid anhydride ester of naphthalene glycol can also be preferably used. In addition, the bis-trimellitic acid anhydride ester of the said tetracarboxylic acid or its acid dianhydride and aromatic diol may be used individually by 1 type, and may use 2 or more types together.

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 Laying-Open No. 9-325494 describes a method of reacting epoxy (meth)acrylate 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 the diol (d), dicarboxylic acid or tricarboxylic acid represented by the general formula (8), or their acid monoanhydride (b), tetracarboxylic acid or their The reaction was performed so that the molar ratio of the acid dianhydride (c) was (d):(b):(c)=1.0:0.01-1.0:0.2-1.0.

For example, in the case of using the acid monoanhydride (b) and the acid dianhydride (c), the amount of the acid component [(b)/2+(c)] relative to the polymerizable unsaturated group-containing diol ( The reaction is carried out so that the molar ratio [(d)/[(b)/2+(c)]] of d) 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 that the temporal stability 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 the formula (2) does not become an acid anhydride, an increase in the content of the unreacted acid dianhydride can be suppressed, so that the alkali-soluble resin composition can be improved. The time stability of the material. In addition, the molar ratio of each component of (b), (c) and (d) can be arbitrarily changed within the above-mentioned range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (2). .

Moreover, the preferable range of the acid value of the alkali-soluble resin represented by General formula (1) is 20 mgKOH/g - 180 mgKOH/g, Preferably it is 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, and when the acid value is 180 mgKOH/g or less, the penetration of the alkaline developer does not become too fast, so peeling can be suppressed Phenomenon. In addition, an acid value can be calculated|required by performing titration with a 1/10N-KOH aqueous solution using a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

Weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin represented by the general formula (1) (HLC-8220GPC, manufactured by Tosoh Co., Ltd.) The 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 a weight average molecular weight is 1000 or more, the fall of the pattern adhesiveness at the time of alkaline image development can be suppressed. Moreover, when a weight average molecular weight (Mw) is less than 100000, it becomes easy to adjust to the solution viscosity of the photosensitive resin composition preferable for application|coating, and alkaline image development does not require time too much.

Next, the photosensitive resin composition using the alkali-soluble resin represented by General formula (1) of this invention is demonstrated.

As the photosensitive resin composition of this invention, it is preferable that content of (A) component is 10 mass % - 90 mass % with respect to the total mass of solid content. Moreover, the content of (B) component is preferably 5 to 200 parts by mass relative to 100 parts by mass of (A) component, and (C) component is preferably 5 parts by mass to 200 parts by mass of the total amount of (A) component and (B) component 100 parts by mass The content 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, trimethylolethyl 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, alkylene oxide-modified hexa(meth)acrylate of phosphazene, hexamethylene oxide Lactone-modified dipentaerythritol hexa(meth)acrylate and other (meth)acrylates; dendrimer-type multifunctional acrylates, etc. Only one of these photopolymerizable monomers may be used alone, or two or more of them may be used in combination.

The content of the component (B) is preferably 5 parts by mass to 200 parts by mass relative to 100 parts by mass of the component (A), more preferably 10 parts by mass to 80 parts by mass relative to 100 parts by mass of the component (A), and still more preferably 10 to 60 parts by mass. When content of (B) component is 5 mass parts or more with respect to 100 mass parts of (A) components, since the quantity which a photoreactive functional group occupies in resin is sufficient, a sufficient crosslinked structure is formed. In addition, since the acid value in the resin component does not become too high, the solubility of the exposed portion with respect to the alkaline developing solution is lowered, so that the formed pattern can be suppressed from becoming thinner than the target line width, and the pattern can be suppressed. the absence of. Moreover, since content of (B) component is 200 mass parts or less with respect to 100 mass parts of (A) components, since the cured film which has sufficient curability can be obtained, a pattern edge can be made clear.

Examples of the (C) photopolymerization initiator in the photosensitive resin composition of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Acetophenones such as propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethyl ketone Aminobenzophenone and other benzophenones; benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 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-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds; 2-trichloromethyl-5-styrene base-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-( p-methoxystyryl)-1,3,4-oxadiazole and other halogenated methyloxadiazole compounds; 2,4,6-tris(trichloromethyl)-1,3,5-triazine , 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5- Triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6- Bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl) -4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3 ,5-triazine and other halogenated methyl-s-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime ), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane- O-acyl oxime compounds such as 1,2-diketo-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-ketooxime-O-acetate, etc. ; Benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthoxanthone, 2-isopropylthiane Sulfur compounds such as anthraquinone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone; azobisisobutyronitrile, benzene Formyl peroxide, cumene peroxide and other organic peroxides; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and other thiol compounds; triethanolamine, triethylamine and other tertiary amines. Further, only one of the photopolymerization initiators may be used alone, or two or more of them may be used in combination.

In particular, in the case of a photosensitive resin composition containing a coloring material, it is preferable to use O-acyl oxime-based compounds (including ketoximes). As a specific compound group, there is an O-acyl oxime-based photopolymerization initiator represented by the general formula (9) or the general formula (10). In the compound group, in the case of using a coloring material at a high pigment concentration and in the case of forming a light-shielding film pattern, it is preferable to use an O-acyl oxime-based photopolymerization initiator having a molar absorption coefficient at 365 nm of 10,000 L/mol·cm or more. agent. In addition, the "photopolymerization initiator" as used in the present invention is used in the sense of including a sensitizer.

[Chemical 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 arylalkyl group having 4 to 12 carbon atoms. , R ₇ is an alkyl group with 1 to 15 carbon atoms, an aryl group with 6 to 18 carbon atoms, and an arylalkyl group with 7 to 20 carbon atoms. 10 alkyl groups, alkoxy groups having 1 to 10 carbon atoms, alkanoyl groups having 1 to 10 carbon atoms, halogen substitution, and the alkylene moiety may contain unsaturated bonds, ether bonds, thioether bonds, and ester bonds. The group may be any of straight chain, branched or cyclic alkyl groups.)

[Chemical 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 having 4 to 10 carbon atoms, a cycloalkylalkyl group, or Alkylcycloalkyl, or a phenyl group 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 an alkenyl group having 2 to 10 carbon atoms, and the alkane A part of the -CH ₂ - group in the group or the alkenyl group may be substituted with an -O- group. Furthermore, a part of the hydrogen atoms in the groups of R ₈ to R ₁₀ may be substituted with a halogen atom.)

The content of the 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 the (A) component and the (B) component. When content of (C)component is 0.1 mass part or more, since there exists a moderate photopolymerization speed|rate, the fall of a sensitivity can be suppressed. Moreover, when content of (C)component is 30 mass parts or less, the line width faithful to a mask can be reproduced, and a pattern edge can be made clear.

(D) Examples of the solvent contained in the photosensitive resin composition include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol mono Alcohols such as butyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α-terpineol or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-methyl ethyl ketone Ketones such as base-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, 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, Glycol ethers such as triethylene glycol monoethyl ether; 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 Esters such as carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, etc. By dissolving and mixing them, a uniform solution-like composition can be obtained. In order to obtain necessary properties such as coatability, these solvents may be used alone or in combination of two or more. 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 said photosensitive resin composition contains a coloring material as (E) component. When used as a resist for light-shielding films, the component (E) is one or more light-shielding components selected from the group consisting of black organic pigments, color-mixing organic pigments, and light-shielding materials, preferably black organic pigments Pigments and/or color mixing organic pigments. In addition, the average secondary particle diameter of the black organic pigment and/or the color mixing organic pigment is preferably 20 nm to 500 nm. The average secondary particle size of the black organic pigments and the color-mixing organic pigments can be measured by a cumulative 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 light-shielding degree, but is preferably 1% by mass to 80% by mass relative to the solid content in the photosensitive resin composition. In the case of a pigment, it 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, lactam black, and the like. Examples of color-mixing organic pigments include: selected from azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine At least two colors of organic pigments such as pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are mixed and simulated blackened. made of paint. As a light-shielding material, carbon black, chromium oxide, iron oxide, titanium black, etc. are contained. The said (E) component can also use the pigment surface-treated suitably according to the function of the target photosensitive resin composition. In addition, only 1 type of the said (E) component may be used independently, and 2 or more types may be used together.

Examples of organic pigments that can be used as the component (E) include, but are not limited to, those having the following numbers in the name of the Color Index.

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 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

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 7, 36, 58, etc.

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

Pigment violet 19, 23, 37, etc.

Moreover, it is preferable to mix|blend in the photosensitive resin composition the coloring material which is (E) component disperse|distributes in the (D) solvent together with the (F) dispersing agent in advance to prepare a coloring material dispersion. Here, since the solvent for dispersing becomes a part of (D)component, it can be used as long as it is the solvent contained in the said (D)component. Among the components (D), propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butyl acetate, and the like are preferable.

1 mass % - 80 mass % are preferable with respect to the total solid content of the photosensitive resin composition of this invention, and, as for content of (E) component, 30 mass % - 60 mass % are more preferable. In addition, the said solid content means the component other than (D)component in the photosensitive resin composition. (B) component which becomes a solid content after photohardening is also contained in the said solid content. When the component (E) is 1 mass % or more, it is easy to set desired light-shielding properties. Moreover, when the (E) component is 80 mass % or less, desired developing characteristics and film forming ability can be obtained.

As the (F) dispersant, known compounds (commercially available compounds such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) used for dispersing coloring materials (pigments) and the like can be used without particular limitation. .

Examples of the dispersing agent as the component (F) include a cationic polymer-based dispersant, an anionic polymer-based dispersant, a nonionic polymer-based dispersant, and a pigment derivative type dispersant (dispersing aid). In particular, the dispersing agent preferably has a cationic functional group such as an imidazole group, a pyrrole 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 in terms of adsorption of coloring materials. /g, a cationic polymer-based dispersant having a number average molecular weight in the range of 1,000 to 100,000. It is preferable that the compounding quantity of the said dispersing agent is 1 mass % - 35 mass % with respect to a coloring material, and it is more preferable that it is 2 mass % - 25 mass %. In addition, high-viscosity substances such as resins generally have a function of stabilizing dispersion, and substances that do not have a dispersion-promoting ability are not regarded as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

In addition, when preparing the coloring material dispersion, not only the dispersing agent (F), but also a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is co-dispersed, whereby it is possible to easily disperse the dispersion. The exposure sensitivity is maintained at a high sensitivity, the adhesiveness at the time of image development is good, and the photosensitive resin composition is less likely to cause the problem of residues. In the coloring material dispersion, the content of the component (A) is preferably 2% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass. When the component (A) is 2 mass % or more, effects after co-dispersion such as improved sensitivity, improved adhesion, and reduced residues can be obtained. Moreover, when (A) component is 20 mass % or less, the cured film (coating film) which disperse|distributed (E) component uniformly can be obtained.

The said coloring material dispersion is mixed with (A) component (when co-dispersing the (A) component when preparing the coloring material dispersion, with the remaining (A) component), (B) component, (C) component, It can be mixed with the remaining (E) component, and can be set as the photosensitive resin composition for light-shielding films.

Moreover, the photosensitive resin composition of this invention can use together another resin component which polymerizes or hardens by light or heat as needed. Examples of other resin components include: epoxy resins such as novolak epoxy resins, bisphenol type epoxy resins, etc. derived from novolaks such as phenol novolacs and cresol novolacs; ) Alkali-soluble resin (excluding component (A)) obtained by reacting acrylic acid and acid anhydride, copolymers with (meth)acrylic acid and/or (meth)acrylic acid esters, and a carboxyl group in the copolymer The alkali-soluble resin etc. obtained by reacting the (meth)acrylate of an epoxy group.

In the photosensitive resin composition of the present invention, a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent, etc. can be blended as necessary. additive.

Examples of the curing agent include amine-based compounds, polyvalent carboxylic acid-based compounds, phenol resins, amino resins, dicyandiamine, and Lewis acid complex compounds that contribute to curing of epoxy resins. Examples of the hardening accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, and the like, which contribute to the hardening of epoxy resins. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenol-based compounds, and the like. Examples of the plasticizer include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of filler materials include: glass fibers, silica, mica, alumina, and the like. Examples of the defoaming agent or leveling agent 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-acryloyloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 - Ureidopropyltriethoxysilane, etc.

The cured film (coating film) of the present invention can be formed by a photolithography method using the photosensitive resin composition of the present invention. The method is a method of first applying a photosensitive resin composition solution on the surface of a substrate, drying the solvent (pre-baking), placing a photomask on the coating film, irradiating ultraviolet rays to harden the exposed portion, and further Development to elute the unexposed portion using an alkaline aqueous solution is performed to form a pattern, and further post-baking is performed as post-curing. Here, examples of the substrate to which the photosensitive resin composition solution is applied include glass, transparent films (eg, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) and the like.

The substrate may be a transparent substrate or a base material other than the transparent substrate. Examples of the transparent substrate to which the photosensitive resin composition is applied include not only glass substrates, but also transparent films (eg, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) that are vapor-deposited or patterned thereon. Substrates of transparent electrodes such as ITO or gold, etc.

As a method of applying the photosensitive resin composition solution on the substrate, not only the known solution dipping method and spray method, but also a roll coater, a land coater machine, a narrow Slot coater or rotary machine method, etc. After coating to a desired thickness by the above-described method, the solvent is dried (pre-baking) to form a film. In addition, the prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the prebaking can be appropriately selected according to the solvent to be used, and for example, it is performed at a temperature of 60° C. to 110° C. for 1 minute to 3 minutes.

The exposure performed after the pre-baking is performed by an ultraviolet exposure apparatus, and only the resist of the part corresponding to a pattern is exposed to light through a photomask. The photosensitive resin composition in the coating film is photocured by appropriately selecting an exposure apparatus and its exposure irradiation conditions, and exposing using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an extreme ultraviolet lamp.

As radiation used for exposure, visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, etc. can be used, for example, and the wavelength range of the radiation is preferably 250 nm to 450 nm. Moreover, as a developing solution suitable for the said alkaline image development, the aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used, for example. The developer can be appropriately selected according to the properties of the resin layer, but it is also effective to add a surfactant as needed. The developing temperature is preferably 20°C to 35°C, and a fine image can be precisely formed using a commercially available developing machine, an ultrasonic cleaner, or the like. Moreover, after alkaline image development, water washing is usually performed. As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle (liquid-coated) development method, and the like can be applied.

Alkaline development after exposure is performed for the purpose of removing the photosensitive resin composition of the unexposed portion, and a desired pattern is formed by the development. As a developing solution suitable for the alkaline development, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, etc. are mentioned, and particularly, carbonic acid containing 0.03 to 1 wt % is preferably used. A weakly alkaline aqueous solution of carbonate such as sodium and potassium carbonate is developed at a temperature of 23° C. to 27° C., and fine images can be precisely formed using a commercially available developing machine, an ultrasonic cleaner, or the like.

After developing as described above, heat treatment (post-baking) is performed at 180° C. to 250° C. for 20 minutes to 100 minutes. However, even when the heat resistance of the substrate etc. used for film formation is low, the preparation of the composition can be designed so that the post-baking conditions of 80° C. to 180° C. and 30 minutes to 100 minutes can be used. . The post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate, and the like. This is performed by heating with an oven, a hot plate, or the like, similarly to the prebaking. The patterned resin film of the present invention is formed through each of the above steps by photolithography.

[Example]

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

First, the synthesis example of the polymerizable unsaturated group-containing alkali-soluble resin including the structure represented by the general formula (1) will be described, and unless otherwise specified, the evaluation of the resin in the synthesis example is as follows generally proceed. Regarding various measurement devices, when the same model is used, the name of the device manufacturer is omitted from the second point. In addition, in Example 1 and Example 2, the glass substrate used for preparation of the board|substrate with the cured film for measurement used the glass substrate which performed the same process in all.

[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 the weight [W 1 (g)] after heating at 160°C for 2 hours was used. ₂ (g)] and obtained by the following equation (1).

Solid content concentration (% by weight)=100×(W ₂ -W ₀ )/(W ₁ -W ₀ ) (1)

[Epoxy equivalent]

After dissolving the resin solution in dioxane, an acetic acid solution of tetraethylammonium bromide was added, a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) was used, and 1/10N-perchloric acid was used. The solution is titrated to obtain.

[acid value]

The resin solution was dissolved in dioxane, and was determined by titration with a 1/10 N-KOH aqueous solution using a potentiometric titration device "COM-1600".

[Molecular weight]

By gel 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) for measurement, and used as a standard polystyrene (Tosoh (Tosoh) Tosoh) Co., Ltd. product, PS-oligomer set) conversion value, and the weight average molecular weight (Mw) was calculated|required.

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

BPFE: Bisphenol Fluorene Epoxy Resin

(Epoxy resin in which Ar is a benzene ring and l is 0 in the general formula (5), epoxy equivalent 256)

BNFE: bisnaphthol fluorene type epoxy resin

(Epoxy resin in which Ar is a naphthalene ring and l is 0 in the general formula (5), epoxy equivalent 281)

HOA-HH: 2-Acryloyloxyethylhexahydrophthalic acid

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

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

BTDA: Benzophenone Tetracarboxylic Dianhydride

BTANE: Bis trimellitic anhydride ester of naphthalene diol (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, at 100°C to 105 The mixture was stirred at °C for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was injected|thrown-in, and it adjusted so that solid content might become 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 a polymerizable unsaturated group-containing alkali-soluble solution. Resin solution (A)-1. The solid content concentration of the obtained resin solution was 57.3 mass %, the acid value (solid content conversion) was 96 mgKOH/g, and the Mw by GPC analysis was 3600.

[Synthesis Example 2]

BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were put into a 250 mL four-necked flask with a reflux cooler, and the temperature was 100°C to 105 The mixture was stirred at °C for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was injected|thrown-in, and it adjusted so that solid content might become 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 a polymerizable unsaturated group-containing alkali-soluble solution. 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 by GPC analysis was 4000.

[Synthesis Example 3]

BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were put into a 250 mL four-necked flask with a reflux cooler, and the temperature was 100°C to 105 The mixture was stirred at °C for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was injected|thrown-in, and it adjusted so that solid content might become 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 a polymerizable unsaturated group-containing alkali-soluble solution. 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 by GPC analysis was 2600.

[Synthesis Example 4]

BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were put into a 250 mL four-necked flask with a reflux cooler, and the temperature was 100°C to 105 The mixture was stirred at °C for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was injected|thrown-in, and it adjusted so that solid content might become 50 mass %.

Next, 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 polymer. Resin solution (A)-4. The solid content concentration of the obtained resin solution was 56.1 mass %, the acid value (solid content conversion) was 83 mgKOH/g, and the Mw by GPC analysis was 7000.

[Synthesis Example 5]

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 put into a 250 mL four-necked flask with a reflux cooler, and the temperature was 100°C. The reaction product was obtained by stirring at -105°C for 12 hours. Then, PGMEA (20.00 g) was injected|thrown-in, and it adjusted so that solid content might become 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 a polymerizable unsaturated group-containing alkali-soluble solution. 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 by GPC analysis was 5300.

[Synthesis Example 6]

BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were put into a 250 mL four-necked flask with a reflux cooler, and the temperature was 100°C to 105 The mixture was stirred at °C for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was injected|thrown-in, and it adjusted so that solid content might become 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 a polymerizable unsaturated group-containing alkali-soluble polymer. Resin solution (A)-6. The solid content concentration of the obtained resin solution was 54.6 mass %, the acid value (solid content conversion) was 92 mgKOH/g, and the Mw by GPC analysis was 4100.

[Synthesis Example 7]

BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were put into a 250 mL four-necked flask with a reflux cooler, and the temperature was 100°C to 105 The mixture was stirred at °C for 12 hours to obtain a reaction product. Then, PGMEA (20.00 g) was injected|thrown-in, and it adjusted so that solid content might become 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 a polymerizable unsaturated group-containing alkali-soluble polymer. 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 by GPC analysis was 5000.

[Synthesis Example 8]

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) was polymerized by stirring under nitrogen flow at 80°C to 85°C 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 a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-8. The solid content concentration of the obtained resin solution was 35.7 mass %, the acid value (solid content conversion) was 50 mgKOH/g, and the Mw by GPC analysis was 19600.

(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 (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-carbazol-3-yl]-,1- (O-acetyl oxime), manufactured by BASF Corporation, "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)

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

[Example 1]

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

[Evaluation]

The following evaluations were performed using the photosensitive resin compositions of Examples 1 to 10, Comparative Example 1, and Comparative Example 2.

(Production of cured film (coating film))

Using a spin coater, the photosensitive resin composition shown in Table 1 was applied to an ultraviolet ray having an illuminance of 1000 mJ/cm ² with a wavelength of 254 nm and washed in advance so that the film thickness after heat curing treatment was 1.5 μm. Glass substrate "EAGLE (EAGLE) XG" (manufactured by Corning) (hereinafter referred to as "glass substrate") with a surface of 50 mm × 50 mm, indium tin oxide vapor-deposited glass substrate (hereinafter referred to as ""glass substrate") ITO substrate") and a molybdenum-aluminum alloy vapor deposition substrate (hereinafter referred to as "MAM substrate") were pre-baked at 90°C for 1 minute using a hot plate to prepare a coated plate. Next, ultraviolet rays of 100 mJ/cm ² were irradiated with a high-pressure mercury lamp having an illuminance of 30 mW/cm ² at a wavelength of 365 nm to perform a photohardening reaction. Then, hardening process was performed at 230 degreeC for 30 minutes using a hot air dryer, and the cured film (coating film) of Example 1 - Example 10 and Comparative Example 1 and Comparative Example 2 was obtained.

About the cured film (coating film) containing the photosensitive resin composition of Examples 1-10 obtained above, the comparative example 1, and the comparative example 2, the following items were evaluated, and the result is shown in Table 2. These evaluation methods were performed as follows. Moreover, regarding the high temperature and high humidity resistance adhesiveness and chemical resistance adhesiveness, not only the cured film (coating film) on the glass substrate but also the cured film (coating film) produced on the ITO substrate and the MAM substrate were evaluated. Evaluate.

(Film thickness measurement)

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

[High temperature and high humidity resistance]

(Evaluation method)

The cured film (coating film) produced on the glass substrate, the ITO substrate, and the MAM substrate was left still for 5 hours under the conditions of a temperature of 121° C., a humidity of 100%, and an air pressure of 2 atm. Then, a cross cut peeling test in which cuts were made in the substrate using a Super Cutter Guide (manufactured by Taiyou Machinery Co., Ltd.) to form 100 pieces of 1 mm×1 mm was carried out. A square grid, cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the grid and then peeled off.

(Evaluation Criteria)

○: All the cured films (coating films) in the mesh are not peeled off

△: Less than 1/3 of the cured film (coating film) in the mesh is peeled off

×: Peeling occurred in 1/3 or more

[Chemical Resistance Adhesion]

(Evaluation method)

The cured films (coating films) prepared on glass substrates, ITO substrates, and MAM substrates were immersed in a petri dish containing N-methyl-2-pyrrolidone at 60° C. for 2 minutes, washed with pure water, and then cleaned. Wipe away moisture. Then, a cross-cut peel test was performed by using a Super Cutter Guide to make cuts in the substrate to form 100 square grids of 1 mm x 1 mm, and after attaching cellophane tape to the grids, peel off.

(Evaluation Criteria)

○: All the cured films (coating films) in the mesh are not peeled off

△: Less than 1/3 of the cured film (coating film) in the mesh is peeled off

×: Peeling occurred in 1/3 or more

[Film hardness 1]

(Evaluation method)

According to the test method of Japanese Industrial Standards (JIS)-K5600-5-4, a load of 750 g was applied to the cured film (coating film) produced on the glass substrate using a pencil hardness tester, and the cured film (coating film) It is expressed by the highest pencil hardness when no damage occurs. The pencil used was "HI-Uni" (manufactured by Mitsubishi Pencil Co., Ltd.). Moreover, this evaluation was implemented as an index|index of the resistance with respect to the force (scratches) of a coating film surface.

(Evaluation Criteria)

○: 3H or more

△: 2H

×: H or less

[Film hardness 2]

(Evaluation method)

The cured film (coating film) produced on the glass substrate was measured using a micro-film hardness tester "HM2000" (manufactured by Fischer Instruments). A Vickers indenter was used as the indenter, a load of 5 mN/μm ² was applied at a load speed of 0.25 mN/sec, the load was removed after holding for 1 second, and the Martens hardness was measured (according to the International Organization for Standardization, ISO)14577). This evaluation was implemented as an index of the resistance of the cured film (coating film) surface with respect to the force (pressing) in the longitudinal direction. In addition, "Martens hardness" means the hardness calculated from the load-insertion depth curve.

(Evaluation Criteria)

○: 65N/ ^mm2 or more

△: 60N/ ^mm2 or more and less than 65N/ ^mm2

×: Less than 60N/mm ²

[Transmittance 1]

(Evaluation method)

Using a transmittance meter "SPECTRO PHOTOMETER SD 5000" (manufactured by Nippon Denshoku Kogyo Co., Ltd.), a cured film with a film thickness of 2 μm was prepared on the glass substrate "EAGLE XG" (coating film) The transmittance|permeability measurement was performed.

(Evaluation Criteria)

○: The transmittance at a wavelength of 400 nm is 95% or more

△: The transmittance at a wavelength of 400 nm is 90% or more and less than 95%

×: Less than 90%

[Transmittance 2]

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

(Evaluation Criteria)

○: The transmittance at a wavelength of 340 nm is less than 20%

△: The transmittance at a wavelength of 340 nm is 20% or more and less than 65%

×: 65% or more

[gas-generating]

(Evaluation method)

The cured film (coating film) produced on the glass substrate "EAGLE XG" was ground with a scraper or the like, and a differential thermal analysis-thermogravimetry apparatus (Thermogravimetry- Differential Thermal Analysis, TG/DTA)) "EXSTAR 6000" (manufactured by Hitachi High-Tech Science Co., Ltd.) measured the obtained powdery cured film (coating film) 10 mg Thermogravimetric loss. The measurement conditions were pre-treated at 120° C. for 30 minutes in the atmosphere, and then kept at 230° C. for 3 hours. The gas generating property was evaluated by the weight reduction rate, which was calculated from the weight reduction before and after heating at 230°C.

(Evaluation Criteria)

◎: The weight reduction rate is less than 3%

○: The weight reduction rate is 3% or more and less than 7%

△: The weight reduction rate is 7% or more and less than 15%

×: The weight reduction rate is 15% or more

[water absorption]

(Evaluation method)

The cured film (coating film) produced on the glass substrate "EAGLE XG" was left to stand for 24 hours at a constant temperature and humidity of 40°C and a humidity of 90%, and then ground with a scraper or the like , the thermogravimetric loss of 10 mg of the obtained powdery cured film (coating film) was measured using a differential thermal analysis-thermogravimetric measuring apparatus (TG/DTA) "EXSTAR 6000". The measurement conditions were made to raise the temperature to 120° C. at 10° C./min in a nitrogen atmosphere, and to hold the temperature for 1 hour. The water absorption was evaluated by the weight loss rate.

(Evaluation Criteria)

○: The weight reduction rate is less than 2%

△: The weight reduction rate is 2% or more and less than 5%

×: The weight reduction rate is 5% or more

[Development characteristics]

(Preparation of Evaluation Samples)

Using a spin coater, the photosensitive resin composition shown in Table 1 was applied on a glass substrate "EAGLE XG" of 125 mm x 125 mm so that the film thickness after heat curing treatment was 1.5 μm, and the The hotplate was pre-baked at 90°C for 1 minute. Then, the photomask was set to have an exposure gap of 150 μm, and ultraviolet rays of 100 mJ/cm ² were irradiated with a high-pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction of the photosensitive portion.

Next, using a 0.05% potassium hydroxide aqueous solution or a 0.2% sodium carbonate aqueous solution at 23° C., the exposed cured film (coating film) was developed under a pressure of 0.1 MPa for 60 seconds, further washed with water, and the cured film (coating film) was The unexposed portion of the film) is removed. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot-air dryer, and obtained the cured film (pattern) of Examples 1-10, the comparative example 1, and the comparative example 2.

(Evaluation Method and Evaluation Criteria)

The formation of thin lines in the obtained pattern was confirmed with an optical microscope, and the evaluation was performed in the following three stages.

○: A pattern with an 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 formed, or there is obvious curling or residue of the pattern

[Example 2]

The preparation components of (A) to (F) were prepared at the ratios shown in Table 3, and the photosensitive resin compositions containing the light-shielding pigment dispersion liquid of Examples 11 to 16 and Comparative Examples 11 to 13 were prepared. (D)-1 in the column of solvent does not contain PGMEA (same as (D)-1) in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution), light-shielding pigment dispersion The amount of solvent in the liquid and the solvent in the surfactant. In addition, all the numerical values in Table 3 represent mass %.

(Light-shielding pigment dispersion)

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

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

[Evaluation]

The following evaluations were performed using the photosensitive resin compositions of Examples 11 to 16 and Comparative Examples 11 to 13. These evaluation results are shown in Table 4.

[Measurement of Optical Density]

Using a spin coater, the photosensitive resin composition shown in Table 3 was applied on a glass substrate of 125 mm×125 mm so that the film thickness after heat curing treatment was 1.1 μm, and prebaked at 90° C. for 1 minute. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film (coating film) of Example 11 - Example 16 and Comparative Example 11 - Comparative Example 13. Next, the optical density (optical density, OD) of the obtained cured film (coating film) was measured using a Macbeth densitometer, and it evaluated by the optical density per unit film thickness.

[Measurement of volume resistivity]

(test methods)

Using a spin coater, each photosensitive resin composition shown in Table 3 was applied on a 100 mm×100 mm glass substrate with a thickness of 1.2 mm in which Cr was vapor-deposited so that the film thickness after the heat curing treatment was 3.5 μm. Except for the electrodes, pre-bake at 90°C for 1 minute. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film (coating film) of Example 11 - Example 16 and Comparative Example 11 - Comparative Example 13. Then, an aluminum electrode was formed on the cured film (coating film), and the board|substrate for volume resistivity measurement was produced. Next, the volume resistivity from the applied voltage of 1V to the applied voltage of 10V was measured using an electrometer "Model 6517A" (manufactured by Keithley). In addition, the measurement was carried out under the condition of holding the voltage for 60 seconds at each applied voltage in a step of 1 V.

[Measurement of Dielectric Constant]

(test methods)

Using a spin coater, each photosensitive resin composition shown in Table 3 was applied on a 100 mm×100 mm glass substrate with a thickness of 1.2 mm in which Cr was vapor-deposited so that the film thickness after the heat curing treatment was 3.5 μm. Except for the electrodes, pre-bake at 90°C for 1 minute. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film (coating film) of Example 11 - Example 16 and Comparative Example 11 - Comparative Example 13. Then, an aluminum electrode was formed on the coating film to prepare a substrate for dielectric constant measurement. Next, using an electrometer (type 6517A), the electrostatic capacitance was measured from a frequency of 1 Hz to a frequency of 100,000 Hz, and the dielectric constant was calculated from the electrostatic capacitance.

[gas-generating]

(Evaluation method)

The cured film (coating film) produced on the glass substrate "EAGLE XG" was ground with a doctor blade or the like, and a differential thermal analysis-thermogravimetric measuring apparatus (TG/DTA) "EXSTAR 6000" was used. "The thermogravimetric loss of 10 mg of the obtained powdery cured film (coating film) was measured. The measurement conditions were pre-treated at 120° C. for 30 minutes in the atmosphere, and then kept at 230° C. for 3 hours.

(Evaluation Criteria)

◎: The weight reduction rate is less than 3%

○: The weight reduction rate is 3% or more and less than 7%

△: The weight reduction rate is 7% or more and less than 10%

×: The weight reduction rate is 10% or more

[Measurement of elastic recovery rate of spacer]

(test methods)

Using a spin coater, each photosensitive resin composition shown in Table 3 was applied on a 125 mm×125 mm glass substrate “EAGLE XG” so that the film thickness after heat curing treatment was 3.0 μm, Prebake at 90°C for 1 minute. Then, it was in close contact with a photomask having a dot pattern, and 100 mJ/cm ² of ultraviolet rays were irradiated with a high-pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction of the photosensitive portion.

Next, using a 0.05% potassium hydroxide aqueous solution, the glass substrate after the exposure was developed for 60 seconds at 24° C. and under a pressure of 0.1 MPa, and the unexposed portion of the cured film (coating film) was removed. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured films (coating films) of Examples 1-6 and Comparative Examples 1-3. The spacing characteristics of the obtained cured film (coating film) pattern were evaluated using an ultra-micro hardness tester "Fischerscope HM2000Xyp" (manufactured by Fischer Instruments). A flat indenter of 100 μm square was pressed at a loading speed of 5.0 mN/sec, and after loading to a load of 50 mN, the load was unloaded at an unloading speed of 5.0 mN/sec, and a displacement curve was prepared.

The elastic recovery rate was calculated according to the following formula (2), assuming that the amount of displacement under a load of 50 mN during loading was L1 and the amount of displacement during unloading was L2.

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

[Development characteristics]

(Preparation of Evaluation Samples)

Using a spin coater, the photosensitive resin composition shown in Table 3 was applied on a glass substrate "EAGLE XG" of 125 mm x 125 mm so that the film thickness after heat curing treatment was 1.5 μm, using The hotplate was pre-baked at 90°C for 1 minute. Then, the photomask was set to have an exposure gap of 150 μm, and ultraviolet rays of 100 mJ/cm ² were irradiated with a high-pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction of the photosensitive portion.

Next, using a 0.05% potassium hydroxide aqueous solution or a 0.2% sodium carbonate aqueous solution at 23° C., the exposed cured film (coating film) was developed under a pressure of 0.1 MPa for 60 seconds, further washed with water, and the cured film (coating film) was The unexposed portion of the film) is removed. Then, the heat-hardening process was performed at 230 degreeC for 30 minutes using a hot air dryer, and the cured film (pattern) of Example 11 - Example 16 and Comparative Example 11 - Comparative Example 13 was obtained.

(Evaluation Method and Evaluation Criteria)

The formation of thin lines in the obtained pattern was confirmed with an optical microscope, and the evaluation was performed in the following three stages.

○: A pattern with an 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 formed, or there is obvious curling or residue of the pattern

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

[Industrial Availability]

The cured film of the photosensitive resin composition of this invention can be used very effectively as a component of the color filter containing an organic electroluminescent element, a quantum dot display, a TFT array, a wavelength conversion element, etc.. Moreover, the resin composition which has a bisnaphthol fluorene skeleton has a function as a light transmission control layer which cut|disconnects the ultraviolet light of a specific range, and is useful.

Claims (8)

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

In formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms to which it is bound may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group, Substituted by cycloalkyl with 3-10 carbons or cycloalkylalkyl, alkoxy with 1-5 carbons, or halogen group; R ₁ are each independently alkylene with 2-4 carbons, and l are each independently G is a number from 0 to 3; G is a substituent represented by the general formula (2) or the general formula (3), Y is a tetravalent carboxylic acid residue; Z is independently a hydrogen atom or is represented by the general formula ( 4) the substituents represented, and one or more are substituents represented by the 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 an alkylarylene group with 2 to 10 carbon atoms, and R ₄ is a group with 2 to 20 carbon atoms. Divalent 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, and m is 1 or 2. 2 . The photosensitive resin composition according to claim 1 , comprising (E) a coloring material. 3 . 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, color-mixing organic pigments, and light-shielding materials. 4 . . 4 . The photosensitive resin composition according to claim 1 , wherein the component (A) is a compound in which Ar in the general formula (1) contains a naphthalene skeleton. 5 . The photosensitive resin composition of Claim 1 whose content of the said (A) component is 10 mass % - 90 mass % with respect to the total mass of solid content, with respect to 100 mass % of (A) component The content of the component (B) is 5 parts by mass to 200 parts by mass, and the content of the component (C) is 0.1 parts by mass to 100 parts by mass of the total amount of the component (A) and the component (B). 30 parts by mass. The photosensitive resin composition of Claim 2 whose content of the said (E) coloring material is 1 mass % - 80 mass % with respect to the total mass of the solid content of the said photosensitive resin composition . 7 . A cured film obtained by curing the photosensitive resin composition according to claim 1 . 8 . A display device having the cured film according to claim 7 .