KR102784271B1 - Photosensitive resin composition, cured material thereof, substrate with that cured material, and producing method of that substrate - Google Patents

Abstract

(Task) To provide a photosensitive resin composition capable of forming a resin film pattern having excellent development adhesion and linearity, and also excellent solvent resistance and alkali resistance, even when a substrate having low heat resistance is used.
(Solution) The photosensitive resin composition of the present invention is a photosensitive resin composition used for forming a cured film on a substrate having a heat-resistant temperature of 140°C or lower, comprising (A) an unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least two or more ethylenically unsaturated bonds, (C) an epoxy compound having two or more epoxy groups, (D) dicyandiamide, (E) a photopolymerization initiator, and (F) a solvent. The total mass of the component (C) and the component (D) is 6 to 24 mass% with respect to the total mass of the solid content.

Description

Photosensitive resin composition, cured film formed by curing the photosensitive resin composition, substrate with cured film attached, and method for producing substrate with cured film attached {PHOTOSENSITIVE RESIN COMPOSITION, CURED MATERIAL THEREOF, SUBSTRATE WITH THAT CURED MATERIAL, AND PRODUCING METHOD OF THAT SUBSTRATE}

The present invention relates to a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, a substrate to which a cured film is attached, and a method for producing a substrate to which a cured film is attached.

Recently, with the aim of making devices more flexible or more one-chip, for example, it has been demanded that a cured film (transparent insulating film, etc.) pattern, a colored film pattern, and a light-shielding film pattern can be formed directly on a plastic substrate (plastic film, resin film) such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate), and that a cured film pattern, a colored film pattern, and a light-shielding film pattern can be formed directly on an organic device attachment substrate equipped with an organic EL or an organic thin-film transistor (TFT), etc., on a glass substrate or silicon wafer.

However, since the plastic substrate and the organic device attachment substrate have low heat resistance of 140°C or less, if a conventional photosensitive resin composition is used to directly form a resin film pattern, a colored film pattern, and a light-shielding film pattern on the plastic substrate or the organic device attachment substrate at a low firing temperature of 140°C or less, there is a problem that the film strength of the formed pattern becomes insufficient, and defects such as film loss, surface roughness, and pattern peeling of the coating occur in the post-process (development, etc.).

Accordingly, a photosensitive resin composition that can be used on a substrate having low heat resistance is being studied. For example, Patent Document 1 discloses a radiation-sensitive composition containing an alkali-soluble resin of an acrylic copolymer, a photopolymerization initiator, and a thermal polymerization initiator. It is stated that the radiation-sensitive composition can form a color filter having sufficient adhesion to a substrate even when fired at a low temperature (100 to 140°C) without yellowing by including a photopolymerization initiator and a thermal polymerization initiator.

Japanese Patent Publication No. 2003-15288

However, according to the inventors' observation, the radiation-sensitive composition described in Patent Document 1 has adhesion to a substrate, but does not obtain the desired development characteristics (e.g., pattern line width, pattern linearity) and solvent resistance.

The present invention has been made in consideration of these points, and has as its object the provision of a photosensitive resin composition which can form a resin film pattern having excellent development adhesion and linearity, and also excellent solvent resistance and alkali resistance, even when a substrate having low heat resistance is used, a cured film formed by curing the photosensitive resin composition, a substrate to which a cured film is attached, and a method for producing a substrate to which a cured film is attached.

The photosensitive resin composition of the present invention is a photosensitive resin composition used for forming a cured film on a substrate having a heat-resistant temperature of 140°C or lower, comprising (A) an unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least two or more ethylenically unsaturated bonds, (C) an epoxy compound having two or more epoxy groups, (D) dicyandiamide, (E) a photopolymerization initiator, and (F) a solvent, wherein the total mass of the component (C) and the component (D) is 6 to 24 mass% with respect to the total mass of the solid content.

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

The cured film-attached substrate of the present invention has the cured film.

The method for manufacturing a substrate having a cured film attached according to the present invention is a method for manufacturing a substrate having a cured film attached by forming a cured film pattern on a substrate having a heat-resistant temperature of 140°C or lower, wherein the photosensitive resin composition is applied onto a substrate, exposed through a photomask, unexposed portions are removed by development, and the cured film pattern is formed by heating at 140°C or lower.

According to the present invention, a photosensitive resin composition capable of forming a resin film pattern having excellent development adhesion and linearity, and also excellent solvent resistance and alkali resistance, even when a substrate having low heat resistance is used, a cured film formed by curing the photosensitive resin composition, a substrate to which a cured film is attached, and a method for producing a substrate to which a cured film is attached can be provided.

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

The alkali-soluble resin containing an unsaturated group (A) included in the photosensitive resin composition of the present invention is described.

An alkali-soluble resin (A) having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (1) of the present invention is obtained by reacting a reaction product of an epoxy compound (a-1) having two epoxy groups in one molecule and a monocarboxylic acid containing an unsaturated group with a dicarboxylic acid or a tricarboxylic acid or an acid dianhydride thereof (b), and a tetracarboxylic acid or an acid dianhydride thereof (c).

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a direct bond, Y is a tetravalent carboxylic acid residue, and Z is each independently a hydrogen atom or a substituent represented by general formula (2). However, at least one of Z is a substituent represented by general formula (2), and n is an integer of 1 to 20.)

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

A method for producing an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by general formula (1) (hereinafter, also referred to simply as “alkali-soluble resin represented by general formula (1)”) is described in detail.

First, an epoxy compound (a-1) having two epoxy groups in one molecule represented by general formula (4) (hereinafter also referred to simply as “epoxy compound (a-1)”) is reacted with an unsaturated group-containing monocarboxylic acid (e.g., (meth)acrylic acid) to obtain an epoxy (meth)acrylate.

(In formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a direct bond.)

Epoxy compound (a-1) is an epoxy compound having two glycidyl ether groups produced by reacting bisphenol and epichlorohydrin.

Examples of bisphenols used as raw materials for epoxy compounds (a-1) include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, Bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, Bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, These include 4,4'-biphenol, 3,3'-biphenol, etc. These can be used alone, or two or more types can be used together.

Examples of the above unsaturated group-containing monocarboxylic acid compound include, in addition to acrylic acid and methacrylic acid, compounds produced by reacting acrylic acid or methacrylic acid with an acid 1-anhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride.

The reaction of the above epoxy compound (a-1) and (meth)acrylic acid can be carried out using a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 discloses that by using about 2 mol of (meth)acrylic acid for 1 mol of an epoxy compound having two epoxy groups, a diol compound containing a polymerizable unsaturated group is obtained. In the present invention, the compound obtained by the above reaction is a diol compound containing a polymerizable unsaturated group, and is a diol (d) containing a polymerizable unsaturated group represented by the general formula (5) (hereinafter also referred to simply as "diol (d) represented by the general formula (5)").

(In formula (5), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, and X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a direct bond.)

In the synthesis of diol (d) represented by general formula (5), and subsequent addition reaction of a polycarboxylic acid or anhydride thereof, and further reaction of a monofunctional epoxy compound having a polymerizable unsaturated group reactive with a carboxyl group, and the production of an alkali-soluble resin represented by general formula (1), the reaction is usually carried out in a solvent using a catalyst as necessary.

Examples of the solvent include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling-point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone and diisobutyl ketone, etc. In addition, there are no particular restrictions on the reaction conditions such as the solvent and catalyst used, but, for example, it is preferable to use a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

In addition, it is preferable to use a catalyst for the reaction between a carboxyl group and an epoxy group, and Japanese Patent Application Laid-Open No. 9-325494 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

Next, by reacting a diol (d) represented by general formula (5) obtained by the reaction of an epoxy compound (a-1) and (meth)acrylic acid, with a dicarboxylic acid or a tricarboxylic acid or an acid dianhydride thereof (b), and a tetracarboxylic acid or an acid dianhydride thereof (c), an alkali-soluble resin represented by general formula (1) can be obtained.

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a direct bond, Y is a tetravalent carboxylic acid residue, and Z is each independently a hydrogen atom or a substituent represented by general formula (2). However, at least one of Z is a substituent represented by general formula (2), and n is an integer of 1 to 20.)

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

The acid component used to synthesize the alkali-soluble resin represented by the general formula (1) is a polyvalent acid component capable of reacting with a hydroxyl group in a diol (d) molecule represented by the general formula (5), and it is necessary to use a dicarboxylic acid or a tricarboxylic acid or an acid dianhydride thereof (b) in combination with a tetracarboxylic acid or an acid dianhydride thereof (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, these carboxylic acid residues may include a bond containing a heteroatom such as -O-, -S-, or a carbonyl group.

As the dicarboxylic acid or tricarboxylic acid or the acid anhydride thereof (b), a chain hydrocarbon dicarboxylic acid or tricarboxylic acid, an alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, an aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or the acid anhydride thereof can be used.

Examples of acid anhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid anhydrides such as 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, and acid anhydrides of dicarboxylic acids or tricarboxylic acids having an optional substituent introduced therein. In addition, examples of acid anhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid anhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid, and acid anhydrides of dicarboxylic acids or tricarboxylic acids having an optional substituent introduced therein. Also, examples of acid anhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid anhydrides such as phthalic acid, isophthalic acid, trimellitic acid, and the like, and acid anhydrides of dicarboxylic acids or tricarboxylic acids to which an optional substituent has been introduced.

Among the acid anhydrides of dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferable. In addition, for dicarboxylic acids or tricarboxylic acids, it is preferable to use these acid anhydrides. The acid anhydrides of the above-mentioned dicarboxylic acids or tricarboxylic acids may be used alone, or two or more may be used in combination.

In addition, as the tetracarboxylic acid or its acid dianhydride (c), chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or their acid dianhydrides can be used.

Examples of chain hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids having a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group introduced therein. In addition, examples of the alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and alicyclic tetracarboxylic acids having a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group introduced therein. In addition, examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and the like.

Among tetracarboxylic acids or their dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferable, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferable. In addition, among tetracarboxylic acids or their dianhydrides, it is preferable to use the acid dianhydride. In addition, the above-mentioned tetracarboxylic acids or their dianhydrides may be used alone, or two or more may be used in combination.

There is no particular limitation on the reaction of the diol (d) represented by the general formula (5) and the acid components (b) and (c), and a known method can be adopted. For example, Japanese Patent Application Laid-Open No. 9-325494 discloses a method of reacting epoxy (meth)acrylate and tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

Here, it is preferable to react the diol (d), dicarboxylic acid or tricarboxylic acid or their acid dianhydride (b), and tetracarboxylic acid or their acid dianhydride (c) represented by general formula (5) so that the terminal of the compound becomes a carboxyl group in a molar ratio of (d):(b):(c) = 1:0.01∼1.0:0.2∼1.0.

For example, when using dicarboxylic acid or tricarboxylic acid or anhydride thereof (b), tetracarboxylic acid or anhydride thereof (c), it is preferable to react so that the molar ratio [(d)/〔(b)/2+(c)〕] of the amount of the acid component to the diol (d) represented by the general formula (5) is 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of the diol containing an unreacted polymerizable unsaturated group does not increase, so the stability over time of the alkali-soluble resin composition can be improved. On the other hand, when the molar ratio exceeds 0.5, the terminal of the alkali-soluble resin represented by the general formula (1) does not become an acid anhydride, so the content of the unreacted acid dianhydride can be suppressed from increasing, and therefore the stability over time of the alkali-soluble resin composition can be improved. In addition, for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by general formula (1), the molar ratio of each component of (d), (b) and (c) can be arbitrarily changed within the above-described range.

In addition, the preferable range of the acid value of the alkali-soluble resin represented by general formula (1) is 20 to 180 mgKOH/g, and it is preferably 80 mgKOH/g or more and 120 mgKOH/g or less. When the acid value is 20 mgKOH/g or more, it is difficult for a residue to remain during alkaline development, and when it is 180 mgKOH/g or less, the penetration of the alkaline developer becomes too fast, so that the peeling phenomenon can be suppressed. In addition, the acid value can be obtained by titrating with a 1/10 N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The weight average molecular weight (Mw) in polystyrene conversion by gel permeation chromatography (GPC) measurement (HLC-8220GPC, manufactured by Tosoh Corporation) of the alkali-soluble resin represented by general formula (1) 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 the adhesion of the pattern during alkaline development can be suppressed. Furthermore, when the weight average molecular weight is less than 100,000, it is easy to adjust the solution viscosity of the photosensitive resin composition to be suitable for application, and alkaline development does not require excessive time.

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

Here, the mass of component (A) is preferably 30 to 80 mass% with respect to the total mass of the solid content when no coloring agent is included, and is preferably 2 to 70 mass% when a coloring agent is included.

The photosensitive resin composition of the present invention comprises (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds.

(B) Component increases the adhesion of the cured film and also increases the solubility of the exposed area in an alkaline developer, thereby increasing the straight line reproducibility of the cured film. However, in order to make it difficult for the cured film to become soft, and also to suppress a decrease in the acid value of the composition, thereby increasing the solubility of the unexposed area in an alkaline developer, and thereby increasing the straight line reproducibility of the cured film, it is preferable that the amount of (B) component is not excessively high.

(B) The content of component is preferably 10 to 60 parts by mass per 100 parts by mass of component (A).

(B) Examples of photopolymerizable monomers having at least two ethylenically unsaturated bonds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, (Meth)acrylic acid esters such as dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like; resinous polymers having a (meth)acryl group as a compound having an ethylenic double bond; In addition, these may be used alone or in combination of two or more.

Examples of the resinous polymer having a (meth)acrylic group as a compound having the above-mentioned ethylenic double bond include a resinous polymer obtained by adding a polyvalent mercapto compound to some of the carbon-carbon double bonds in the (meth)acrylate group of a polyfunctional (meth)acrylate. Specifically, there is a resinous polymer obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by general formula (6) with a polyvalent mercapto compound represented by general formula (7).

(In formula (6), R ₉ is a hydrogen atom or a methyl group, and R ₁₀ is the remainder of the k hydroxyl groups of R ₁₁ (OH) _k donated to the ester bond in the formula. Preferred R ₁₁ (OH) _k is a polyhydric alcohol based on a non-aromatic straight-chain or branched-chain hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by connecting multiple molecules of the polyhydric alcohol via an ether bond by dehydration condensation of the alcohol, or an ester of these polyhydric alcohols or polyhydric alcohol ethers and a hydroxy acid. k and l are independently integers of 2 to 20, and k ≥ l.)

(In formula (7), R ₁₂ is a single bond or a C1 to C6 hydrocarbon group having a valence of 2 to 6, and p is 2 when R ₁₂ is a single bond, and is an integer from 2 to 6 when R ₁₂ is a group having a valence of 2 to 6.)

Examples of the polyfunctional (meth)acrylate represented by the general formula (6) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, epichlorohydrin-modified hexahydrophthalic acid di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified (Meth)acrylic acid esters such as trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate (meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, alkoxy-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate are included. These compounds may be used alone, or two or more types may be used in combination.

Examples of polyhydric mercapto compounds represented by general formula (7) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. These compounds may be used alone, or two or more may be used in combination.

In addition, in the synthesis of the above resinous polymer, a polymerization inhibitor may be added as needed. Examples of the polymerization inhibitor include hydroquinone-based compounds and phenol-based compounds. Specific examples thereof include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert-butylphenol (BHT), and the like.

The mixing ratio of component (A) and component (B) is preferably 30/70 to 90/10 in a weight ratio (A)/(B), more preferably 60/40 to 80/20. When the mixing ratio of component (A) is 30/70 or more, the cured film after photocuring is unlikely to become brittle, and furthermore, since the acid value of the film in the unexposed area is unlikely to decrease, the decrease in solubility in an alkaline developer can be suppressed. Therefore, the problem of the pattern edge being rough or not becoming sharp is unlikely to occur. In addition, when the mixing ratio of component (A) is 90/10 or less, the ratio of the photoreactive functional group in the resin is sufficient, so that the formation of the desired crosslinked structure can be performed. In addition, since the acid value in the resin component is not too high, the solubility in an alkaline developer in the exposed area is unlikely to increase, so that the formed pattern becomes thinner than the target line width or the pattern is suppressed from being lost.

The photosensitive resin composition of the present invention comprises (C) an epoxy compound having two or more epoxy groups.

(C) Examples of epoxy compounds having two or more epoxy groups include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, copolymers of monomers having (meth)acrylic groups containing (meth)acrylic acid glycidyl as a unit, represented by copolymers of methacrylic acid and glycidyl methacrylate. 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celoxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) formula ε-caprolactone (e.g., Eporide GT401: manufactured by Daicel Corporation), epoxy compounds having an epoxycyclohexyl group represented by HiREM-1 manufactured by Shikoku Kasei Kogyo Co., Ltd., polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), These include epoxy polybutadiene (e.g., NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd.), epoxy compounds having a silicone skeleton, etc.

(C) Among the epoxy compounds having two or more epoxy groups, an epoxy compound having a 3,4-epoxycyclohexyl group or an epoxy compound having a glycidyl group is preferable, and an epoxy compound having two or more glycidyl groups is more preferable. By using an epoxy compound having two or more glycidyl groups, a change in pattern line width due to time can be suppressed. In addition, the reason why an epoxy resin having two or more epoxy groups is preferable is because the greater the number of functional groups in one molecule, the more easily the epoxy resin becomes high molecular weight during heat curing, and thus the solvent resistance of the cured film is easily improved.

(C) The epoxy equivalent of the epoxy compound of component is preferably 100 to 300 g/eq, more preferably 100 to 250 g/eq. In addition, the number average molecular weight (Mn) of the epoxy compound of component (C) is preferably 100 to 5000. When the epoxy equivalent is 100 to 300 g/eq and the number average molecular weight (Mn) of the epoxy compound is 100 to 5000, a cured film having good solvent resistance can be formed after securing developing adhesion at the time of development. In addition, when the epoxy equivalent is 300 g/eq or less, it is possible to design a photosensitive resin composition in which the developing speed is within an appropriate range, and the solvent resistance of the cured film can also be secured. In addition, these compounds may use only one type of compound, or two or more types may be used in combination.

The photosensitive resin composition of the present invention contains (D) dicyandiamide. By using dicyandiamide as a curing agent for an epoxy compound, even when the photosensitive resin composition of the present invention is fired at a low temperature of 140°C or lower, the line width reproducibility, linear reproducibility, and solvent resistance of the cured film can be sufficiently improved. For example, compared to a system using an acid anhydride as a curing agent, it is useful to use dicyandiamide as a curing agent because it has high reactivity, can secure the solvent resistance of the cured film even in a small amount, and has excellent storage stability.

The ratio of the equivalent number (E _ep ) of the epoxy group of component (C) to the equivalent number (E _am ) of the amino group of dicyandiamide of component (D) is preferably E _ep /E _am = 0.5 to 2.0, and more preferably E _ep /E _am = 0.7 to 1.5. When E _ep /E _am is 0.5 or more, the epoxy compound can be sufficiently cured, so that unreacted epoxy compound can be suppressed from remaining in the photosensitive resin composition. In addition, when E _ep /E _am is 2.0 or less, the adhesion and straight line reproducibility of the cured film can be sufficiently improved.

In addition, the total mass of the (C) component and the (D) component is preferably 6 to 24 mass%, and more preferably 8 to 22 mass%, based on the total mass of the solid content. By including 6 to 24 mass% of the (C) component and the (D) component, the line width reproducibility, straight line reproducibility, and content resistance of the formed cured film can be sufficiently improved.

The photosensitive resin composition of the present invention contains (E) a photopolymerization initiator.

(E) Examples of components include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Biimidazole compounds such as 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole; Halomethyldiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-Tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-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, Halomethyl-s-triazine compounds, such as 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; O-acyl oxime compounds, such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, and 1-(4-methylsulfanylphenyl)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 azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and pentaerythritol tetrakis(3-mercaptopropionate); tertiary amines such as triethanolamine and triethylamine, etc. In addition, these photopolymerization initiators may be used alone, or two or more may be used in combination.

In particular, when using a photosensitive resin composition including a coloring material, it is preferable to use O-acyl oxime compounds (including ketoxime). Specific examples of the compound group preferably include an O-acyl oxime photopolymerization initiator represented by the general formula (3) or the general formula (8). Among these compound groups, when using the coloring material at a high concentration and when forming a light-shielding film pattern, it is more preferable to use an O-acyl oxime photopolymerization initiator having a molar absorption coefficient at 365 nm of 10,000 L/mol cm or more. Specific examples of the compound group include an O-acyl oxime photopolymerization initiator represented by the general formula (3). In addition, the "photopolymerization initiator" as used in the present invention is used to mean including a sensitizer.

(In formula (3), R ₆ and R ₇ are each independently a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group, and R ₈ is a C1 to C15 alkyl group, a C6 to C18 aryl group, or a C7 to C20 arylalkyl group. Here, the alkyl group and the aryl group may be substituted with a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 alkanoyl group, or a halogen, and the alkylene moiety may include an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, the alkyl group may be any linear, branched, or cyclic alkyl group.

(In formula (8), R ₁₃ and R ₁₄ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₁₅ is independently a linear or branched alkyl group or an alkenyl group having 2 to 10 carbon atoms, and a part of the -CH ₂ - group in the alkyl group or alkenyl group may be substituted with an -O- group. Furthermore, a part of the hydrogen atoms in the groups R ₁₃ to _{R 15} may be substituted with a halogen atom.)

The mass of the (E) component is preferably 0.1 to 30 mass% with respect to the total mass of the (A) component and the (B) component, and more preferably 1 to 25 mass%. When the mass of the (E) component is 0.1 mass% or more with respect to the total mass of the (A) component and the (B) component, an appropriate photopolymerization speed is achieved, so that a decrease in sensitivity can be suppressed. Furthermore, when it is 30 mass% or less, a faithful line width with respect to the mask can be reproduced, and the pattern edge can be made sharp.

The photosensitive resin composition of the present invention contains (F) a solvent.

(F) Examples of solvents included 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- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Glycol ethers such as 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, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-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, a uniform solution composition can be made. These solvents may be used alone or in combination of two or more in order to provide necessary properties such as applicability.

(F) The content of the component varies depending on the target viscosity, but is preferably 60 to 90 mass% in the photosensitive resin composition solution.

The photosensitive resin composition of the present invention may contain a (G)imidazole compound as a curing accelerator.

Examples of the above (G)imidazole compounds include imidazole, 1H-imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, and the like.

In addition, the mass of the (G) imidazole compound is preferably 0.05 to 2 mass%, more preferably 0.1 to 1 mass%, based on the total mass of the solid content of the (C) epoxy compound and (D) dicyandiamide. By setting the mass of the (G) imidazole compound to 0.05 mass% or more based on the total mass of the solid content of the (C) epoxy compound and (D) dicyandiamide, the reaction with the epoxy resin can be promoted, and the solvent resistance of the cured film can be improved. In addition, by setting the mass of the (G) imidazole compound to 2 mass% or less, dicyandiamide, which has low solubility in solvents, does not precipitate in the photosensitive resin composition, thereby promoting the reaction with the epoxy compound.

The photosensitive resin composition of the present invention may contain (H) a coloring agent.

It is preferable that the above coloring material is a coloring material selected from the group consisting of organic pigments or inorganic pigments, and it is more preferable that the above coloring material is a light-blocking material selected from the group consisting of organic black pigments or inorganic black pigments.

(H) The content of the coloring agent as the component can be arbitrarily determined according to the desired light-shielding degree. It is preferably 20 to 80 mass% based on the solid content in the photosensitive resin composition, and more preferably 40 to 70 mass%. If the coloring agent is 20 mass% or more based on the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. If the coloring agent is 80 mass% or less based on the solid content in the photosensitive resin composition, the content of the photosensitive resin, which is the original binder, does not decrease, so the desired developing characteristics and film-forming performance can be obtained.

(H) Examples of black organic pigments, which are components, include perylene black, aniline black, cyanine black, lactam black, etc. Examples of mixed color organic pigments include at least two colors selected from organic pigments, such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, srene pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments, which are mixed to create a pseudo-black color. Black inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, etc. Depending on the function of the intended photosensitive resin composition, these (H) components may be used alone or in combination of two or more. Among the above pigments, carbon black is preferable from the viewpoints of light-shielding properties, surface smoothness, dispersion stability, and compatibility with resin. In addition, when using an organic pigment, one that has undergone atomization processing (one having a specific surface area of 50 m2/g or more by the BET method) is preferable in order to achieve fine dispersion with an average particle diameter of 50 nm or less.

Examples of organic pigments that can be used as the above (H) component include, but are not limited to, those with the following numbers in the color index name.

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.

In addition, it is preferable to disperse the coloring material of the (H) component in advance in a solvent together with a dispersant to make a coloring material dispersion, and then mix it as a photosensitive resin composition for a colored film. Here, the solvent for dispersing can be any of the above-mentioned ones. Among the above-mentioned solvents, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are preferable.

The dispersant may be a known dispersant such as various polymer dispersants. Examples of the dispersant include, without particular limitation, known compounds that have been conventionally used for pigment dispersion (compounds sold under the names of dispersant, dispersion wetting agent, dispersion accelerator, etc.). Examples of the dispersant include a cationic polymer-based dispersant, an anionic polymer-based dispersant, a nonionic polymer-based dispersant, a pigment derivative-type dispersant (dispersion assistant), etc. In particular, a cationic polymer-based dispersant having a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary, or tertiary amino group as an adsorption site for the pigment, and an amine value of 1 to 100 mgKOH/g and a number average molecular weight of 1,000 to 100,000 is preferable. The blending amount of the dispersant is preferably 1 to 30 mass% with respect to the colorant, and more preferably 2 to 25 mass%.

In addition, when preparing a coloring material dispersion, a part of the unsaturated group-containing alkali-soluble resin of component (A) may be co-dispersed in addition to the dispersant. By co-dispersing a part of the unsaturated group-containing alkali-soluble resin of component (A), a photosensitive resin composition can be obtained which is easy to maintain a high exposure sensitivity, has good adhesion during development, and is unlikely to cause a residue problem. The blending amount of component (A) at that time is preferably 2 to 20 mass% in the coloring material dispersion, and is more preferably 5 to 15 mass%. When component (A) is 2 mass% or more, the effects of improved sensitivity, improved adhesion, and reduced residue due to co-dispersion can be obtained. When component (A) is 20 mass% or less, even when the content of the coloring material is particularly large, the viscosity of the coloring material dispersion does not become excessively high, so that it can be uniformly dispersed. The obtained colorant dispersion can be mixed with components (A) to (G), and other components can be added as needed to adjust the viscosity to a viscosity suitable for film forming conditions, thereby producing a photosensitive resin composition used in the manufacturing method of the present invention.

The photosensitive resin composition of the present invention may contain (I) silica particles.

(I) The silica particles, which are the component, are not particularly limited in their manufacturing method (gas phase reaction or liquid phase reaction) or in their shape (spherical or non-spherical). In addition, silica particles that have undergone surface treatment, such as treatment with a silane coupling agent, can also be used without particular limitations.

The type of silica particles, which are the (I) component used in the present invention, is not particularly limited. Solid silica particles may be used, or hollow silica particles may be used. In addition, "hollow silica particles" are silica particles having cavities inside the particles.

By using the above silica particles, the refractive index of a light shielding film including the above silica particles can be lowered.

The average particle diameter of the above silica particles is preferably 1 to 95 nm, and more preferably 5 to 90 nm. By using silica particles having a small average particle diameter, rattling on the side of the fine line pattern can be suppressed. In addition, there is an effect of reducing the unevenness of the surface of the cured film (coating film), and unevenness of reflectivity within the surface of the cured film (coating film) can be suppressed.

In addition, the content of the silica particles is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to the total mass of the photosensitive resin composition. When the content of the silica particles is within the above range, low reflectivity can be achieved while ensuring good patterning properties.

The average particle diameter of the above silica particles can be measured by the Qumrant method using a particle size distribution meter “Particle Size Analyzer FPAR-1000” (manufactured by Otsuka Electronics Co., Ltd.) of the dynamic light scattering method.

In addition, the refractive index of the silica particles may be 1.10 to 1.47. In addition to being able to use the refractive index of ordinary silica particles of 1.45 to 1.47, by using hollow silica particles having a low refractive index, the refractive index of the light shielding film may be made lower than the refractive index of a light shielding film containing only ordinary silica particles.

In addition, the refractive index of the silica particles can be obtained from a transparent mixture obtained by mixing the silica particles processed into a powder form and a standard refractive liquid having a known refractive index. In this case, the refractive index of the standard refractive liquid of the mixture is taken as the refractive index of the silica particles. In addition, the refractive index of the silica particles can be measured using an Abbe refractometer.

In addition, since it is possible to suppress reflection caused by the difference in refractive index between the layer formed on the cured film (coating) and the cured film (coating), reflection can be suppressed without separately installing an anti-reflection film, etc.

The shape of the above silica particles may be spherical or elliptical. It is preferable that the shape of the silica particles used in the present invention is spherical.

The above silica particles preferably have a sphericity of 1.0 to 1.5. When the sphericity of the silica particles is in this range, the particle shape approaches a sphere. Therefore, it is possible to uniformly fill a light-shielding film having a thin film thickness, and a light-shielding film can be formed in which the silica particles are not exposed to the outside from the film surface while maintaining the smoothness of the film surface. Therefore, a light-shielding film having a low refractive index and sufficient strength can be obtained. When attempting to obtain a light-shielding film capable of realizing such low reflection on the film surface side, the selection of a photopolymerization initiator is also an important factor, and it is preferable to use an oxime ester photopolymerization initiator generally used in light-shielding films and add 0.5 to 5% of a thiol compound in the solid content.

The sphericity of the above silica particles can be obtained from the ratio of the longest and shortest diameters of the particles (the average value of 100 random silica particles). Here, the longest and shortest diameters of the silica particles are values obtained by photographing the silica particles with a transmission electron microscope and measuring the longest and shortest diameters of the silica particles from the obtained microscopic image.

The silica particles of the above (I) component are a silica particle dispersion dispersed in a solvent and can be mixed with other compounding ingredients. The dispersant can be a known compound used for dispersing pigments (light-blocking components) (compounds sold commercially under the names of dispersant, dispersion wetting agent, dispersion accelerator, etc.) without any particular limitation.

The photosensitive resin composition of the present invention may contain additives such as a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent, etc., as needed. Here, examples of the thermal polymerization inhibitor and the antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, etc. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of the filler include glass fiber, silica, mica, alumina, etc. Examples of the antifoaming agent or leveling agent include silicone-based, fluorine-based, and acrylic compounds. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, etc. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

The method for manufacturing a cured film of the present invention is a manufacturing method comprising: applying the photosensitive resin composition described above on a substrate having a heat-resistant temperature of 140°C or lower, exposing through a photomask, removing an unexposed portion by development, and heating at 140°C or lower to form a predetermined cured film pattern.

Examples of the substrate used in the method for manufacturing a cured film of the present invention include a resin film (plastic substrate) such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) having a heat-resistant temperature of 140°C or lower, a substrate on which an electrode such as ITO or gold is deposited or patterned on a resin film, and the like. Here, the "heat-resistant temperature" means a temperature at which problems such as deformation do not occur even if the substrate is exposed during a processing process such as pattern formation of a cured film on the substrate. In addition, the resin film changes depending on the degree of stretching treatment, but it is necessary that it does not exceed at least the glass transition temperature (Tg).

In addition, examples of other substrates used in the method for manufacturing a cured film of the present invention include those having high heat resistance of the substrate itself, such as a glass substrate, a silicon wafer, and a polyimide film, but having a thin film or the like having low heat resistance formed on the substrate. Specific examples of other substrates include an organic device attachment substrate having an organic EL (OLED) or an organic thin film transistor (TFT) formed on glass, a silicon wafer, or a polyimide film. In addition, the heat resistance temperature of the low heat resistance substrate targeted in the present invention varies depending on the type of resin or the device, but is preferably 80 to 140°C. In addition, the organic device attachment substrate also includes those having a protective film, protective film, or the like formed after forming the organic device. This is because, even if the heat resistance of these protective films or protective films themselves is 150°C or higher, in order to ensure the function of the organic device, if they have a heat resistance of practically only 140°C or lower, they are considered to be substrates with organic devices attached.

The method for applying the photosensitive resin composition of the present invention onto a substrate may be any method, such as a method using a roller coater, a land coater, a slit coater or a spinner, in addition to a known solution immersion method or spraying method. By these methods, after applying to a desired thickness, a film is formed by removing the solvent (prebaking). The prebaking is performed by heating using an oven, a hot plate or the like. The heating temperature and heating time in the prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 60 to 110°C (set so as not to exceed the heat-resistant temperature of the substrate) for 1 to 3 minutes.

The exposure performed after the prebake is performed by an ultraviolet exposure device, and by exposing through a photomask, only the resist in the portion corresponding to the pattern is exposed. The exposure device and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a deep ultraviolet lamp, and the photosensitive resin composition in the coating is photocured. Preferably, photocuring is performed by irradiating a certain amount of light having a wavelength of 365 nm.

As the radiation used for exposure, for example, visible light, ultraviolet rays, ultraviolet rays, electron rays, X-rays, etc. can be used, but the wavelength range of the radiation is preferably 250 to 450 nm. In addition, as a developer suitable for this alkaline development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. These developers can be appropriately selected according to the characteristics of the resin layer, but a surfactant may be added as necessary. The development temperature is preferably 20 to 35°C, and a fine image can be precisely formed using a commercially available developer or ultrasonic cleaner. In addition, after alkaline development, it is usually washed with water. As a developing method, a shower developing method, a spray developing method, a dip developing method, a puddle developing method, etc. can be applied.

Alkaline development after exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of developers suitable for this alkaline development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydroxides of alkali metals, etc. In particular, it is preferable to perform development at a temperature of 23 to 28°C using a weakly alkaline aqueous solution containing 0.05 to 3 mass% of a carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate. In addition, a fine image can be precisely formed using a commercially available developer or ultrasonic cleaner.

After development, it is preferable to perform heat treatment (post-bake) under the conditions of a temperature of 80 to 140°C (set so as not to exceed the heat-resistant temperature of the substrate) and a time of 20 to 90 minutes, and it is more preferable to perform it under the conditions of a temperature of 90 to 120°C and a heating time of 30 to 60 minutes. The above-mentioned post-bake is performed for the purpose of increasing the adhesion between the patterned cured film and the substrate. This is performed by heating with an oven, a hot plate, or the like, similar to the pre-bake. The patterned cured film of the present invention is formed through each process by the above photolithography method.

(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.

First, the following explains the synthesis examples of unsaturated group-containing alkali-soluble resins represented by general formula (1). The evaluation of the resins in these synthesis examples was performed as follows unless otherwise stated.

[Solid content concentration]

Among the synthetic examples, 1 g of the resin solution obtained was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)], and the weight after heating at 160°C for 2 hours [W ₂ (g)] was obtained from the following formula.

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

[Epoxy Equivalent]

After dissolving the resin solution in dioxane, an acetic acid solution of tetraethylammonium bromide was added, and titration was performed with a 1/10 N perchloric acid solution using a potentiometric titration device “COM-1600” (produced by Hiranuma Sangyo Co., Ltd.) to obtain the value.

[Sanga]

The resin solution was dissolved in dioxane and titrated with a 1/10N-KOH aqueous solution using a potentiometric titration device “COM-1600” (produced by Hiranuma Sangyo Co., Ltd.).

[Molecular weight]

Gel permeation chromatography (GPC) "HLC-8220GPC" (Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2) + TSKgel SuperH-3000 (1) + TSKgel SuperH-4000 (1) + TSKgel SuperH-5000 (1) (Tosoh Corporation), temperature: 40°C, speed: 0.6 ml/min) was measured, and the weight average molecular weight (Mw) was obtained as a value converted to standard polystyrene (Tosoh Corporation, PS-oligomer kit).

[Molecular absorption coefficient]

The molar absorption coefficient of the acyl oxime photopolymerization initiator was measured using an ultraviolet-visible-near-infrared spectrophotometer “UH4150” (manufactured by Hitachi High-Tech Science Co., Ltd.).

[Average particle diameter]

The average particle diameter of silica particles was measured using a particle size distribution meter “Particle Size Analyzer FPAR-1000” (manufactured by Otsuka Electronics Co., Ltd.) of dynamic light scattering method and the Qumrant method.

Additionally, the abbreviations used in the synthetic examples and comparative synthetic examples are as follows.

DCPMA: Dicyclopentanyl methacrylate

GMA: Glycidyl Methacrylate

St: Styrene

AA: Acrylic acid

SA: Anhydrous succinic acid

BPFE: Bisphenol fluorene type epoxy compound (reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane)

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

THPA: Tetrahydrophthalic anhydride

DPHA: A mixture of dipentaerythritol pentaacrylate and hexaacrylate

AIBN: Azobisisobutyronitrile

TDMAMP: Trisdimethylaminomethylphenol

HQ: Hydroquinone

TEA: Triethylamine

TEAB: Tetraethylammonium bromide

PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]

PGMEA (300 g) was placed in a 1 L four-necked flask equipped with a reflux condenser, the inside of the flask was replaced with nitrogen, and the temperature was raised to 120°C. A mixture of AIBN (10 g) dissolved in a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) was added dropwise from a dropping funnel to the flask over 2 hours, and the mixture was stirred at 120°C for 2 hours to obtain a copolymer solution.

Next, after replacing the inside of the flask with air, AA (24.0 g, 95% of glycidyl groups), TDMAMP (0.8 g), and HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 120°C for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. SA (30.0 g, 90% of the mole number of AA added) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution, and the mixture was reacted at 120°C for 4 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-1. The solid content concentration of the resin solution was 46.0 mass%, the acid value (converted to solid content) was 76 mgKOH/g, and the Mw by GPC analysis was 5300.

[Synthesis Example 2]

BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were charged into a 500 ml 4-necked flask equipped with a reflux condenser, and stirred at 100 to 105°C for 20 hours to react. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask, and stirred at 120 to 125°C for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-2. The solid content concentration of the obtained resin solution was 56.1 mass%, the acid value (converted to solid content) was 103 mgKOH/g, and the Mw by GPC analysis was 3600.

The photosensitive resin compositions of Examples 1 to 30 and Comparative Examples 1 to 18 were prepared by mixing the above-mentioned mixing components in the ratios shown in Tables 1 to 5. Also, all numerical values in Tables 1 to 5 represent parts by mass.

(unsaturated alkaline soluble resin)

(A)-1: Resin solution obtained in the above synthesis example 1 (solid content concentration 46.0 mass%)

(A)-2: Resin solution obtained in the above synthesis example 2 (solid content concentration 56.1 mass%)

In addition, in Tables 1 to 5, an alkali-soluble resin containing a polymerizable unsaturated group is described as the resin.

(photopolymerizable monomer)

(B): A mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA (acrylic equivalent 96-115), manufactured by Nippon Kayaku Co., Ltd.)

(epoxy compound)

(C)-1: Triphenylmethane type epoxy resin (EPPN-501H, epoxy equivalent 160, manufactured by Nippon Kayaku Co., Ltd.)

(C)-2: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 (epoxy equivalent 180), manufactured by Daicel Corporation)

(C)-3: 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (Celoxide 2021P, epoxy equivalent 130, manufactured by Daicel Corporation)

(C)-4: HiREM-1 (Epoxy equivalent 113, Shikoku Kasei High School)

(C)-5: Butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) formula ε-caprolactone (epoxy equivalent 197, manufactured by Daicel Corporation)

(hardener)

(D)-1: Dicyandiamide (DICY7, manufactured by Mitsubishi Chemical Co., Ltd.)

(D)-2: Trimellitic anhydride

(photopolymerization initiator)

(E)-1: Oxime ester photopolymerization initiator (ADEKA ACRUSE NCI-831, manufactured by ADEKA Co., Ltd., “ADEKA ACRUSE” is a registered trademark of the company)

(E)-2: Pentaerythritol tetrakis(3-mercaptopropionate)

(solvent)

(F)-1: Propylene glycol monomethyl ether acetate (PGMEA)

(F)-2: Diethylene glycol ethyl methyl ether (EDM)

(curing accelerator)

(G): PGMEA solution containing 2.0 mass% of 1,2-dimethylimidazole

(coloring material)

(H)-1: Pigment dispersion of PGMEA solvent containing 25.0 mass% of resin-coated carbon black and 5.0 mass% of polymer dispersant (solid content 30.0 mass%)

(H)-2: Pigment dispersion (solid content concentration 35.0 mass%) in PGMEA solvent containing 25.0 mass% of carbon black, 2.0 mass% of polymer dispersant, and 8.0 mass% of dispersion resin (unsaturated group-containing alkali-soluble resin (A)-2 of Synthesis Example 2)

(silica particles)

(I)-1: Silica PGMEA dispersion “YA010C” (manufactured by Admatex Co., Ltd., solid content concentration 20 mass%, average particle diameter 10 nm)

(I)-2: Silica PGMEA dispersion “YA050C” (manufactured by Admatex Co., Ltd., solid content concentration 40 mass%, average particle diameter 50 nm)

(I)-3: Silica PGMEA dispersion “YC100C” (manufactured by Admatex Co., Ltd., solid content concentration 50 mass%, average particle diameter 100 nm)

(I)-4: Hollow silica isopropanol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd., solid content concentration 20 mass%, average particle diameter 75 nm, void ratio 46 volume%)

(Surfactant)

(J): Mega Pack F-475 (manufactured by DIC Corporation, “Mega Pack” is a registered trademark of the company)

[evaluation]

The following evaluations were conducted using cured films (coatings) formed by curing the photosensitive resin compositions of Examples 1 to 30 and Comparative Examples 1 to 18. The evaluation results are shown in Tables 6 to 10.

(Production of cured film (coating film) for evaluating phenomenon characteristics)

The photosensitive resin compositions shown in Tables 1 to 5 were applied using a spin coater on a 125 mm × 125 mm glass substrate "#1737" (Corning Corp.) (hereinafter referred to as the "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet rays having a wavelength of 254 nm and an intensity of 1000 mJ/cm2 with a low-pressure mercury lamp in advance, so that the film thickness after heat-curing became 1.2 μm, and a hot plate was used to perform prebaking at 90°C for 1 minute to produce a cured film (coating). Next, the exposure gap was adjusted to 100 μm, and a negative photomask with line/space = 10 μm/50 μm was placed on the cured film (coating), and 80 mJ/cm2 of ultraviolet rays were irradiated with an ultra-high-pressure mercury lamp with an i-line intensity of 30 mW/cm2 to perform a photocuring reaction of the photosensitive portion.

Next, the exposed cured film (coating) was developed for 10 seconds and 20 seconds from the development time (break time = BT) at which the pattern begins to appear using a 0.04% potassium hydroxide solution at 25°C with a shower pressure of 1 kgf/cm2, and then spray washing was performed at 5 kgf/cm2, and the unexposed portion of the cured film (coating) was removed to form a cured film pattern on a glass substrate, and main curing (post-baking) was performed at 100°C for 60 minutes using a hot air dryer, thereby obtaining substrates with cured films attached thereto according to Examples 1 to 30 and Comparative Examples 1 to 18.

[Phenomena Characteristics Evaluation]

(pattern line width)

(Evaluation method)

The pattern line width after the main curing (post-bake) was measured using a measuring microscope “XD-20” (manufactured by Nikon Co., Ltd.) for a pattern line width of 10 μm for a mask width. In addition, the pattern line width was evaluated for BT+10 seconds and BT+20 seconds.

(evaluation criteria)

○: The pattern line width is within the range of 10±2㎛.

×: The pattern line width is outside the range of 10±2㎛.

(pattern linearity)

(Evaluation method)

The 10㎛ mask pattern of the main curing (post-bake) was observed using an optical microscope. In addition, the pattern linearity was evaluated in the case of BT+10 seconds and BT+20 seconds. In addition, △ or higher was considered as passing.

(evaluation criteria)

○: No roughness is observed at the pattern edge.

△: Roughness is observed in some areas of the pattern edge.

×: Roughness is observed throughout the pattern edge portion.

(pattern adhesion)

(Evaluation method)

The 10 μm mask pattern after main curing (post-bake) was observed using an optical microscope. In addition, the pattern adhesion was evaluated under the development condition of BT+20 seconds, and △ or higher was considered as passing.

(evaluation criteria)

○: No peeling is visible in the pattern

△: Peeling is visible in a very small part of the pattern.

×: Most of the pattern is peeled off

(Production of cured film (coating) for optical density (OD) evaluation)

The photosensitive resin compositions shown in Tables 1 to 5 were applied using a spin coater on a 125 mm × 125 mm glass substrate "#1737" (Corning Corp.) (hereinafter referred to as the "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet rays having a wavelength of 254 nm and an intensity of 1000 mJ/cm2 with a low-pressure mercury lamp in advance, so that the film thickness after heat-curing became 1.2 μm, and a hot plate was used to perform prebaking at 90°C for 1 minute to produce a cured film (coating). Next, the exposure gap was adjusted to 100 μm, and a negative photomask with line/space = 10 μm/50 μm was placed on the cured film (coating), and 80 mJ/cm2 of ultraviolet rays were irradiated with an ultra-high-pressure mercury lamp with an i-line intensity of 30 mW/cm2, so as to perform a photocuring reaction of the photosensitive portion.

Next, the exposed cured film (coating) was developed for 20 seconds from the development time (break time = BT) at which the pattern begins to appear with a shower pressure of 1 kgf/cm2 using a 0.04% potassium hydroxide solution at 25°C, and then spray-rinsed at 5 kgf/cm2 to remove the unexposed portion of the cured film (coating) to form a cured film pattern on a glass substrate, and a hot air dryer was used to perform main curing (post-bake) at 100°C for 60 minutes to obtain a substrate having a cured film attached thereto according to Examples 1 to 30 and Comparative Examples 1 to 18.

[Optical density evaluation]

(Evaluation method)

The optical density (OD) of the cured film (coating) produced was evaluated using a Macbeth transmission densitometer. In addition, the film thickness of the cured film (coating) formed on the substrate was measured, and the value of the optical density (OD) divided by the film thickness was defined as OD/㎛.

Optical density (OD) was calculated using the following formula (1).

Optical density (OD) = -log ₁₀ T (1)

(T represents transmittance)

[Content Evaluation]

(Evaluation method)

As in the case of optical density (OD) evaluation, the surface of the cured film (coating) produced was rubbed repeatedly 20 times with an oily rag (waste) immersed in PGMEA. Also, △ or higher was considered as passing.

(evaluation criteria)

○: No dissolution was observed on the surface of the cured film (coat), and no scratches were formed.

△: Dissolution is observed in a very small portion of the surface of the cured film (coat), and scratches are also observed in a very small portion.

×: The surface of the cured film (coating) is softened and most of it is scratched.

[Evaluation of pattern line width changes due to aging]

(Evaluation method)

For the photosensitive resin compositions of Examples 1 to 4, 6, 8, 10, 12, 14, 16 to 30 and Comparative Examples 1 to 4, 6, 8, 17, and 18, after storing them at 5°C for 1 month, an evaluation substrate was produced in the same manner as for the development characteristic evaluation, and the pattern linewidth was measured in the same manner as for the pattern linewidth evaluation. The evaluation of the change in the pattern linewidth over time was performed under the development condition of BT+20 seconds. In addition, △ or higher was considered as passing.

(evaluation criteria)

○: The change rate of line width is within 5% compared to immediately after the photosensitive resin composition is manufactured.

△: The change rate of line width is 5 to 20% compared to immediately after the photosensitive resin composition is manufactured.

×: The change rate of line width is 20% or more compared to immediately after the photosensitive resin composition is manufactured.

(Production of cured film (coating) for reflectivity evaluation)

The photosensitive resin compositions shown in Tables 1 to 5 were applied using a spin coater on a 125 mm × 125 mm glass substrate "#1737" (Corning Corp.) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet rays having a wavelength of 254 nm and an intensity of 1000 mJ/cm2 with a low-pressure mercury lamp in advance, so that the film thickness after heat-curing became 1.2 ㎛, and a hot plate was used for prebaking at 85°C for 1 minute to produce a cured film (coating). Subsequently, a hot air dryer was used for main curing (post-baking) at 100°C for 60 minutes, to obtain substrates with cured films according to Examples 5 to 30 and Comparative Examples 5 to 18.

[Reflectivity Evaluation]

(Evaluation method)

The reflectance on the cured film (coating) side of the substrate to which the produced cured film (coating) was attached was measured at an incident angle of 2° using an ultraviolet-visible-near-infrared spectrophotometer “UH4150” (manufactured by Hitachi High-Tech Science Co., Ltd.).

From the evaluation results of Examples 5 to 12 and 17 to 30, it was found that by setting the content of the coloring material, which is the (H) component, to 20 to 80 mass% based on the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained, and at the same time, desired development characteristics (pattern line width, pattern linearity) can be obtained. This is thought to be because the content of the photosensitive resin, which is the original binder, is sufficient to appropriately achieve development characteristics, particularly pattern linearity.

From the evaluation results of Examples 1 to 30 and Comparative Examples 1 to 16, it was found that a cured film (coating) having excellent solvent resistance was obtained by setting the total mass of the (C) component and the (D) component in the total solid content to 6 to 24 mass% with respect to the total mass of the solid content. This is thought to be because when the total mass of the (C) component and the (D) component is 5 mass% or more, solvent resistance can be secured, and when it is 25 mass% or less, sufficient pattern adhesion can be secured, so that pattern formation by development can be appropriately performed.

From the results of Examples 1 to 20, 24 to 30, and Examples 21 to 23, it was found that by using an epoxy compound having two or more glycidyl groups as the (C) component, the change in pattern line width due to time can be suppressed compared to an epoxy compound having an epoxycyclohexyl group. This is thought to be because by applying an epoxy compound having a glycidyl group, the reaction between the carboxyl group of the photosensitive resin and the epoxy group at a temperature below room temperature can be suppressed.

In addition, from the results of Examples 1 to 20, 24 to 30 and Comparative Examples 17 and 18, it was found that by using an epoxy compound having a glycidyl group as the (C) component and dicyandiamide as the (D) component, the change in pattern linewidth due to changes over time can be significantly suppressed. This is thought to be because, for example, when an acid anhydride is used as a curing agent for an epoxy compound, the pattern linewidth is likely to change during development if the acid anhydride is ring-opened due to changes over time, whereas dicyandiamide has excellent stability under low temperatures, so it is difficult for the pattern linewidth to change over time.

From the results of Examples 1 to 30, it was found that when the ratio of the epoxy equivalent of component (C) to the equivalent of the amino group of dicyandiamide (D) is in the range of 0.5 to 2.0, the line width reproducibility, linear reproducibility, and solvent resistance of the formed cured film can be sufficiently improved. This is thought to be because the epoxy compound can be sufficiently cured, thereby suppressing unreacted epoxy compound from remaining in the photosensitive resin composition.

From the results of Examples 26 to 29, it was found that the reflectance measured from the surface of the coating film could be reduced by adding (I) silica particles having an average particle diameter of 1 to 95 nm. This is thought to be because the use of silica particles having a small average particle diameter can reduce the unevenness of the surface of the cured film (coating film) and suppress the unevenness of the reflectance within the surface of the cured film (coating film).

As is clear from the results of Examples 1 to 30 and Comparative Examples 1 to 18, it was found that by using a photosensitive resin composition containing an unsaturated group-containing alkali-soluble resin of the general formula (1) of the present invention and dicyandiamide as an epoxy curing agent, a cured film capable of forming a detailed pattern can be produced even at a low-temperature firing temperature of 140°C or lower.

The photosensitive resin composition of the present invention can form a cured film pattern having a line width of 10±2 ㎛, excellent development adhesion and linearity, and good solvent resistance, even without including a process of heat-curing at a temperature exceeding 140°C as a process for forming a cured film pattern. Therefore, a cured film pattern having the above-described properties can be formed on a resin film such as PET or PEN having a heat-resistant temperature of 140°C or lower, and an organic device attachment substrate having an organic EL or organic TFT on a glass substrate or a silicon wafer. The photosensitive resin composition of the present invention is suitable for forming a cured film such as a transparent film pattern, an insulating film pattern, a black matrix, a partition pattern, or the like required when forming a color filter, an organic EL pixel, or a touch panel, on a substrate having a low heat-resistant temperature, and these cured film attachment substrates can be used for the manufacture of display devices such as liquid crystals or organic EL, and the manufacture of solid-state photographing elements such as CMOS, and touch panels.

Claims (14)

A photosensitive resin composition used to form a cured film on a substrate having a heat-resistant temperature of 140°C or lower.
(A) An alkali-soluble resin containing an unsaturated group,
(B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds, and
(C) An epoxy compound having two or more epoxy groups,
(D) Dicyandiamide, and
(E) Photopolymerization initiator and,
(F)Solvent,
Including,
(A) The unsaturated group-containing alkali-soluble resin of component is an unsaturated group-containing alkali-soluble resin represented by general formula (1).
A photosensitive resin composition in which the sum of the masses of components (C) and (D) is 6 to 24 mass% with respect to the total mass of the solid content.

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a direct bond, Y is a tetravalent carboxylic acid residue, and Z is each independently a hydrogen atom or a substituent represented by general formula (2). However, at least one of Z is a substituent represented by general formula (2), and n is an integer of 1 to 20.)

(In formula (2), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.) delete In the first paragraph,
The epoxy compound of the above (C) component is a photosensitive resin composition having an epoxy equivalent of 100 to 300 g/eq. In the first paragraph,
A photosensitive resin composition in which the epoxy compound of the above (C) component is an epoxy compound having two or more glycidyl groups. In the first paragraph,
A photosensitive resin composition in which the ratio of the equivalent number (E _ep ) of the epoxy group of the above-mentioned (C) component and the equivalent number (E _am ) of the amino group of dicyandiamide of the (D) component is E _ep /E _am = 0.5 to 2. In the first paragraph,
A photosensitive resin composition comprising an imidazole compound (G) as a curing accelerator, wherein the mass of the curing accelerator is 0.05 to 2 mass% with respect to the total mass of the solid content of the epoxy compound of the component (C) and the dicyandiamide of the component (D). In the first paragraph,
A photosensitive resin composition comprising a (H) coloring agent selected from the group consisting of organic pigments or inorganic pigments. In paragraph 7,
A photosensitive resin composition in which the above (H) coloring agent is a light-blocking agent selected from the group consisting of a black organic pigment, a mixed color organic pigment, or a black inorganic pigment. In the first paragraph,
(I) A photosensitive resin composition containing silica particles, wherein the average particle diameter of the silica particles is 1 to 95 nm. In the first paragraph,
A photosensitive resin composition wherein the above (E) photopolymerization initiator is an acyl oxime photopolymerization initiator having a molar absorption coefficient of 10,000 L/mol cm or more at 365 nm. In Article 10,
A photosensitive resin composition in which the above (E) photopolymerization initiator is an acyl oxime photopolymerization initiator represented by general formula (3).

( _R6 , _R7 are each independently a C1∼C15 alkyl group, a C6∼C18 aryl group, a C7∼C20 arylalkyl group, or a C4∼C12 heterocyclic group, and R8 is a C1∼C15 alkyl group, a C6∼C18 aryl group, or a C7∼C20 arylalkyl group. Here, the alkyl group and the aryl group may be substituted with a C1∼C10 alkyl group, a C1∼C10 alkoxy group, a C1∼C10 alkanoyl group, 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 linear, branched, or cyclic alkyl group.) A cured film formed by curing the photosensitive resin composition according to any one of claims 1, 3 to 11. A cured film-attached substrate having a cured film as described in claim 12. A method for manufacturing a substrate having a cured film attached thereto by forming a cured film pattern on a substrate having a heat-resistant temperature of 140°C or lower,
A method for producing a substrate with a cured film attached, comprising: applying the photosensitive resin composition according to any one of claims 1, 3 to 11 onto a substrate, exposing through a photomask, removing unexposed portions by development, and heating at 140° C. or lower to form a cured film pattern.