JP2020166253A - Photosensitive resin composition, cured film formed by curing photosensitive resin composition, substrate with cured film, and method for manufacturing substrate with cured film - Google Patents

Abstract

To provide a photosensitive resin composition from which a resin film pattern can be formed that is excellent in development adhesiveness and linearity even when a substrate having low heat resistance is used, and also excellent in solvent resistance, alkali resistance and the like.SOLUTION: The photosensitive resin composition of the present invention is to be used to form a cured film on a substrate having a heat-resistant temperature of 140°C or lower, and the composition comprises (A) an unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) an epoxy compound having at least two epoxy groups, (D) dicyandiamide, and (E) a photopolymerization initiator, and (F) a solvent. The total mass of the (C) component and the (D) component is 6 to 24 mass% with respect to the whole mass of the solid content.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition, a cured film obtained by curing a photosensitive resin composition, a substrate with a cured film, and a method for producing a substrate with a cured film.

In recent years, for the purpose of making devices flexible and one-chip, for example, a cured film (transparent) is directly applied to a plastic substrate (plastic film, resin film) such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate). Insulation film, etc.) pattern, colored film pattern, and light-shielding film pattern can be formed, and a cured film pattern is directly applied to a substrate with an organic device provided with an organic EL, an organic thin film transistor (TFT), etc. on a glass substrate or a silicon wafer. , It is required to be able to form a colored film pattern and a light-shielding film pattern.

However, since the above-mentioned plastic substrate and the substrate with an organic device have a low heat resistance of 140 ° C. or less, the conventional photosensitive resin composition is used to directly attach the plastic substrate or the substrate with an organic device to the plastic substrate or the substrate with an organic device at a low firing temperature of 140 ° C. or less. When a resin film pattern, a colored film pattern, and a light-shielding film pattern are formed, the film strength of the formed pattern becomes insufficient, and in a post-process (development process, etc.), there are problems such as film loss of the coating film, surface roughness, and pattern peeling. There is a problem that occurs.

Therefore, a photosensitive resin composition that can be used for a substrate having low heat resistance has been 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. The radiation-sensitive composition has sufficient adhesion to a substrate even when fired at a low temperature (100 to 140 ° C.) that does not cause yellowing due to the inclusion of a photopolymerization initiator and a thermal polymerization initiator. It is said that a color filter can be formed.

Japanese Unexamined Patent Publication No. 2003-15288

However, according to the findings of the present inventors, the radiation-sensitive composition described in Patent Document 1 has desired development characteristics (for example, pattern line width, pattern linearity) and solvent resistance, although it has adhesion to a substrate. I couldn't get sex.

The present invention has been made in view of this point, and even when a substrate having low heat resistance is used, a resin having excellent development adhesion and linearity, as well as excellent solvent resistance and alkali resistance. An object of the present invention is to provide a photosensitive resin composition capable of forming a film pattern, a cured film obtained by curing the photosensitive resin composition, a substrate with a cured film, and a method for producing a substrate with a cured film.

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, and comprises (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, and (E) a photopolymerization initiator. The total mass of the component (C) and the component (D) containing the solvent (F) is 6 to 24% by mass with respect to the total mass of the solid content.

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

The substrate with a cured film of the present invention has the above-mentioned cured film.

The method for producing a substrate with a cured film of the present invention is a method for producing a substrate with a cured film by forming a cured film pattern on a substrate having a heat resistant temperature of 140 ° C. or lower, and the above-mentioned photosensitive resin composition is applied onto the substrate. The unexposed portion is removed by development, and the mixture is heated at 140 ° C. or lower to form a cured film pattern.

According to the present invention, a photosensitive resin composition capable of forming a resin film pattern having excellent development adhesion and linearity and excellent solvent resistance and alkali resistance even when a substrate having low heat resistance is used. It is possible to provide a cured film obtained by curing a product, a photosensitive resin composition, a substrate with a cured film, and a method for producing a substrate with a cured film.

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

The (A) unsaturated group-containing alkali-soluble resin contained in the photosensitive resin composition of the present invention will be described.

The alkali-soluble resin (A) having a carboxy group and a polymerizable unsaturated group in one molecule represented by the general formula (1) of the present invention is an epoxy compound (a-) having two epoxy groups in one molecule. The reaction product of 1) and the unsaturated group-containing monocarboxylic acid is reacted with a dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), and a tetracarboxylic acid or its acid dianhydride (c). Obtained by

(In the formula (1), R ₁ , R _2, R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an atomic or methyl group, where X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, and Z is independently represented by a hydrogen atom or the general formula (2). However, one or more of Z are substituents represented by the 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.)

An alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by the general formula (1) (hereinafter, also simply referred to as "alkali-soluble resin represented by the general formula (1)"). The manufacturing method will be described in detail.

First, an unsaturated group is contained in an epoxy compound (a-1) having two epoxy groups in one molecule represented by the general formula (4) (hereinafter, also simply referred to as “epoxy compound (a-1)”). A monocarboxylic acid (eg, (meth) acrylic acid) is reacted to give an epoxy (meth) acrylate.

(In formula (4), R ₁ , R _2, R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and X is −CO. -, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, Fluoren-9,9-jiyl Group or direct bond.)

The epoxy compound (a-1) is an epoxy compound having two glycidyl ether groups by reacting bisphenols with epichlorohydrin.

Examples of bisphenols used as raw materials for the epoxy compound (a-1) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4-hydroxy-). 3,5-Dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) 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, 4,4'-biphenol, Includes 3,3'-biphenol and the like. Only one of these may be used alone, or two or more thereof may be used in combination.

Examples of the unsaturated group-containing monocarboxylic acid compound include a compound obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride or phthalic anhydride in addition to acrylic acid and methacrylic acid. Etc. are included.

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

(In formula (5), R ₁ , R _2, R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an 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-, fluorene-9,9-diyl group or direct bond.)

Synthesis of diol (d) represented by the general formula (5), subsequent addition reaction of polyvalent carboxylic acid or its anhydride, and monofunctional epoxy having a polymerizable unsaturated group having reactivity with a carboxy group. In the production of the alkali-soluble resin represented by the general formula (1) by reacting a compound or the like, the reaction is usually carried out in a solvent using a catalyst as needed.

Examples of solvents include cellosolvent solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high boiling ether or ester solvents such as jiglime, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate; cyclohexanone, A ketone solvent such as diisobutyl ketone is included. The reaction conditions such as the solvent and the catalyst used are not particularly limited, but for example, it is preferable to use a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature as the reaction solvent.

Further, it is preferable to use a catalyst in the reaction between the carboxy group and the epoxy group, and Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine and tris (2). , 6-Dimethoxyphenyl) Phosphines such as phosphines are described.

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

(In the formula (1), R ₁ , R _2, R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an atomic or methyl group, where X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, and Z is independently represented by a hydrogen atom or the general formula (2). However, one or more of Z are substituents represented by the 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 for synthesizing the alkali-soluble resin represented by the general formula (1) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by the general formula (5). Therefore, it is necessary to use dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) in combination with 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. Further, these carboxylic acid residues may contain a bond containing a hetero element such as -O-, -S-, and a carbonyl group.

Examples of the dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) include chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or Those acid monoanhydrides and the like can be used.

Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralinic acid, malonic acid, glutaric acid, citric acid, Includes acid monoanhydrides such as tartrate, oxoglutaric acid, pimellinic acid, sebacic acid, suberic acid, diglycolic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced. Examples of acid monoanhydrides of alicyclic dicarboxylic acid or tricarboxylic acid include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid and norbornandicarboxylic acid, and optionally. Dicarboxylic acid or acid monoanhydride of tricarboxylic acid into which the substituent of the above is introduced is included. Examples of acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid and trimellitic acid, and dicarboxylic acids or tricarboxylic acids into which arbitrary substituents have been introduced. Includes acid monoanhydride.

Among the dicarboxylic acids or tricarboxylic acid monoanhydrides, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferable, and succinic acid, itaconic acid and tetrahydrophthalic acid are preferable. Is more preferable. Further, in the dicarboxylic acid or tricarboxylic acid, it is preferable to use those acid monoanhydrides. As the above-mentioned acid monoanhydride of dicarboxylic acid or tricarboxylic acid, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, and their acid dianhydrides. Can be used.

Examples of chain hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain type in which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced. Hydrocarbon tetracarboxylic acid and the like are included. Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptantetracarboxylic acid, norbornantetracarboxylic acid, and chain hydrocarbon groups. An alicyclic tetracarboxylic acid or the like into which a substituent such as a saturated hydrocarbon group has been introduced is included. Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid and the like.

Among the tetracarboxylic acids or acid dianhydrides thereof, biphenyltetracarboxylic dians, benzophenonetetracarboxylic acids and diphenyl ether tetracarboxylic acids are preferable, and biphenyltetracarboxylic acids and diphenyl ether tetracarboxylic acids are more preferable. Further, in the case of tetracarboxylic acid or its acid dianhydride, it is preferable to use the acid dianhydride. As for the above-mentioned tetracarboxylic acid or acid dianhydride thereof, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

The reaction between the diol (d) represented by the general formula (5) and the acid components (b) and (c) is not particularly limited, and a known method can be adopted. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method for reacting an epoxy (meth) acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ° C.

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

For example, when dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), tetracarboxylic acid or its acid dianhydride (c) is used, it is relative to the diol (d) represented by the general formula (5). It is preferable to react so that the molar ratio [(d) / [(b) / 2+ (c)]] of the amount of the acid component [(b) / 2+ (c)] 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 is not increased, so that the stability over time of the alkali-soluble resin composition is enhanced. Can be done. 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 that the content of the unreacted acid dianhydride increases. Therefore, the stability of the alkali-soluble resin composition over time can be improved. For the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (1), the molar ratio of each component of (d), (b) and (c) can be arbitrarily set within the above range. Can be changed.

The acid value of the alkali-soluble resin represented by the general formula (1) is preferably in the range of 20 to 180 mgKOH / g, preferably 80 mgKOH / g or more and 120 mgKOH / g or less. When the acid value is 20 mgKOH / g or more, the residue is less likely to remain during alkaline development, and when the acid value is 180 mgKOH / g or less, the penetration of the alkaline developer does not become too fast, so peeling development should be suppressed. Can be done. The acid value can be determined by titrating with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) by gel permeation chromatography (GPC) measurement (HLC-8220 GPC, manufactured by Tosoh Corporation) is usually 1000 to 100,000. , 2000 to 20000, more preferably 2000 to 6000. When the weight average molecular weight is 1000 or more, it is possible to suppress a decrease in pattern adhesion during alkaline development. Further, when the weight average molecular weight is less than 100,000, it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and it does not take too much time for alkaline development.

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 the component (A) is preferably 30 to 80% by mass with respect to the total mass of the solid content when the coloring material is not contained, and is 2 to 70% by mass when the coloring material is contained. Is preferable.

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

The component (B) makes the adhesion of the cured film higher, and also makes the exposed portion more soluble in the alkaline developer to make the linear reproducibility of the cured film higher. However, in order to make the cured film less brittle, suppress the decrease in the acid value of the composition, increase the solubility of the unexposed portion in the alkaline developer, and improve the linear reproducibility of the cured film. , (B) The amount of the component is preferably not too high.

The content of the component (B) is preferably 10 to 60 parts by mass with respect to 100 parts by mass of the 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, and tetraethylene glycol. Di (meth) acrylate, tetramethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethyl propantri (meth) acrylate, trimethylol ethanetri (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, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa. It has (meth) acrylic acid esters such as (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and an ethylenic double bond. The compound includes a dendritic polymer having a (meth) acrylic group and the like. It should be noted that these may be used alone or in combination of two or more.

An example of a dendritic polymer having a (meth) acrylic group as a compound having an ethylenic double bond is a part of a carbon-carbon double bond in the (meth) acrylate group of a polyfunctional (meth) acrylate. A dendritic polymer obtained by adding a polyvalent mercapto compound to the mixture is included. Specifically, a dendritic polymer obtained by reacting a (meth) acryloyl group of a polyfunctional (meth) acrylate represented by the general formula (6) with a polyvalent mercapto compound represented by the general formula (7). is there.

(In formula (6), R ₉ is a hydrogen atom or a methyl group, and R ₁₀ is the rest of the k hydroxyl groups of R ₁₁ (OH) _k that donate l hydroxyl groups to the ester bond in the formula. Partial. Preferred R ₁₁ (OH) _k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or multiple molecules of the polyvalent alcohol. Is a polyhydric alcohol ether linked via an ether bond by dehydration condensation of alcohol, or is an ester of these polyhydric alcohols or polyhydric alcohol ethers with a hydroxy acid. K and l are 2 independently. It is an integer of ~ 20 and k ≧ l.)

(In formula (7), R ₁₂ is a single bond or a 2 to 6 valent C1 to C6 hydrocarbon group, p is 2 when R ₁₂ is a single bond, and R ₁₂ is 2 to 6 valent. When it is the group of, it is an integer 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, trimethylolpropane di (meth) acrylate, and tetraethylene glycol di (meth). ) Acrylic, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolethanetri ( Meta) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (Meta) 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 hexahydrophthal Acid di (meth) acrylate, hydroxypentaerythritol 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) Acrylic, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, alkoxy-modified tri Includes (meth) acrylic acid esters such as trimethylolpropane tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

Examples of the polyvalent mercapto compound represented by the general formula (7) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, and trimethylol. Propanetri (mercaptoacetate), trimethylpropantri (mercaptopropionate), pentaerythritoltetra (mercaptoacetate), pentaerythritoltri (mercaptoacetate), pentaerythritoltetra (mercaptopropionate), dipentaerythritol hexa (mercapto) Acetate), dipentaerythritol hexa (mercaptopropionate), etc. are included. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

In addition, when synthesizing the dendritic polymer, a polymerization inhibitor may be added if necessary. Examples of the polymerization inhibitor include hydroquinone compounds and phenol compounds. Specific examples of these include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert-butylphenol (BHT) and the like.

The blending ratio of the component (A) and the component (B) is preferably 30/70 to 90/10, preferably 60/40 to 80/20, in terms of weight ratio (A) / (B). More preferred. When the compounding ratio of the component (A) is 30/70 or more, the cured film after photocuring is less likely to become brittle, and the acid value of the coating film is less likely to decrease in the unexposed portion, so that the film is soluble in an alkaline developer. Can be suppressed. Therefore, problems such as jagged pattern edges and non-sharpening are unlikely to occur. Further, when the compounding ratio of the component (A) is 90/10 or less, the ratio of the photoreactive functional group in the resin is sufficient, so that a desired crosslinked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility in the alkaline developer in the exposed area is unlikely to be high, so that the formed pattern becomes thinner than the target line width and the pattern is missing. It can be suppressed.

The photosensitive resin composition of the present invention contains (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 compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, phenol novolac type epoxy compound, and cresol novolac type epoxy compound (for example, EPPN). -501H: Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compound, phenol novolac compound containing naphthalene skeleton (for example, NC-7000L: Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compound, trisphenol methane type epoxy The unit contains glycidyl (meth) acrylate represented by a compound, a tetrakisphenol ethane type epoxy compound, a polyhydric alcohol glycidyl ether, a polyvalent carboxylic acid glycidyl ester, and a copolymer of methacrylic acid and glycidyl methacrylate (meth). ) Copolymer of monomer having acrylic group, 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, seroxide 2021P: manufactured by Daicel Co., Ltd.), tetrabutanetetracarboxylate (3,4-) Epoxycyclohexylmethyl) modified ε-caprolactone (eg, Epolide GT401: manufactured by Daicel Co., Ltd.), epoxy compound having an epoxycyclohexyl group represented by HiREM-1 manufactured by Shikoku Kasei Kogyo Co., Ltd., and polyfunctional having a dicyclopentadiene skeleton. Epoxy compounds (eg HP7200 series: manufactured by DIC Co., Ltd.), 1,2-epoxy-4- (2-oxylanyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol (eg EHPE3150: stock) Includes epoxidized polybutadiene (for example, NISSO-PB / JP-100: manufactured by Nippon Soda Co., Ltd.), an epoxy compound having a silicone skeleton, and the like.

(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, it is possible to suppress changes in the pattern line width over time. Further, it is preferable to use an epoxy resin having two or more epoxy groups because the larger the number of functional groups in one molecule, the easier it is for the epoxy resin to increase in molecular weight during thermosetting, so that the solvent resistance of the cured film is improved. It will be easier.

The epoxy equivalent of the epoxy compound of the component (C) is preferably 100 to 300 g / eq, and more preferably 100 to 250 g / eq. The number average molecular weight (Mn) of the epoxy compound of the 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 obtained while ensuring development adhesion during development. can do. Further, 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 in an appropriate range, and the solvent resistance of the cured film can be ensured. As these compounds, only one kind of compound may be used, or two or more kinds thereof may be used in combination.

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

(C) the ratio of the equivalent number _{E am} number of equivalents _{E ep} and (D) amino groups of component dicyandiamide epoxy groups of component _is preferably E _ep / E am = 0.5~2.0 , E _ep / E _am = 0.7 to 1.5, more preferably. When _Eep / _Em is 0.5 or more, the epoxy compound can be sufficiently cured, so that the unreacted epoxy compound can be suppressed from remaining in the photosensitive resin composition. Further, when _Eep / _Em is 2.0 or less, the adhesion and linear reproducibility of the cured film can be sufficiently improved.

The total mass of the component (C) and the component (D) is preferably 6 to 24% by mass, more preferably 8 to 22% by mass, based on the total mass of the solid content. .. By containing 6 to 24% by mass of the component (C) and the component (D), the line width reproducibility, linear reproducibility, and solvent resistance of the cured film formed can be sufficiently enhanced.

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

Examples of the component (E) include acetophenones, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone and other acetophenones; benzophenone. , 2-Chlorobenzophenone, p, p'-bisdimethylaminobenzophenone and other benzophenones; benzyl, 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-di (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-styryl-1,3,4-oxadiazol, Halos such as 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methyldiazole 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) Halomethyl-s-triazine compounds such as -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine; 1,2- Octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-phenylsulfanylphenyl) pig N-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanyl) O-acyloxime compounds such as phenyl) butane-1-onoxime-O-acetate; benzyldimethylketal, thioxanson, 2-chlorothioxanone, 2,4-diethylthioxanone, 2-methylthioxanone, 2 -Sulfur compounds such as isopropylthioxanson; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone; azobisisobutylnitrile, benzoyl peroxide, cumempaoxide and the like. Organic peroxides; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, pentaerythritol tetrakis (3-mercaptopropionate); tertiary such as triethanolamine and triethylamine. Includes amines and the like. As these photopolymerization initiators, only one of them may be used alone, or two or more of them may be used in combination.

In particular, when the photosensitive resin composition contains a coloring material, it is preferable to use O-acyloxym compounds (including ketooxime). Examples of the specific compound group preferably include an O-acyloxime-based photopolymerization initiator represented by the general formula (3) or the general formula (8). Among these compound groups, when a colorant is used at a high pigment concentration or when a light-shielding film pattern is formed, an O-acyloxime-based photopolymerization in which the molar extinction coefficient at 365 nm is 10,000 L / mol · cm or more is started. It is more preferable to use an agent. As a specific compound group, there is an O-acyloxime-based photopolymerization initiator represented by the general formula (3). The term "photopolymerization initiator" as used in the present invention is used to include a sensitizer.

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

In formula (8), R ₁₃ and R ₁₄ are independently linear or branched alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 4 to 10 carbon atoms, or cycloalkylalkyl groups. Alternatively, it is an alkylcycloalkyl group or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₁₅ is an independently linear or branched alkyl having 2 to 10 carbon atoms. is a group or an alkenyl group, -CH 2 in the alkyl or alkenyl group _-. some of the groups may be substituted by -O- group further hydrogen atoms in radicals of R ₁₃ to R ₁₅ May be partially substituted with halogen atoms.)

The mass of the component (E) is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total mass of the components (A) and (B). When the mass of the component (E) is 0.1% by mass or more with respect to the total mass of the components (A) and (B), the photopolymerization rate is appropriate, so that the decrease in sensitivity is suppressed. it can. Further, when it is 30% by mass or less, the line width faithful to the mask can be reproduced and the pattern edge can be sharpened.

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

Examples of the solvent contained in the (F) photosensitive resin composition include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-. Alcohols such as 2-butanone and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone; toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons; cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, diethylene glycol ethylmethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, Esters such as 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 are included. By dissolving and mixing these together, a uniform solution-like composition can be obtained. These solvents may be used alone or in combination of two or more in order to obtain required properties such as coatability.

The content of the component (F) varies depending on the target viscosity, but is preferably 60 to 90% by 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 compound include imidazole, 1H imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl. Includes imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and the like.

The mass of the (G) imidazole compound is preferably 0.05 to 2% by mass, preferably 0.1 to 1% by mass, based on the total mass of the solid contents of the (C) epoxy compound and (D) dicyandiamide. More preferably. By setting the mass of the (G) imidazole compound to 0.05% by mass or more with respect to the total mass of the solid content of the (C) epoxy compound and (D) dicyandiamide, the reaction with the epoxy resin can be promoted. The solvent resistance of the cured film can be improved. Further, by setting the mass of the (G) imidazole compound to 2% by mass or less, the reaction with the epoxy compound can be promoted without precipitating dicyandiamide, which is not highly soluble in a solvent, in the photosensitive resin composition. ..

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

The colorant is preferably a colorant selected from the group consisting of organic pigments or inorganic pigments, and more preferably a light-shielding material selected from the group consisting of organic black pigments or inorganic black pigments.

The content of the coloring material as the component (H) can be arbitrarily determined according to the desired degree of shading. It is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, based on the solid content in the photosensitive resin composition. When the coloring material is 20% by mass or more with respect to the solid content in the photosensitive resin composition, sufficient light-shielding property can be obtained. When the colorant is 80% by mass or less with respect to the solid content in the photosensitive resin composition, the content of the photosensitive resin serving as the original binder does not decrease, so that the desired development characteristics and film formation You can get the ability.

Examples of the black organic pigment as the component (H) include perylene black, aniline black, cyanine black, lactam black and the like. Examples of mixed color organic pigments include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, slene pigments, perylene pigments, perinone pigments, quinophthalone pigments, and diketo. At least two colors selected from organic pigments such as pyrolopyrrole pigments and thioindigo pigments are mixed and pseudo-blackened. Examples of the black inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black and the like. Depending on the function of the target photosensitive resin composition, only one of these components (H) may be used alone, or two or more thereof may be used in combination. Among the above pigments, carbon black is preferable from the viewpoint of light-shielding property, surface smoothness, dispersion stability, and affinity with resin. When an organic pigment is used, it is preferably atomized (the specific surface area by the BET method is 50 m ² / g or more) 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 component (H) include, but are not limited to, those having 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 etc. , 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.

Further, it is preferable that the coloring material of the component (H) is previously dispersed in a solvent together with a dispersant to prepare a coloring material dispersion liquid, and then blended as a photosensitive resin composition for a coloring film. Here, the solvent described above can be used as the solvent to be dispersed. Among the above-mentioned solvents, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and the like are preferable.

As the dispersant, known dispersants such as various polymer dispersants can be used. As an example of the dispersant, known compounds conventionally used for pigment dispersion (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. 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 aid), and the like. In particular, it has 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 point to a pigment, has an amine value of 1 to 100 mgKOH / g, and has a number average molecular weight. It is preferably a cationic polymer dispersant having a value of 10 to 100,000. The blending amount of the dispersant is preferably 1 to 30% by mass, more preferably 2 to 25% by mass with respect to the coloring material.

Further, when preparing the colorant dispersion liquid, a part of the unsaturated group-containing alkali-soluble resin of the component (A) may be co-dispersed in addition to the above-mentioned dispersant. By covariating a part of the unsaturated group-containing alkali-soluble resin of the component (A), it is easy to maintain high exposure sensitivity, and the adhesion during development is good and the problem of residue is unlikely to occur. It can be a resin composition. At that time, the blending amount of the component (A) is preferably 2 to 20% by mass, more preferably 5 to 15% by mass in the colorant dispersion liquid. When the component (A) is 2% by mass or more, effects such as sensitivity improvement, adhesion improvement, and residue reduction can be obtained by covariance. When the component (A) is 20% by mass or less, even when the content of the coloring material is particularly large, the colorant dispersion liquid can be uniformly dispersed without becoming too viscous. The obtained colorant dispersion liquid is mixed with the components (A) to (G), and if necessary, other components are added to adjust the viscosity to be suitable for the film forming conditions, thereby achieving the production method of the present invention. It can be a photosensitive resin composition to be used.

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

The silica particles as the component (I) are not particularly limited in the production method such as gas phase reaction or liquid phase reaction and the shape (spherical or non-spherical). Further, silica particles surface-treated by a silane coupling agent treatment or the like can also be used without particular limitation.

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

By using the silica particles, the refractive index of the light-shielding film containing the silica particles can be lowered.

The average particle size of the silica particles is preferably 1 to 95 nm, more preferably 5 to 90 nm. By using silica particles having a small average particle diameter, rattling on the side surface of the fine line pattern can be suppressed. In addition, it has the effect of reducing the unevenness on the surface of the cured film (coating film), and can suppress variations in the reflectance in the surface of the cured film (coating film).

The content of the silica particles is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, based on the total mass of the photosensitive resin composition. When the content of the silica particles is within the above range, good patterning property can be ensured while achieving low reflectance.

The average particle size of the silica particles can be measured by the cumulant method using a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) by a dynamic light scattering method.

Further, those having a refractive index of 1.10 to 1.47 can be used. In addition to being able to use ordinary silica particles having a refractive index of 1.45 to 1.47, by using hollow silica particles having a low refractive index, the refractive index of a light-shielding film containing only ordinary silica particles is higher than that of the ordinary silica particles. It is also possible to lower the refractive index of the light-shielding film.

The refractive index of the silica particles can be determined from a transparent mixed solution obtained by mixing the silica particles in powder form with a standard refractive index having a known refractive index. In this case, the refractive index of the standard refractive index of the mixed solution is defined as the refractive index of the silica particles. The refractive index of the silica particles can be measured using an Abbe refractive index meter.

Further, since the reflection caused by the difference in the refractive index between the layer formed on the cured film (coating film) and the cured film (coating film) can be suppressed, the reflection can be performed without separately providing an antireflection film or the like. It can be suppressed.

The shape of the silica particles may be a true spherical shape or an elliptical shape. The shape of the silica particles used in the present invention is preferably spherical.

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

The sphericity of the silica particles can be obtained from the ratio of the longest diameter to the shortest diameter of the particles (the average value of any 100 silica particles). Here, the longest diameter and the shortest diameter of the silica particles are values obtained by photographing the silica particles with a transmission electron microscope and measuring the longest diameter and the shortest diameter of the silica particles from the obtained micrograph.

The silica particles as the component (I) can be mixed with other compounding components as a silica particle dispersion dispersed in a solvent. As the dispersant, known compounds used for dispersing pigments (light-shielding components) (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) and the like can be used without particular limitation. ..

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

In the method for producing a cured film of the present invention, the above-mentioned photosensitive resin composition is applied onto a substrate having a heat resistant temperature of 140 ° C. or lower, exposed through a photomask, and an unexposed portion is removed by development. This is a manufacturing method in which a predetermined cured film pattern is formed by heating at a temperature of ° C. or lower.

Examples of the substrate used in the method for producing a cured film of the present invention include resin films (plastic substrates) such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) having a heat resistant temperature of 140 ° C. or less, and resin films. The substrate and the like are also included in which electrodes such as ITO and gold are vapor-deposited or patterned. Here, the "heat-resistant temperature" refers to a temperature at which problems such as deformation do not occur even if the substrate is exposed in a processing process such as pattern formation of a cured film on the substrate. Although the resin film changes depending on the degree of stretching treatment, it is necessary that the resin film does not exceed at least the glass transition temperature (Tg).

Further, as an example of another substrate used in the method for producing a cured film of the present invention, a thin film having high heat resistance of the substrate itself but having low heat resistance such as a glass substrate, a silicon wafer and a polyimide film can be used on the substrate. The formed ones are included. Specific examples of other substrates include a substrate with an organic device in which an organic EL (OLED) or an organic thin film transistor (TFT) is formed on a glass, a silicon wafer, or a polyimide film. The heat-resistant temperature of the substrate having low heat resistance, which is the subject of the present invention, varies depending on the type of resin and the device, but is preferably 80 to 140 ° C. The substrate with an organic device includes a substrate on which a protective film, a protective film, etc. are formed after the formation of the organic device. Even if the heat resistance of these protective films and the protective film itself is 150 ° C. or higher, if the heat resistance is substantially 140 ° C. or lower in order to ensure the function of the organic device, a substrate with an organic device can be used. This is because it is applicable.

The method of applying the photosensitive resin composition of the present invention on a substrate is any method such as a known solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coater machine, a spinner machine, or the like. Can also be adopted. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (prebaking). Pre-baking is performed by heating in an oven, a hot plate, or the like. The heating temperature and heating time in the prebake are appropriately selected according to the solvent used, and are performed 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 prebaking is performed by an ultraviolet exposure apparatus, and by exposing through a photomask, only the resist of the portion corresponding to the pattern is exposed. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp to photocure the photosensitive resin composition in the coating film. Preferably, it is photocured 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, far ultraviolet rays, electron beams, X-rays and the like can be used, but the wavelength range of the radiation is preferably 250 to 450 nm. Further, as a developing solution suitable for this alkaline development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like can be used. These developers can be appropriately selected according to the characteristics of the resin layer, but a surfactant may be added if necessary. The development temperature is preferably 20 to 35 ° C., and a fine image can be precisely formed by using a commercially available developing machine, an ultrasonic cleaner, or the like. After alkaline development, it is usually washed with water. As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied.

Alkaline development after exposure is performed for the purpose of removing the resist in the unexposed portion, and this development forms a desired pattern. Examples of the developing solution suitable for this alkaline development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of an alkali metal hydroxide, and the like. In particular, it is preferable to develop at a temperature of 23 to 28 ° C. using a weak alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate. In addition, a fine image can be precisely formed by using a commercially available developing machine, an ultrasonic cleaner, or the like.

After development, heat treatment (post-baking) is preferably performed under the conditions of 80 to 140 ° C. (set so as not to exceed the heat resistant temperature of the substrate) and 20 to 90 minutes, and the temperature is 90 to 120 ° C. and the heating time is 30. More preferably, it is carried out under the condition of ~ 60 minutes. The post-baking is performed for the purpose of enhancing the adhesion between the patterned cured film and the substrate. This is done by heating in an oven, hot plate, etc., similar to prebaking. The patterned cured film of the present invention is formed through each step by the above photolithography method.

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

First, the synthesis examples of the unsaturated group-containing alkali-soluble resin represented by the general formula (1) will be described. Unless otherwise specified, the evaluation of the resins in these synthesis examples was carried out as follows.

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

[Epoxy equivalent]
After dissolving the resin solution in dioxane, add an acetic acid solution of tetraethylammonium bromide, and titrate with a 1 / 10N-perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). It was.

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Molecular weight]
Gel Permeation Chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuperH-5000 (1) 1) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), and weight average molecular weight (Mw) as a standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) conversion value. Asked.

[Mole absorption coefficient]
The molar extinction coefficient of the acyloxime-based photopolymerization initiator was measured using an ultraviolet-visible near-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[Average particle size]
The average particle size of the silica particles was measured by the cumulant method using a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) by a dynamic light scattering method.

The abbreviations used in the synthesis example and the comparative synthesis example are as follows.
DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid SA: Succinic anhydride BPFE: Bisphenol fluorene type epoxy compound (9,9-bis (4-hydroxyphenyl) fluorene reaction with chloromethyloxylane object)
BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride THPA: tetrahydrophthalic anhydride DPHA: mixture of dipentaerythritol pentaacrylate and hexaacrylate AIBN: azobisisobutyronitrile TDMAMP: trisdimethyl Aminomethylphenol 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 return condenser, the inside of the flask system was replaced with nitrogen, and then the temperature was raised to 120 ° C. AIBN (10 g) was 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)) in this flask. The mixture was added dropwise from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.

Then, after replacing the inside of the flask system with air, AA (24.0 g, 95% of glycidyl group), TDAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution. 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 number of moles added with AA) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution and reacted at 120 ° C. for 4 hours to cause an unsaturated group-containing alkali. Soluble resin (A) -1 was obtained. The solid content concentration of the resin solution was 46.0% by mass, the acid value (solid content equivalent) 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 in a 500 ml four-necked flask equipped with a return condenser. The reaction was carried out by stirring at 100 to 105 ° C. for 20 hours. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged in the flask, and the mixture was stirred at 120 to 125 ° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A). ) -2 was obtained. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (solid content conversion) was 103 mgKOH / g, and the Mw by GPC analysis was 3600.

The above-mentioned compounding components were blended in the ratios shown in Tables 1 to 5 to prepare photosensitive resin compositions of Examples 1 to 30 and Comparative Examples 1 to 18. The numerical values in Tables 1 to 5 represent parts by mass. In Tables 1 to 5, the polymerizable unsaturated group-containing alkali-soluble resin is listed as the resin.

(Unsaturated group-containing alkali-soluble resin)
(A) -1: Resin solution obtained in Synthesis Example 1 (solid content concentration 46.0% by mass)
(A) -2: Resin solution obtained in Synthesis Example 2 (solid content concentration 56.1% by mass)

(Photopolymerizable monomer)
(B): 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: 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct (EHPE3150 (epoxy equivalent 180), manufactured by Daicel Co., Ltd.)
(C) -3: 3', 4'-epoxycyclohexylmethyl 3', 4'-epoxycyclohexanecarboxylate (celloxide 2021P, epoxy equivalent 130, manufactured by Daicel Corporation)
(C) -4: HiREM-1 (epoxy equivalent 113, manufactured by Shikoku Chemicals Corporation)
(C) -5: Tetra butanetetracarboxylate (3,4-epoxycyclohexylmethyl) modified ε-caprolactone (epoxy equivalent 197, manufactured by Daicel Corporation)

(Hardener)
(D) -1: Dicyandiamide (DICY7, manufactured by Mitsubishi Chemical Corporation)
(D) -2: Trimellitic anhydride

(Photopolymerization initiator)
(E) -1: Oxime ester-based photopolymerization initiator (ADEKA CORPORATION NCI-831, manufactured by ADEKA CORPORATION, "ADEKA CORPORATION" is a registered trademark of the same 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% by mass of 1,2-dimethylimidazole

(Coloring material)
(H) -1: Pigment dispersion of PGMEA solvent with 25.0% by mass of resin-coated carbon black and 5.0% by mass of polymer dispersant (solid content concentration 30.0% by mass)
(H) -2: Carbon black 25.0% by mass, polymer dispersant 2.0% by mass, dispersion resin (unsaturated group-containing alkali-soluble resin (A) -2 of Synthesis Example 2) 8.0% by mass Pigment dispersion of PGMEA solvent (solid content concentration 35.0% by mass)

(Silica particles)
(I) -1: Silica PGMEA dispersion "YA010C" (manufactured by Admatex Co., Ltd., solid content concentration 20% by mass, average particle diameter 10 nm)
(I) -2: Silica PGMEA dispersion "YA050C" (manufactured by Admatex Co., Ltd., solid content concentration 40% by mass, average particle diameter 50 nm)
(I) -3: Silica PGMEA dispersion "YC100C" (manufactured by Admatex Co., Ltd., solid content concentration 50% by mass, average particle diameter 100 nm)
(I) -4: Hollow silica isopropanol dispersion (manufactured by JGC Catalytic Chemicals Co., Ltd., solid content concentration 20% by mass, average particle size, 75 nm, void ratio 46% by volume)

(Surfactant)
(J): Mega Fvck F-475 (manufactured by DIC Corporation, "Mega Fvck" is a registered trademark of the company)

[Evaluation]
The following evaluations were carried out using a cured film (coating film) obtained by curing the photosensitive resin compositions of Examples 1 to 30 and Comparative Examples 1 to 18. The evaluation results are shown in Tables 6-10.

(Preparation of cured film (coating film) for evaluation of development characteristics)
The surface of the photosensitive resin compositions shown in Tables 1 to 5 was washed by irradiating the surface with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm ² in advance with a low-pressure mercury lamp, and the surface was washed. (Manufactured) (hereinafter referred to as "glass substrate"), coated with a spin coater so that the film thickness after heat curing treatment is 1.2 μm, and prebaked at 90 ° C. for 1 minute using a hot plate. A cured film (coating film) was prepared. Next, the exposure gap was adjusted to 100 μm, a negative photomask with a line / space of 10 μm / 50 μm was placed on the cured film (coating film), and an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm ² was used to cover 80 mJ / cm. ^The photocuring reaction of the photosensitive portion was carried out by irradiating with the ultraviolet rays of ² .

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.04% potassium hydroxide solution at 25 ° C. for 10 seconds from the development time (break time = BT) at which the pattern began to appear. After developing for 20 seconds, a 5 kgf / cm ² spray wash was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and the hot air dryer was used. The film was main-cured (post-baked) at 100 ° C. for 60 minutes to obtain substrates with a cured film according to Examples 1 to 30 and Comparative Examples 1 to 18.

[Development characteristic evaluation]
(Pattern line width)
(Evaluation method)
The pattern line width after the main curing (post-baking) was measured using a length measuring microscope "XD-20" (manufactured by Nikon Corporation) with a mask width of 10 μm. The pattern line width was evaluated in the case of BT + 10 seconds and the case of BT + 20 seconds.

(Evaluation criteria)
◯: The pattern line width is within the range of 10 ± 2 μm ×: The pattern line width is outside the range of 10 ± 2 μm

(Pattern linearity)
(Evaluation method)
A 10 μm mask pattern of main curing (post-baking) was observed using an optical microscope. The pattern linearity was evaluated in the case of BT + 10 seconds and the case of BT + 20 seconds. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: No knurling on the pattern edge part Δ: Jaggedness on the pattern edge part is observed in part ×: Jaggedness on the pattern edge part is observed throughout

(Pattern adhesion)
(Evaluation method)
The 10 μm mask pattern after the main curing (post-baking) was observed using an optical microscope. The pattern adhesion was evaluated under the development condition of BT + 20 seconds, and a value of Δ or more was regarded as acceptable.

(Evaluation criteria)
◯: No peeling is seen in the pattern △: Peeling is seen in a small part of the pattern ×: Most of the pattern is peeled

(Preparation of cured film (coating film) for optical density (OD) evaluation)
The surface of the photosensitive resin compositions shown in Tables 1 to 5 was washed by irradiating the surface with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm ² in advance with a low-pressure mercury lamp, and the surface was washed. (Manufactured) (hereinafter referred to as "glass substrate"), coated with a spin coater so that the film thickness after heat curing treatment is 1.2 μm, and prebaked at 90 ° C. for 1 minute using a hot plate. A cured film (coating film) was prepared. Next, the exposure gap was adjusted to 100 μm, a negative photomask with a line / space of 10 μm / 50 μm was placed on the cured film (coating film), and an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm ² was used to cover 80 mJ / cm. ^The photocuring reaction of the photosensitive portion was carried out by irradiating with the ultraviolet rays of ² .

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.04% potassium hydroxide solution at 25 ° C., and 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, a spray water wash of 5 kgf / cm ² was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 100 using a hot air dryer. Main curing (post-baking) was performed at ° C. for 60 minutes to obtain substrates with a cured film according to Examples 1 to 30 and Comparative Examples 1 to 18.

[Optical density evaluation]
(Evaluation method)
The optical density (OD) of the produced cured film (coating film) was evaluated using a Macbeth transmission densitometer. Further, the film thickness of the cured film (coating film) formed on the substrate was measured, and the value obtained by dividing the value of the optical density (OD) by the film thickness was defined as OD / μm.

The optical density (OD) was calculated by the following mathematical formula (1).
Optical density (OD) = -log ₁₀ T (1)
(T indicates transmittance)

[Solvent resistance evaluation]
(Evaluation method)
The surface of the cured film (coating film) prepared in the same manner as for the optical density (OD) evaluation was continuously rubbed 20 times with a waste cloth immersed in PGMEA. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: No dissolution is seen on the surface of the cured film (coating film) and no scratches are made. Δ: Dissolution is seen on a small part of the surface of the cured film (coating film) and only a small part is scratched. : The surface of the cured film (coating film) is softened and most of it is scratched.

[Evaluation of pattern line width change over time]
(Evaluation method)
After storing 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 at 5 ° C. for 1 month. A substrate for evaluation was prepared in the same manner as for evaluation of development characteristics, and the pattern line width was measured by the same method as for pattern line width evaluation. The evaluation of the pattern line width change with time was performed under the development condition of BT + 20 seconds. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: The rate of change of the line width is within 5% as compared with immediately after the production of the photosensitive resin composition Δ: The rate of change of the line width is 5 to 20% as compared with immediately after the production of the photosensitive resin composition. Yes: The rate of change in line width is 20% or more compared to immediately after the production of the photosensitive resin composition.

(Preparation of cured film (coating film) for reflectance evaluation)
The surface of the photosensitive resin compositions shown in Tables 1 to 5 was washed by irradiating the surface with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm ² in advance with a low-pressure mercury lamp, and the surface was washed. (Manufactured) (hereinafter referred to as "glass substrate"), coated with a spin coater so that the film thickness after heat curing treatment is 1.2 μm, and prebaked at 85 ° C. for 1 minute using a hot plate. A cured film (coating film) was prepared. Next, the main curing (post-baking) was performed at 100 ° C. for 60 minutes using a hot air dryer to obtain substrates with a cured film according to Examples 5 to 30 and Comparative Examples 5 to 18.

[Reflectance evaluation]
(Evaluation method)
Reflectance on the cured film (coating) side at an incident angle of 2 ° using the ultraviolet-visible near-infrared spectral luminous intensity "UH4150" (manufactured by Hitachi High-Tech Science Corporation) for the prepared substrate with the cured film (coating). Was measured.

From the evaluation results of Examples 5 to 12 and 17 to 30, the content of the coloring material as the component (H) was set to 20 to 80% by mass with respect to the solid content in the photosensitive resin composition to provide light-shielding property. It was found that the desired development characteristics (pattern line width, pattern linearity) can be obtained as well as sufficient. It is considered that this is because the content of the photosensitive resin, which is the original binder, is sufficient to optimize the development characteristics, particularly the linearity of the pattern.

From the evaluation results of Examples 1 to 30 and Comparative Examples 1 to 16, the total mass of the component (C) and the component (D) in the total solid content was 6 to 24% by mass with respect to the total mass of the solid content. It was found that a cured film (coating film) having excellent solvent resistance could be obtained. This is because solvent resistance can be ensured when the total mass of the components (C) and (D) is 5% by mass or more, and sufficient adhesion of the pattern can be ensured when the total mass is 25% by mass or less. It is considered that this is because the pattern can be properly formed by development.

Comparing the results of Examples 1 to 20 and 24 to 30 with those of Examples 21 to 23, by using an epoxy compound having two or more glycidyl groups as the component (C), an epoxy compound having an epoxycyclohexyl group can be used. In comparison, it was found that the change in pattern line width over time can be suppressed. It is considered that this is because the reaction between the carboxy group and the epoxy group of the photosensitive resin at a temperature of room temperature or lower can be suppressed by applying the epoxy compound having a glycidyl group.

Further, from the results of Examples 1 to 20, 24 to 30, and Comparative Examples 17 and 18, by using an epoxy compound having a glycidyl group as the component (C) and dicyandiamide as the component (D), a pattern line due to aging changes. It was found that the width change can be remarkably suppressed. This is because, for example, when an acid anhydride is used as a curing agent for an epoxy compound, the pattern line width tends to change during development if the acid anhydride opens due to aging, whereas dicyandiamide is used at a low temperature. It is considered that this is because the pattern line width does not easily change due to aging because of its excellent stability.

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

From the results of Examples 26 to 29, it was found that the reflectance measured from the coating film surface can be reduced by adding (I) silica particles having an average particle diameter of 1 to 95 nm. This is because by using silica particles having a small average particle diameter, the unevenness on the surface of the cured film (coating film) can be reduced, and the variation in reflectance in the surface of the cured film (coating film) can be suppressed. it is conceivable that.

As is clear from the results of Examples 1 to 30 and Comparative Examples 1 to 18, 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. It was found that by using the cured film, a cured film capable of forming a fine pattern can be produced even in low-temperature firing at 140 ° C. or lower.

The photosensitive resin composition of the present invention has a line width within the range of 10 ± 2 μm, and has development adhesion and a straight line, even if the process of forming a cured film pattern does not include a step of thermosetting at a temperature exceeding 140 ° C. It is possible to form a cured film pattern having excellent properties and good solvent resistance. Therefore, as described above, for resin films such as PET and PEN having a heat resistant temperature of 140 ° C. or lower, and a substrate with an organic device provided with an organic EL or an organic TFT on a glass substrate or a silicon wafer. A cured film pattern having characteristics can be formed. The photosensitive resin composition of the present invention has a cured film such as a transparent film pattern, an insulating film pattern, a black matrix, a partition wall pattern, etc., which is required for forming a color filter, an organic EL pixel, or a touch panel, at a heat resistant temperature. It is suitable for being provided on a low substrate, and these substrates with a cured film can be used for manufacturing display devices such as liquid crystals and organic EL, and solid-state photographing elements such as CMOS and touch panels.

Claims (14)

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

(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an atomic or methyl group, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, and Z is independently represented by a hydrogen atom or the general formula (2). However, one or more of Z are substituents represented by the 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 photosensitive resin composition according to claim 1 or 2, wherein the epoxy compound of the component (C) has an epoxy equivalent of 100 to 300 g / eq. The photosensitive resin composition according to any one of claims 1 to 3, wherein the epoxy compound of the component (C) is an epoxy compound having two or more glycidyl groups. The ratio of the equivalent number _{E ep} of epoxy groups in component (C), the number of equivalents _{E am} amino group of dicyandiamide (D) component _is E _ep / E am = 0.5~2, claim The photosensitive resin composition according to any one of 1 to 4. The curing accelerator contains the (G) imidazole compound, and the mass of the curing accelerator is 0.05 to the total mass of the solid content of the epoxy compound of the component (C) and the dicyandiamide of the component (D). The photosensitive resin composition according to any one of claims 1 to 5, which is 2% by mass. The photosensitive resin composition according to any one of claims 1 to 6, which comprises a (H) coloring material selected from the group consisting of organic pigments or inorganic pigments. The photosensitive resin composition according to claim 7, wherein the coloring material (H) is a light-shielding material selected from the group consisting of a black organic pigment, a mixed color organic pigment, or a black inorganic pigment. (I) The photosensitive resin composition according to any one of claims 1 to 8, which contains silica particles and has an average particle diameter of 1 to 95 nm. The photosensitive resin according to any one of claims 1 to 9, wherein the (E) photopolymerization initiator is an acyloxime-based photopolymerization initiator having a molar extinction coefficient at 365 nm of 10000 L / mol · cm or more. Composition. The photosensitive resin composition according to claim 10, wherein the (E) photopolymerization initiator is an acyloxime-based photopolymerization initiator represented by the general formula (3).

(R ₆ and R ₇ are independently alkyl groups of C1 to C15, aryl groups of C6 to C18, arylalkyl groups of C7 to C20 or heterocyclic groups of C4 to C12, and R8 is a heterocyclic group of C1 to C15. Alkyl groups, C6-C18 aryl groups or C7-C20 arylalkyl groups, wherein the alkyl and aryl groups are C1-C10 alkyl groups, C1-C10 alkoxy groups, C1-C10 alkanoyl groups, It may be substituted with halogen, the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, an ester bond, and the alkyl group may be a linear, branched or cyclic alkyl group. May be.) A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 11. A substrate with a cured film having the cured film according to claim 12. A method for producing a substrate with a cured film by forming a cured film pattern on a substrate having a heat resistant temperature of 140 ° C. or lower, wherein the photosensitive resin composition according to any one of claims 1 to 11 is applied onto the substrate. A method for producing a substrate with a cured film, which is applied to a substrate, exposed through a photomask, an unexposed portion is removed by development, and heated at 140 ° C. or lower to form a cured film pattern.