TW202043297A - Method for manufacturing substrate with cured film, substrate with cured film, photosensitive resin composition, cured film obtained by curing photosensitive resin composition, and display device having cured film or substrate with cured film - Google Patents

Abstract

This invention provides a method for manufacturing a substrate with a cured film.

A method for manufacturing a substrate with a cured film according to the present invention is a method for producing a substrate with a cured film by forming a cured film pattern having light scattering properties on the substrate, wherein an photosensitive resin composition having an inorganic particle with average particle diameter of 100 to 700 nm is applied onto a substrate, exposed through a photomask, and the unexposed portions are removed by development, and heated to form a predetermined cured film pattern.

Description

Method for manufacturing a substrate with a cured film, a substrate with a cured film, a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a display device having a cured film or a substrate with a cured film

The present invention relates to a method for manufacturing a substrate with a cured film, a substrate with a cured film, a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a display device having a cured film or a substrate with a cured film .

In recent years, not only research on high heat-resistant substrates such as glass substrates or silicon wafers that can be used at high temperatures above 200 ℃, but also for the purpose of making the device flexible or chipping, research on the low heat-resistant PET (polyethylene) Patterns are formed on plastic substrates (plastic films, resin films) such as ethylene terephthalate), PEN (polyethylene naphthalate), or organic EL devices, organic TFTs and other substrates with organic devices , And the pattern uses a photosensitive resin composition with light scattering function.

Here, if the photosensitive resin composition used for pattern formation by high-temperature firing is combined with the heat resistance of the substrate and low-temperature firing is used, the film strength of the pattern formed on the plastic substrate and the substrate with organic device will change. Insufficient gain. In the subsequent steps (for example, solvent resistance during resist coating or alkali resistance during alkali development, etc.), there are problems such as film reduction, surface roughness, pattern peeling, etc. situation.

Therefore, a photosensitive resin composition having light scattering properties that can be used for both high-temperature and low-temperature firing is being sought.

For example, Patent Document 1 discloses a photosensitive composition consisting of a TiO ₂ filler, a photopolymerizable (meth)acrylic monomer, an alkali-soluble resin, a photopolymerization initiator, and an organic solvent It is constructed to form a pattern with light scattering function. The above-mentioned photosensitive composition is designed to have photolithographic etching characteristics suitable for use in display devices, and has a light-scattering property that allows blue light to be scattered by a TiO ₂ filler to a wider angle than the incident angle.

In addition, Patent Document 2 discloses a resin composition for a light scattering layer which contains at least one resin (A) as a binder material and fluorine as a light scattering particle (B) , And contain at least one metal oxide fine particle selected from the group consisting of ZrO ₂ and TiO ₂ as the metal oxide fine particle (C). The above-mentioned resin composition for a light-scattering layer is designed to provide a resin composition for a light-scattering layer that can provide a light extraction efficiency improvement rate with low wavelength dependence and can be used in a wide wavelength range.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2013-156304 A

[Patent Document 2] JP 2015-022794 A

However, according to the findings of the inventors, the photosensitive composition system described in Patent Document 1 has low solvent resistance, while the resin composition for light scattering layer described in Patent Document 2 cannot achieve desired light scattering properties. picture of. In addition, neither the photosensitive composition described in Patent Document 1 nor the resin composition for light scattering layer described in Patent Document 2 can sufficiently satisfy the adhesion and linear reproducibility of the cured film.

The present invention was made in view of these points, and its object is to provide a method for manufacturing a substrate with a cured film, a substrate with a cured film, a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, And a display device with a cured film and a substrate with a cured film, and the photosensitive resin composition is independent of the heat-resistant temperature of the substrate, and can be directly formed on the substrate with light scattering function, and at the same time adhesion, linearity, and solvent resistance Such as excellent hardened film.

The method of manufacturing a substrate with a cured film of the present invention is to form a light-scattering cured film pattern on the substrate to manufacture a substrate with a cured film. The manufacturing method is based on photosensitive materials containing inorganic particles with an average particle diameter of 100 to 700 nm. The resin composition is applied on a substrate, exposed through a light mask, unexposed areas are removed by development, and heated to form a predetermined cured film pattern.

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

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

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

The method of manufacturing a substrate with a cured film of the present invention is to form a light-scattering cured film pattern on a substrate with a heat-resistant temperature of 150°C or less to manufacture a substrate with a cured film. The manufacturing method uses the above-mentioned photosensitive resin composition It is applied on a substrate, exposed through a light mask, unexposed parts are removed by development, and heated at 150°C or less to form a predetermined cured film pattern.

According to the present invention, it is possible to provide a method for manufacturing a substrate with a cured film, a substrate with a cured film, a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a cured film with a cured film In the display device of the substrate, the photosensitive resin composition is independent of the heat resistance temperature of the substrate, and can directly form a cured film with light scattering function and excellent adhesion, linearity, solvent resistance, etc. on the substrate.

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

The photosensitive resin composition of the present invention contains (A) an unsaturated group-containing alkali-soluble resin. As long as it has an acid value for imparting alkali developability, and can be combined with the photopolymerizable monomer of the component (B), the resin can be used without particular limitation. Among these resins, generally speaking, resins with a highly aromatic skeleton have specific gravity The tendency to be larger than that of aliphatic resins is estimated to be that when the resin concentration is the same, the specific gravity of the resin solution can be increased. This can increase the tendency of the dispersion stability of the metal oxide particles with a specific gravity greater than that of the resin. Therefore, by using the resin represented by the general formula (1), a photosensitive resin composition having sufficient dispersion stability of metal oxide particles can be obtained. Among them, when X represented by the general formula (1) is a -9,9-diyl group, an unsaturated group-containing alkali-soluble resin (cardo resin) having a polycyclic aromatic skeleton is used, Because the effect becomes greater, it can be regarded as the dispersion stability of metal oxide particles in Cardo resin has been improved. From this fact, it is estimated that the light scattering properties of the cured film formed by curing the photosensitive resin composition of the present invention can be improved. In addition, when the cardo resin is patterned by photolithography etching, it has a characteristic of excellent adhesion during development, and when a filler of metal oxide particles is coexisted, this characteristic can be effectively utilized.

The mass of the component (A) in the photosensitive resin composition of the present invention is preferably 20 to 70% by mass relative to the total mass of the solid content.

Here, when the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150°C or less, the content of component (A) is preferably 20 to 60% by mass relative to the total mass of solid components. , When using cardo resin, 35 to 55% by mass is more preferable. In addition, when using other resins such as acrylic copolymers, 20 to 50% by mass is more preferable. Relative to the total mass of the solid content, if the mass of the component (A) is 20% by mass or more, even if it contains metal oxide particles, the pattern can be stably formed during alkali development, and it can be used for dissolution development without residues. The design of the photosensitive resin composition of the pattern, relative to the total mass of solid components, if the mass of component (A) is 60% by mass or less, the fineness of the cured film can be improved. In addition, the rationality of the production process during alkali development can be improved, and the photohardenability can be fully ensured.

Furthermore, when the photosensitive resin composition of the present invention is a composition fired at a high temperature exceeding 150°C, the content of the component (A) is preferably 35 to 70% by mass relative to the total mass of the solid content. When using cardo resin, 45 to 60% by mass is more preferable. When using other acrylic copolymer resins, it is preferably 35 to 55% by mass or less. If the content of component (A) is 35% by mass or more, even if it contains metal oxide particles, it will be developed during alkali development, and the desired pattern can be obtained without residue. If the content of component (A) is 70% by mass or less, Can improve the fineness of the hardened film. In addition, the rationality of the production process during alkali development can be improved, and the photohardenability can be fully ensured.

The 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 made of dicarboxylic acid or tricarboxylic acid or the mono anhydride (b), and Tetracarboxylic acid or its dianhydride (c) is obtained by reacting a reactant of an epoxy compound (a-1) having two epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid.

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

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

A detailed description of the alkali-soluble resin having a carboxyl 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)") Manufacturing method.

First, let the epoxy compound (a-1) represented by the general formula (3) having two epoxy groups in one molecule (hereinafter, also referred to simply as the epoxy compound represented by the general formula (3) (a-1)") It reacts with an unsaturated group-containing monocarboxylic acid (for example, (meth)acrylic acid) to obtain epoxy (meth)acrylate.

(In formula (3), R ₁ , R _2, R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group with 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-, 茀-9,9-diyl or direct bonding. )

The epoxy compound (a-1) represented by the general formula (3) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin.

Examples of bisphenols used as the raw material of the epoxy compound (a-1) include: bis(4-hydroxyphenyl) ketone and bis(4-hydroxy-3,5-dimethylphenyl) ketone , Bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxy-3,5-dimethylphenyl) sulfide, bis(4- Hydroxy-3,5-dichlorophenyl) 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) pyrene, 9,9-bis(4-hydroxy-3-methylphenyl) pyrene, 9,9-bis(4-hydroxy-3-chlorophenyl)茀, 9,9-bis(4-hydroxy-3-bromophenyl) 茀, 9,9-bis(4-hydroxy-3-fluorophenyl) 茀, 9,9-bis(4-hydroxy-3- Methoxyphenyl) quince, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) quince, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) quince , 9,9-bis(4-hydroxy-3,5-dibromophenyl) pyridium, 4,4'-biphenol, 3,3'-biphenol, etc. These systems may be used alone or in combination of two or more.

Examples of the above-mentioned unsaturated group-containing monocarboxylic acid compounds include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with monoacid anhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride Wait.

The reaction system of the epoxy compound (a-1) represented by the general formula (3) and (meth)acrylic acid can use a known method. For example, in Japanese Patent Laid-Open No. 4-355450, it is stated that With respect to 1 mole of the epoxy compound having two epoxy groups, about 2 moles of (meth)acrylic acid is used to obtain a diol containing a polymerizable unsaturated group. In the present invention, the compound obtained by the above reaction is a diol containing a polymerizable unsaturated group, and is a diol containing a polymerizable unsaturated group represented by the general formula (4) (d) (hereinafter, also only It is called "the diol (d) represented by the general formula (4)").

(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 carbons, a halogen atom or a phenyl group, and R ₅ is a hydrogen atom or a methyl group, X series -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 茀-9 , 9-diyl or direct bonding.)

The synthesis of the diol (d) represented by the general formula (4), and the addition reaction of the polycarboxylic acid or its anhydride synthesized thereafter, further make the monomer with a polymerizable unsaturated group reactive with a carboxyl group In the production of the alkali-soluble resin represented by the general formula (1), the reaction of functional epoxy compounds and the like is usually carried out by using a catalyst in a solvent as needed.

Examples of solvents include: cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; diglyme, ethyl carbitol acetate, butyl High-boiling ether or ester solvents such as carbitol acetate and propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone and diisobutyl ketone. Also, the reaction clauses regarding the solvents and catalysts used The components are not particularly limited, 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, in the reaction of the carboxyl group and the epoxy group, a catalyst is preferably used. Japanese Patent Application Laid-Open No. 9-325494 describes ammonium bromide, triethylbenzylammonium chloride, etc. Phosphines such as salt, triphenylphosphine, ginseng (2,6-dimethoxyphenyl)phosphine, etc.

Next, the diol (d) represented by the general formula (4) obtained by reacting the epoxy compound (a-1) represented by the general formula (3) with (meth)acrylic acid, and the dicarboxylic acid Or tricarboxylic acid or these acid anhydrides (b), and tetracarboxylic acid or its dianhydride (c) are reacted to obtain a base having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (1) Soluble resin.

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

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

In order to synthesize the alkali-soluble resin represented by the general formula (1), the acid component used is a polybasic acid component that can react with the hydroxyl group in the molecule of the diol (d) represented by the general formula (4), and dicarboxylic acid must be used in combination Acid or tricarboxylic acid or the mono anhydride (b), and tetracarboxylic acid or its dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may also include hetero-element-containing bonds such as -O-, -S-, and carbonyl groups.

Dicarboxylic acid or tricarboxylic acid or these mono-anhydrides (b) can use chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid Carboxylic acid, or these monoacid anhydrides, etc.

Examples of the monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, and malonic acid Mono anhydrides such as glutaric acid, citric acid, tartaric acid, pendant oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., and dicarboxylic acid or tricarboxylic acid introduced with any substituent Acid anhydrides, etc. In addition, examples of mono anhydrides of alicyclic dicarboxylic acid or tricarboxylic acid include: cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid , Mono-anhydrides such as hexahydro-trimellitic acid, and mono-anhydrides of dicarboxylic acids or tricarboxylic acids with optional substituents. In addition, examples of the monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like, and dicarboxylic acid or tricarboxylic acid with optional substituents. Mono anhydride.

Among the monoanhydrides of dicarboxylic or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid are preferred, and succinic acid and itaconic acid are preferred. Tetrahydro Phthalic acid is more preferable. Furthermore, among dicarboxylic acids or tricarboxylic acids, these monoanhydrides are preferably used. The above-mentioned dicarboxylic acid or tricarboxylic acid monoanhydride system may be used alone or in combination of two or more kinds.

Moreover, chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or these dianhydrides etc. can be used for a tetracarboxylic acid or its dianhydride (c) system.

Examples of chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acid introduced with substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups. Carboxylic acid, etc. In addition, examples of the aforementioned alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and Alicyclic tetracarboxylic acid etc. introduced with substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups. In addition, examples of aromatic tetracarboxylic acids include: Pyromellitic Acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfonic acid tetracarboxylic acid Acid etc.

Among the tetracarboxylic acids or their dianhydrides, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, diphenyl ether tetracarboxylic acid are preferred, and biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid Acid is better. Moreover, among tetracarboxylic acid or its dianhydride, it is preferable to use its dianhydride. In addition, the above-mentioned tetracarboxylic acid or its dianhydride system may be used alone or in combination of two or more kinds.

The reaction between the diol (d) represented by the general formula (4) and the acid components (b) and (c) is not particularly limited, and a known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting epoxy (meth)acrylate with tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

Here, in order to make the terminal of the compound a carboxyl group, the diol (d), dicarboxylic acid or tricarboxylic acid represented by formula (4) or the mono anhydride (b), tetracarboxylic acid or its dianhydride The molar ratio of (c) becomes (d):(b):(c)=1:0.01 to 1.0:0.2 to 1.0 to make the reaction better.

For example, when using monoacid anhydride (b) and dianhydride (c), relative to the diol (d) represented by formula (4), the amount of acid component [(b)/2+(c)] The ear ratio [(d)/[(b)/2+(c)]] becomes 0.5 to 1.0 to make the reaction better. Here, when the molar ratio is 1.0 or less, since the content of the diol containing unreacted polymerizable unsaturated groups is not increased, the stability of the alkali-soluble resin composition over time can be improved. On the other hand, when the molar ratio exceeds 0.5, since the end of the alkali-soluble resin represented by formula (1) does not become an acid anhydride, the increase in the content of unreacted dianhydride can be suppressed, so that the aging of the alkali-soluble resin composition can be improved stability. In addition, for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by formula (1), the molar ratio of each component of (d), (b) and (c) can be arbitrarily changed within the above-mentioned range.

Moreover, the preferred range of the acid value of the alkali-soluble resin represented by the general formula (1) is 20 to 180 mgKOH/g, more preferably 40 mgKOH/g or more and 140 mgKOH/g or less, and 80 mgKOH/g or more and 120 mgKOH /g or less is even better. When the acid value is 20 mgKOH/g or more, residues are less likely to remain during alkali development, and when it is 180 mgKOH/g or less, the penetration of the alkali developer does not become excessively fast, so peeling development can be suppressed. In addition, the acid value system can be determined by titration with a 1/10 N-KOH aqueous solution using a potential difference titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

Gel permeation chromatography (GPC) measurement of alkali-soluble resin represented by general formula (1) (HLC-8220GPC, manufactured by TOSOH Co., Ltd.) The weight average molecular weight (Mw) in terms of polystyrene is usually 1,000 to 100,000, preferably 2,000 to 20,000, more preferably 2,000 to 6,000. The weight average molecular weight is above 1000 When it is used, the adhesion of the pattern during alkali development can be suppressed. In addition, 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 require excessive time during alkali development.

The photosensitive resin composition (B) of the present invention contains a photopolymerizable monomer having at least two ethylenically unsaturated bonds. The component (B) further improves the adhesion of the cured film, and also improves the solubility of the exposed part to the alkali developer and further improves the linear reproducibility of the cured product. However, it is not easy to embrittle the cured film, and it suppresses the decrease in the acid value of the composition and improves the solubility of the unexposed part to the alkali developer. In order to improve the linear reproducibility of the cured product, the amount of component (B) Not many good lines.

Here, when the photosensitive resin composition of the present invention is a composition sintered at a low temperature of 150° C. or less, the content of the component (B) is preferably 5 to 40% by mass relative to the total mass of the solid content. When using cardo resin as the component (A), the mass of the component (B) is preferably 5 to 20% by mass relative to the total mass of the solid content. In addition, when resins of other acrylic copolymers are used as the component (A), the mass of the component (B) is preferably 10 to 35% by mass relative to the total mass of the solid content.

In addition, when the photosensitive resin composition of the present invention is a composition fired at a high temperature exceeding 150°C, the mass of the component (B) is preferably 10 to 40% by mass relative to the total mass of the solid content When using cardo resin as the component (A), the mass of the component (B) is preferably 10 to 35% by mass relative to the total mass of the solid content. When using other acrylic copolymer resins as the (A) component, the mass of the (B) component is preferably 20 to 40% by mass relative to the total mass of the solid content.

With respect to the total mass of the solid content, by setting the mass of the component (B) to 5 to 40% by mass, it is possible to design a photosensitive resin composition having desired characteristics. For example, the The linearity and fineness of the cured film formed by curing the photosensitive resin composition.

(B) Examples of photopolymerizable monomers with at least two ethylenically unsaturated bonds include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylenedi Alcohol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane (Meth)acrylate, trimethylolethane tri(meth)acrylate, neopenteritol di(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra (Meth) acrylate, dineopentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dineopentaerythritol penta(meth) Acrylate, dineopentyl hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene (phosphazene) alkylene oxide modified hexa(meth)acrylate, caprolactone Modification of (meth)acrylates such as dineopentaerythritol hexa(meth)acrylate, dendrimers having a (meth)acryloyl group as a compound having an ethylenic double bond, etc. In addition, these systems may be used alone or in combination of two or more.

An example of the dendritic polymer of the compound having a (meth)acryloyl group as an ethylenic double bond includes: the carbon-carbon double in the (meth)acryloyl group of the polyfunctional (meth)acrylate A dendritic polymer obtained by adding a part of the bond to a polythiol-based compound. Specifically, there are: the (meth)acrylic group of the polyfunctional (meth)acrylate represented by the general formula (5) and the thiol group of the polythiol compound represented by the general formula (6) The dendritic polymer obtained by the reaction.

(In the formula (5), R ₆ is a hydrogen atom or a methyl group, and R ₇ is the remaining part of the k hydroxyl groups of R ₉ (OH) _k in which one hydroxyl group is supplied to the ester bond in the formula. Preferably, R ₉ (OH) _k is a polyol based on a non-aromatic linear or branched hydrocarbon skeleton with a carbon number of 2 to 8, or the plural molecules of the polyol are bonded via an ether bond by alcohol dehydration condensation Concatenated polyol ethers, or these polyols or esters of polyol ethers and hydroxy acids. k and l are independently integers from 2 to 20, k≧l.)

(In formula (6), R ₈ is a single bond or a C1 to C6 hydrocarbon group of 2 to 6 valences, when R ₈ is a single bond, p is 2, and when R ₈ is a 2 to 6 valence group, p is 2 to Integer of 6.)

Examples of the multifunctional (meth)acrylate represented by the general formula (5) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate (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, neopentyl four Alcohol di(meth)acrylate, neopentyl erythritol tri(meth)acrylate, neopentyl erythritol tetra(meth)acrylate, dineopentyl erythritol penta(meth)acrylate, dineopentaerythritol Alcohol hexa(meth)acrylate, trineopentaerythritol octa(meth)acrylate, trineopentaerythritol Hepta (meth) acrylate, caprolactone modified neopentyl erythritol tri (meth) acrylate, caprolactone modified neopentyl erythritol tetra (meth) acrylate, caprolactone modified dineopentyl Tetraol hexa(meth)acrylate, epichlorohydrin modified hexahydrophthalic acid di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth) Meth) acrylate, ethylene oxide modified neopentyl glycol di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, ethylene oxide modified trimethylol Trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate (meth)acrylate, ginseng((meth)) Acrylic oxyethyl) trimeric isocyanate, alkoxy modified trimethylolpropane tri(meth)acrylate, dineopentaerythritol poly(meth)acrylate, alkyl modified dineopentyl Alcohol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate and other (meth)acrylates. These compounds may be used alone or in combination of two or more.

Examples of polythiol-based compounds represented by general formula (6) include: 1,2-dithiol ethane, 1,3-dithiol propane, 1,4-dithiol butane, Dithiol ethane mercaptan, trimethylolpropane tris (thiol acetate), trimethylolpropane tris (thiol propionate), neopentyl erythritol tetra (thiol ethyl) Acid ester), neopentyl erythritol three (thiol acetate), neopentyl erythritol tetra (thiol propionate), dineopentaerythritol hexa (thiol acetate), dineopentyl Tetrahydrin hexa (thiol propionate) and the like. These compounds may be used alone or in combination of two or more.

In addition, during the synthesis of the above-mentioned dendritic polymer, a polymerization inhibitor may be added as needed. Examples of the polymerization inhibitor include hydroquinone-based compounds and phenol-based compounds. Specific examples of these include: hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert Butylphenol (BHT) and so on.

The photosensitive resin composition of this invention contains (C) epoxy compound. The content of the (C) component relative to the solid content is preferably 8 to 24% by mass. If the photosensitive resin composition contains the component (C) in a sufficient amount, the solvent resistance of the cured product can be sufficiently improved. However, in order to sufficiently improve the adhesion and linear reproducibility of the cured product, the amount of the component (C) is preferably not too much.

For example, when the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150°C or less, the photosensitive resin composition preferably contains a larger amount of (C) component. The mass of the component (C) at this time is preferably 8 to 24% by mass relative to the solid content, and more preferably 12 to 24% by mass relative to the solid content.

Furthermore, when the photosensitive resin composition of the present invention is a composition that is fired at a high temperature exceeding 150°C, the component (C) is easily cured sufficiently, so the photosensitive resin composition preferably contains the component (C) in a smaller amount . The mass of the component (C) in this case is preferably 8 to 20% by mass relative to the solid content, and more preferably 8 to 18% by mass relative to the solid content.

(C) Examples of epoxy compounds include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol novolak type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy Compound, phenol aralkyl type epoxy compound, phenol novolak compound containing naphthalene skeleton (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compound, phenol methane type ring Oxygen compounds, phenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers containing methacrylic acid and glycidyl methacrylic acid are represented (methyl ) Copolymers of monomers having (meth)acrylic groups with glycidyl acrylate as a unit, represented by 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate Alicyclic epoxy compound, multifunctional with dicyclopentadiene skeleton Epoxy compound (for example, HP7200 series: manufactured by DIC Co., Ltd.), 1,2-epoxy-4-(2-oxirane group) of 2,2-bis(hydroxymethyl)-1-butanol Cyclohexane adduct (for example, EHPE3150: manufactured by DAICEL Co., Ltd.), epoxy-based polybutadiene (for example, NISSO-PB‧JP-100: manufactured by Japan Soda Co., Ltd.), having a polysiloxane skeleton The epoxy compound and so on.

(C) The epoxy equivalent of the epoxy compound of the component is preferably 100 to 300 g/eq, and more preferably 100 to 200 g/eq. In addition, the number average molecular weight (Mn) of the epoxy compound of the component (C) is preferably 100 to 5,000. In addition, only one kind of these compounds may be used alone, or two or more kinds may be used in combination.

In addition, the epoxy equivalent of the epoxy compound of the component (C) is to dissolve the resin solution in dioxane, and then add the acetic acid solution of tetraethylammonium bromide. The potentiometric titration device "COM-1600" (Hiranuma Sangyo Co., Ltd. Co., Ltd.) It is determined by titration with a 1/10 N-perchloric acid solution. In addition, the number average molecular weight (Mn) of the epoxy compound of the component (C) can be calculated in terms of polystyrene using gel permeation chromatography (GPC) measurement (HLC-8220GPC, manufactured by TOSOH Co., Ltd.) .

The photosensitive resin composition of the present invention preferably contains metal oxide particles as the (D) component. The metal oxide particles are preferably inorganic particles with an average particle size of 100 to 700 nm, more preferably TiO _{2 with} an average particle size of 100 to 700 nm.

The above-mentioned TiO ₂ system is only required to form a cured film (coating film) capable of exhibiting a light scattering function, and the particle diameter or shape is not particularly limited. The average particle size of TiO ₂ is 100 to 700 nm, preferably 200 to 600 nm. If the average particle size of TiO ₂ is 100 nm or more, the light scattering properties of the cured product can be sufficiently improved. If the average particle size of TiO ₂ is 700 nm or less, the adhesion and linear reproducibility of the cured product can be sufficiently improved.

In addition, the average particle size of the above-mentioned TiO ₂ is a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) using a dynamic light scattering method, and can be determined by the cumulant method.

In addition, the component (D) may contain metal oxide fine particles having a refractive index of 1.9 to 2.3 instead of TiO _{2 having} an average particle diameter of 100 to 700 nm. The metal oxide fine particles having a refractive index of 1.9 to 2.3 are not particularly limited as long as the formed cured film (coating film) can exhibit a light scattering function.

Examples of the metal oxide fine particles having a refractive index of 1.9 to 2.3 include ZnO, ZrO ₂ and the like. Generally, the higher the refractive index of the metal oxide, the higher the light-scattering property, but on the other hand, when the light-scattering property is too strong, the light transmittance of straight traveling light becomes lower. In addition, the refractive index of the metal oxide fine particles can be measured with an ABBE refractometer with light having a wavelength of 589 nm.

In addition, the average particle size of the aforementioned ZnO and ZrO ₂ is preferably 150 to 500 nm, and more preferably 150 to 400 nm. If the average particle size of the metal oxide is 150nm or more, the light scattering property of the cured film can be fully improved. If the average particle size of the metal oxide is 500nm or less, the adhesion and linear reproducibility of the cured film can be fully improved .

In addition, the average particle size of the metal oxide fine particles is determined by the cumulant method using a particle size distribution meter "particle size analyzer FPAR-1000" using the dynamic light scattering method.

(D) The component system can improve the light scattering properties of the cured film. However, if the amount of component (D) contained in the photosensitive resin composition of the present invention is too large, the adhesion, linear reproducibility, fineness, and solvent resistance of the cured film will decrease, and the light penetration of the film will be reduced. The permeability is also reduced. therefore, The mass of the component (D) is preferably 1% by mass or more and 35% by mass or less with respect to the total mass of the solid components.

In addition, when the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150°C or less, the content of component (D) is 1% by mass or more and less than 35% by mass relative to the total mass of solid content % Is more preferable, more preferably 2% by mass or more and less than 25% by mass, and still more preferably 2% by mass or more and less than 20% by mass.

On the other hand, when the photosensitive resin composition of the present invention is a composition fired at a high temperature exceeding 150°C, the content of component (D) is 1% by mass or more and less than the total mass of solid components 35% by mass is preferable, and 2% by mass or more and less than 25% by mass is more preferable.

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

(E) Examples of ingredients include: acetonitrile, 2,2-diethoxy acetonitrile, p-dimethyl acetonitrile, p-dimethylamino propyl benzene, dichloro acetonitrile benzene , Acetylbenzenes such as trichloroacetbenzene, p-tertiary-butyl acetonitrile, etc.; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylamino diphenyl Benzophenones such as ketones; Benzoin ethers such as benzyl, Benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. ; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-( o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, etc. Biimidazole compounds; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1 ,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halogenated methyldiazole compounds; 2, 4,6-Ginseng (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-methoxyphenyl) Naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2- (4-Methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine and other halomethyl-s-triazine compounds; 1,2-octane Alkanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyloxime), 1-(4-phenylhydrothiophenyl)butane-1,2 -Diketone-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1- (4-Methylhydrothiophenyl) butane-1-ketoxime-O-acetate and other O-acetoxy oxime compounds; benzyl dimethyl ketal, thioxanthone, 2 -Chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and other sulfur compounds; 2-ethylanthraquinone, eight Anthraquinones such as methyl anthraquinone, 1,2-benzo anthraquinone, 2,3-diphenyl anthraquinone; azobisisobutyronitrile, benzyl peroxide, cumene peroxide Organic peroxides such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc.; triethanolamine, triethylamine, etc. Grade amine and so on. In addition, these photopolymerization initiator systems may be used alone or in combination of two or more kinds.

In particular, when the amount of metal oxides added is large, or when the amount of photopolymerization initiator added is to be reduced, or when a heat hardening process at a high temperature of 150°C is not used, it is necessary to perform light hardening more effectively. In the case of a high-sensitivity photopolymerization initiator, it is preferable to use O-acetoxime-based compounds (including ketoximes). Among these, the compound group represented by general formula (7) or general formula (8) can be applied as a higher-sensitivity photopolymerization initiator. Among them, it is better to use the molar absorption coefficient at 365nm when low-temperature curing is used for more effective photo-curing. O-acetoxime-based photopolymerization initiator of 10000L/mol‧cm or more. In addition, the "photopolymerization initiator" in the present invention is used in the sense of including a sensitizer.

(In formula (7), R ₁₀ and R ₁₁ each independently represent an alkyl group with 1 to 15 carbons, an aryl group with 6 to 18 carbons, an aryl alkyl group with 7 to 20 carbons, or a carbon number 4 to The heterocyclic group of ₁₂ , R ₁₂ represents an alkyl group with 1 to 15 carbons, an aryl group with 6 to 18 carbons, and an arylalkyl group with 7 to 20 carbons. Here, the alkyl group and the aryl group have the carbon number Alkyl groups of 1 to 10, alkoxy groups of 1 to 10 carbons, alkoxy groups of 1 to 10 carbons, which may be substituted by halogen, and the alkylene part may contain unsaturated bonds, ether bonds, and thioether bonds , Ester bond. In addition, the alkyl group may be any one of linear, branched, or cyclic.)

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

Here, with respect to the total mass of the (A) component and the (B) component, the mass of the (E) component is preferably 0.1 to 30% by mass, and more preferably 1 to 25% by mass. When the mass of (E) component is 0.1% by mass or more with respect to the total mass of (A) component and (B) component, it has a moderate photopolymerization speed, so that the decrease in sensitivity can be suppressed. In addition, when the mass of (E) component is 30% by mass or less relative to the total mass of (A) component and (B) component, since the sensitivity of the composition to exposure will not be too high, the mask can be faithfully used The line width is reproduced and the edge of the pattern can be made steep.

The photosensitive resin composition of this invention contains (F) solvent.

(F) Examples of solvents contained in the photosensitive resin composition include: methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene Alcohol monobutyl ether, 3-hydroxy-2-butanone, diacetone alcohol and other alcohols; α- or β-terpene alcohol and other terpenes; acetone, methyl ethyl ketone, cyclohexanone, N -Methyl-2-pyrrolidone and other ketones; toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons; 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 mono Glycol ethers such as ethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether; 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, propylene glycol monoethyl ether acetate and other esters. By using these to dissolve and mix, it can be formed into a uniform solution Liquid composition. These solvents can be used alone or in combination of two or more types in order to provide necessary characteristics such as coatability.

(F) The content of the component changes according to the target viscosity, but it is preferably 60 to 90% by mass in the photosensitive resin composition solution.

The photosensitive resin composition of the present invention may contain (G) an epoxy compound curing agent and/or curing accelerator. When the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150°C or less, the curing of component (C) is likely to be insufficient. Therefore, in order to fully cure component (C), the photosensitive resin composition is It is preferable to include the component (G).

Examples of the curing agent of the epoxy compound of the component (G) include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyanodiamide, Lewis acid complexes, and the like. In the present invention, it is preferable to use a polycarboxylic acid compound.

Examples of polycarboxylic acid compounds include polycarboxylic acid, polycarboxylic acid anhydrides, and polycarboxylic acid thermally decomposable esters. The so-called polyvalent carboxylic acid refers to a compound having two or more carboxyl groups in one molecule, for example, includes: succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2 -Dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetra Hydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid , Cyclohexane-1,2,4,5-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, etc. Examples of anhydrides of polycarboxylic acids include anhydrides of the above-mentioned compounds. This system can be an intermolecular acid anhydride, but generally an acid anhydride formed by ring closure in the molecule is used. Examples of thermally decomposable esters of polycarboxylic acids are the tertiary butyl ester, 1-(alkyloxy)ethyl ester, 1-(alkyl hydrogensulfanyl) ethyl ester of the above-mentioned compounds (but, alkyl-based A saturated or unsaturated hydrocarbon group with 1 to 20 carbon atoms. The hydrocarbon group may have a branched structure or a ring structure, and may be substituted by any substituent). Also, polycarboxylation The compound system may also use a polymer or copolymer having two or more carboxyl groups, and the carboxyl group may be an anhydride or a thermally decomposable ester.

In addition, examples of the above-mentioned polymer or copolymer include: a polymer or copolymer containing (meth)acrylic acid as a constituent, a copolymer containing maleic anhydride as a constituent, a combination of tetracarboxylic dianhydride and diamine or Compounds etc. formed by reaction of diols to open the ring of acid anhydrides. Among these, it is preferable to use phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,4-trihydrophthalic acid, Anhydrides of carboxylic acids. Relative to 1 mol of epoxy group of epoxy compound, the blending ratio when using polycarboxylic acid compound as hardener of epoxy compound is 0.5 to 1.5 mol of carboxyl group of polycarboxylic acid compound. 0.6 to 1.2 mol.

As the curing accelerator of the epoxy compound of the component (G), known compounds known as curing accelerators, curing catalysts, latent curing agents, etc., can be used. Examples of hardening accelerators for epoxy compounds include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acid, organometallic compounds, imidazoles, and the like. Among the above hardening accelerators, 1,8-diazabicyclo[5.4.0]undecane-7-ene or 1,5-diazabicyclo[4.3.0]non-5- Ene or the salts of these.

The amount of the hardening accelerator added is preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the epoxy compound. If the addition amount of the hardening accelerator is 0.05 parts by mass or more, the addition amount can be adjusted according to the appearance of the chemical resistance of the resin film pattern after thermal hardening. Moreover, if the addition amount of the hardening accelerator is 2 parts by mass or less, the hardening rate of the epoxy compound can be set to an appropriate range.

When the photosensitive resin composition of the present invention is a composition fired at a low temperature of 150°C or less, the total mass of the (C) component and (G) component relative to the total mass of the solid content The quality is preferably 15% by mass or more and 35.% by mass or less, and more preferably 20% by mass or more and 30% by mass or less. If the total mass of the (C) component and (G) component is 15% by mass or more relative to the total mass of the solid components, the curability can be sufficiently ensured when it is cured at a low temperature of 150°C or less. In addition, if the total mass of the (C) component and (G) component is 35% by mass or less relative to the total mass of the solid content, it will not adversely affect the patterning properties, linearity, and solvent resistance during alkali development. Can improve hardening.

When the photosensitive resin composition of the present invention is a composition that is fired at a high temperature exceeding 150°C, it may be free of (G) component, and the total mass of (C) component and (G) component relative to the total mass of solid components It is preferably 8 to 25% by mass.

Next, the method of manufacturing plural substrates with cured films of the present invention will be explained. The cured film (coating film) of the present invention can be formed by the photolithography etching method using the photosensitive resin composition of the present invention.

A manufacturing method is to form a light-scattering cured film pattern on the substrate of the present invention to manufacture a substrate with a cured film. The method is to coat a photosensitive resin composition containing inorganic particles with an average particle diameter of 100 to 700 nm. It is spread on a substrate, exposed through a light mask, unexposed parts are removed by development, and heated to form a predetermined cured film pattern.

A method of manufacturing a substrate with a hardened film by forming a light-scattering hardened film pattern on a substrate with a heat-resistant temperature of 150°C or less according to the present invention. The method is to apply the above-mentioned photosensitive resin composition to the substrate Above, exposure is performed through a light mask, unexposed areas are removed by development, and heating is performed at 150°C or less to form a predetermined cured film pattern.

A manufacturing method is to form a light-scattering cured film pattern on a substrate with a heat-resistant temperature of over 150°C in the present invention to produce a substrate with a cured film. The photosensitive resin composition described above is applied on a substrate, exposed through a light mask, and unexposed portions are removed by development, and heated at over 150°C to form a predetermined cured film pattern.

The method of coating the photosensitive resin composition of the present invention on a substrate is a well-known solution dipping method and spraying method, and a land coater machine using a roller coater, or a die slit coating method can also be used. Any method such as cloth machine or rotating machine method. By these methods, after coating to a desired thickness, the solvent is removed (after pre-baking) to form a film. The pre-baking is performed by heating by an oven, a hot plate, etc. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent used, for example, at a temperature of 60 to 110°C (set not to exceed the heat-resistant temperature of the substrate) for 1 to 3 minutes.

The exposure performed after the pre-baking is performed by an ultraviolet exposure device, and the exposure is performed through a light mask, whereby only the resist corresponding to the pattern is exposed to light. The exposure device and its exposure and irradiation conditions are appropriately selected, and light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and far ultraviolet lamps are used for exposure to light-harden the photosensitive resin composition in the coating film. Preferably, it is photohardened by irradiating a certain amount of light with a wavelength of 365 nm.

The radiation used in the exposure can be, for example, visible rays, ultraviolet rays, extreme ultraviolet rays, electron rays, X-rays, etc., but the wavelength range of the radiation rays is preferably 250 to 450 nm. In addition, as a developer system suitable for the alkaline development, for example, aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like can be used. These developer systems can be appropriately selected according to the characteristics of the resin layer, but surfactants can be added as needed. The developing temperature is preferably 20 to 35°C, and a commercially available developing machine or ultrasonic cleaner can be used to precisely form a fine image. In addition, after alkali development, it is usually washed with water. The development processing method can be applied to shower development method, spray development method, dip (dip) development method, paddle type (liquid holding) development method, etc.

The alkali development after exposure is performed for the purpose of removing the resist in the unexposed part, and the desired pattern is formed by the development. The developer system suitable for the alkaline development includes, for example, carbonate aqueous solutions of alkali metals or alkaline earth metals, aqueous hydroxides of alkali metals, etc., but it is particularly preferable to use carbonates containing sodium carbonate, potassium carbonate, lithium carbonate, etc. A weak alkaline aqueous solution of 0.05 to 3.0% by mass is developed at a temperature of 23 to 28°C, and a commercially available developing machine or ultrasonic cleaner can be used to precisely form a fine image.

When forming a light-scattering cured film pattern on a substrate with a heat-resistant temperature of 150°C or less, it is preferable to set it at a temperature of 80 to 140°C (set not to exceed the heat-resistant temperature of the substrate) and 20 to 90 minutes after development. The conditions are heat treatment (post-baking), preferably at a temperature of 90 to 120°C and a heating time of 30 to 60 minutes. The above-mentioned post-baking is performed for the purpose of improving the adhesion between the patterned cured film and the substrate. This is performed by heating by an oven, a hot plate, etc., similarly to the pre-baking. The patterned cured film of the present invention is formed through the steps implemented by the above photolithographic etching method.

When a light-scattering cured film pattern is formed on a substrate with a heat-resistant temperature of more than 150°C, it is preferable to set it at a temperature of 80 to 250°C (set not to exceed the heat-resistant temperature of the substrate) and 20 to 90 minutes after development The heat treatment (post-baking) is preferably performed under the conditions of a temperature of 180 to 230°C and a heating time of 30 to 60 minutes. The above-mentioned post-baking is performed for the purpose of improving the adhesion between the patterned cured film and the substrate. This is performed by heating by an oven, a hot plate, etc., similarly to the pre-baking. The patterned cured film of the present invention is formed through the steps implemented by the above photolithographic etching method.

By the above method, the photosensitive resin composition containing TiO ₂ with an average particle diameter of 100 to 700 nm as the component (D) is cured to form a cured film, and the visible light region has a transmittance of 70% or more. When the substrate with cured film is irradiated with white light vertically, the angle of the direct light traveling straight without scattering is set to 0°, the intensity of scattered light at 60° relative to that of scattered light at 5° can be obtained A substrate with a hardened film with a strength of 20% or more. Therefore, it can be suitably used for a display device as a light scattering layer.

By the above method, the above-mentioned photosensitive resin composition containing metal oxides (ZnO, ZrO ₂ ) with a refractive index of 1.9 to 2.3 as the component (D) is cured to form a cured film, and the transmittance in the visible light region When the angle of 80% is set to 0°, it is possible to obtain a substrate with a hardened film with the intensity of scattered light at 45° of 15% or more relative to the intensity of scattered light at 5°. Therefore, it can be suitably used for a display device as a light scattering layer.

[Example]

Hereinafter, the implementation modes of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited by these.

First, the description will be given from the synthesis example of the alkali-soluble resin represented by the general formula (1), but the evaluation of the resin in these synthesis examples is carried out as follows unless otherwise stated. For various measuring devices, when using the same model, omit the device manufacturer name from the second place. In addition, in Example 1 and Example 2, the glass substrate used for the production of the substrate with a cured film for measurement was a glass substrate subjected to all the same treatments.

[Solid content concentration]

1g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and heated at 160°C for 2 hours. Weight [W ₂ (g) ] Calculate from the following formula.

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

〔Epoxy equivalent〕

After dissolving the resin solution in dioxane, add the acetic acid solution of tetraethylammonium bromide, and titrate with a 1/10N-perchloric acid solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) Find out.

〔Acid value〕

After dissolving the resin solution in dioxane, titrate it with a 1/10 N-KOH aqueous solution using a potential difference titration device "COM-1600".

〔Molecular weight〕

Gel Permeation Chromatography (GPC) "HLC-8220GPC" (solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuperH- 5000 (1 piece) (manufactured by TOSOH Co., Ltd., temperature: 40°C, speed: 0.6 ml/min), measured as standard polystyrene (manufactured by TOSOH Co., Ltd., PS-oligomer set) conversion value And the weight average molecular weight (Mw) was calculated|required.

〔The average particle size〕

Use the particle size distribution meter "particle size analyzer FPAR-1000" of the dynamic light scattering method, and calculate it by the cumulant method.

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

DCPMA: Dicyclopentyl methacrylate

GMA: Glycidyl methacrylate

St: Styrene

AA: Acrylic

SA: Succinic anhydride

BPFE: Bisphenol pyridine type epoxy compound (9,9-bis(4-hydroxyphenyl) pyridine and chloromethyl ethylene oxide reactant)

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

THPA: Tetrahydrophthalic anhydride

PTMA: neopentylerythritol tetra (thiol acetate)

DPHA: a mixture of dineopentaerythritol pentaacrylate and hexaacrylate

TEAB: Tetraethylammonium bromide

AIBN: Azobisisobutyronitrile

TDMAMP: ginseng dimethyl amino methyl phenol

HQ: Hydroquinone

TEA: Triethylamine

BzDMA: Benzyl dimethyl amine

PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]

In a 500ml four-neck flask with a reflux cooler, fill with BPFE (114.4g, 0.23 mol), AA (33.2g, 0.46 mol), PGMEA (157g) and TEAB (0.48g), and fill it between 100 and 105 It was stirred at °C for 20 hours to react. Then, the flask was filled with BPDA (35.3g, 0.12 mol), THPA (18.3g, 0.12 mol), and stirred at 120 to 125°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A )-1. The solid content concentration of the obtained resin solution is 56.1% by mass, and the acid value (solid content is Calculated) is 103 mgKOH/g, and the weight average molecular weight (Mw) obtained by GPC analysis is 3,600.

[Synthesis example 2]

Put PGMEA (300g) in a 1-liter four-necked flask with reflux cooler, replace with nitrogen in the flask system, and raise the temperature to 120°C. In this flask, AIBN (10g) was dissolved in the monomer mixture (DCPMA (77.1g, 0.35 mol), GMA (49.8g, 0.35 mol), St (31.2g, 0.30 mol) and the mixture was dropped from the mixture. The funnel was dropped over 2 hours, and further stirred at 120°C for 2 hours to obtain a copolymer solution.

Then, after replacing with air in the flask system, AA (24.0g (95% of glycidyl group)), TDMAMP (0.8g) and HQ (0.15g) were added to the resulting copolymer solution, and stirred at 120°C In 6 hours, a copolymer solution containing a polymerizable unsaturated group was obtained. Furthermore, SA (30.0 g (90% of the molar number of AA)) and TEA (0.5 g) were added to the obtained copolymer solution containing polymerizable unsaturated groups, and reacted at 120°C for 4 hours to obtain a polymer solution containing polymerizable unsaturated groups. Alkali-soluble copolymer resin solution (A)-2 of sexual unsaturated group. The solid content concentration of the resin solution was 41.7% by mass, the acid value (in terms of solid content) was 76 mgKOH/g, and the weight average molecular weight (Mw) obtained by GPC analysis was 5,300.

[Synthesis Example 3]

In a 1L four-necked flask, add PTMA (20g, thiol 0.19 mol), DPHA (212g, acrylic 2.12 mol), PGMEA (58g), HQ (0.1g), and BzDMA (0.01g), The reaction was carried out at 60°C for 12 hours to obtain a dendritic polymer solution (B)-3 (solid content concentration: 80% by mass). Confirm the dendritic polymerization obtained by iodide titration The disappearance of the thiol group of the substance. The weight average molecular weight (Mw) of the obtained dendritic polymer was 10,000.

The abbreviations shown in Tables 1, 2, 4, 5, 7, 8, 10, and 11 are as follows.

(Alkali-soluble resin containing polymerizable unsaturated groups)

(A)-1: The resin solution obtained in Synthesis Example 1 above (solid content concentration 56.1% by mass)

(A)-2: The resin solution obtained in Synthesis Example 2 above (solid content concentration 41.7% by mass)

(Photopolymerizable monomer)

(B)-1: Mixture of dineopentaerythritol pentaacrylate and hexaacrylate (DPHA (Acrylic acid equivalent 96 to 115), manufactured by Nippon Kayaku Co., Ltd.)

(B)-2: A mixture of neopentylerythritol triacrylate and tetraacrylate (M-450 (acrylic acid equivalent 88), manufactured by Toagosei Co., Ltd.)

(B)-3: The dendrimer obtained in Synthesis Example 3 above

(Epoxy compound)

(C)-1: 3,4-Epoxycyclohexanecarboxylic acid (3',4'-epoxycyclohexyl)methyl (CELOXIDE 2021P (epoxy equivalent 135), manufactured by DAICEL 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 Co., Ltd.)

(C)-3: Butanetetracarboxylic acid tetrakis(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (EPOLEAD GT401 (epoxy equivalent 220), manufactured by DAICEL Co., Ltd.)

〔Dispersion of metal oxide〕

(Titanium dioxide dispersion)

(D)-1: Titanium dioxide dispersion (average particle size 50nm) concentration of 75% by mass, titanium dioxide dispersion in propylene glycol monomethyl ether acetate solvent

(D)-2: Titanium dioxide dispersion (average particle size 120nm) concentration of 75% by mass, titanium dioxide dispersion in propylene glycol monomethyl ether acetate solvent

(D)-3: Titanium dioxide dispersion (average particle size 270nm) concentration of 75% by mass, titanium dioxide dispersion in propylene glycol monomethyl ether acetate solvent

(D)-4: Titanium dioxide dispersion (average particle size 410nm) concentration of 75% by mass, titanium dioxide dispersion in propylene glycol monomethyl ether acetate solvent

(D)-5: Titanium dioxide dispersion (average particle size 620nm) concentration of 75% by mass, titanium dioxide dispersion in propylene glycol monomethyl ether acetate solvent

(D)-6: Titanium dioxide dispersion (average particle size 970nm) concentration of 75% by mass, titanium dioxide dispersion in propylene glycol monomethyl ether acetate solvent

(ZnO dispersion and ZrO ₂ dispersion)

(D)-7: ZnO dispersion (average particle size 200nm, refractive index 2.0) concentration 20% by mass, ZnO dispersion in propylene glycol monomethyl ether acetate solvent

(D)-8: ZnO dispersion (average particle size 350nm, refractive index 2.0) concentration of 20% by mass, ZnO dispersion of propylene glycol monomethyl ether acetate solvent

(D)-9: ZrO ₂ dispersion (average particle size 170nm, refractive index 2.2) concentration of 20%, ZrO ₂ dispersion of propylene glycol monomethyl ether acetate solvent

(D)-10: ZrO ₂ dispersion (average particle size 240nm, refractive index 2.2) concentration of 20% by mass, ZrO ₂ dispersion of propylene glycol monomethyl ether acetate solvent

(D)-11: TiO ₂ dispersion (average particle size 400nm, refractive index 2.5) concentration of 75% by mass, TiO ₂ dispersion of propylene glycol monomethyl ether acetate solvent

(D)-12: Al ₂ O ₃ dispersion (average particle size 300 nm, refractive index 1.77) concentration 20% by mass, Al ₂ O ₃ dispersion in propylene glycol monomethyl ether acetate solvent

(Photopolymerization initiator)

(E): 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyloxime) (IRGACURE OXE-01, manufactured by BASF Corporation, " IRGACURE'' is a registered trademark of BASF Corporation)

(Solvent)

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

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

(F)-3: 3-Methoxy-3-methyl-1-butyl acetate (MMBA)

(F)-4: Methyl 3-methoxypropionate (MMP)

(F)-5: Cyclohexanone (ANON)

(Hardening agent and hardening accelerator)

(G)-1: Benzene 1,2,4-tricarboxylic acid-1,2-anhydride

(G)-2: PGMEA solution containing 2.0% by mass of 1,8-diazabicyclo[5.4.0]undecane-7-ene (DBU(R)), manufactured by SAN-APRO Co., Ltd.)

(Other additives)

(H)-1: Surfactant (MEGAFAC F-447, manufactured by DIC Co., Ltd., "MEGAFAC" is a registered trademark of DIC)

(H)-2: Surfactant (DOWSIL SH3775, manufactured by DOW, "DOWSIL" is a registered trademark of DOW)

(H)-3: Antioxidant (neopentylerythritol 4-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, IRGANOX 1010, manufactured by BASF Corporation, "IRGANOX" (It is a registered trademark of BASF)

(H)-4: Coupling agent (3-glycidoxypropyltrimethoxysilane)

[Example 1]

The photosensitive resin composition using the titanium dioxide dispersion liquid as the component (D) was prepared as Examples 1 to 16 and Comparative Examples 1 to 4. The blending components are shown in Tables 1 and 2. The numerical values in Tables 1 and 2 all indicate mass%. In addition, (B)-3 is the amount of dendrimer without solvent.

[Assessment]

The photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4 were used to produce a substrate with a cured film for evaluation of development characteristics.

(Production of substrate with cured film for evaluation of development characteristics)

On a 125mm×125mm glass substrate "# 1737" (manufactured by CORNING) (hereinafter referred to as "glass substrate"), which has been cleaned by low-pressure mercury lamp with ultraviolet light of 1000mJ/cm ² at a wavelength of 254 nm and an illuminance of 1000 mJ/cm ² in advance, The photosensitive resin compositions shown in Tables 1 and 2 were coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and prebaked at 90°C for 2 minutes using a hot plate, and Create a cured film (coating film). Then, the above-mentioned hardened film (coating film) is covered with a negative light mask with line width/pitch=20μm/20μm, and an ultra-high pressure mercury lamp with an i-ray illuminance of 30mW/cm ² is irradiated with ultraviolet light of 50mJ/cm ² for photohardening reaction.

Then, the exposed cured film (coating film) is developed by 25°C, 0.04% potassium hydroxide solution at a shower pressure of 1kgf/cm ² from the developing time (BREAK TIME=BT) when the pattern starts to appear After treatment for 20 seconds, spray water washing at 5kgf/cm ^{2 to} remove the unexposed part of the cured film (coating film) to form a cured film pattern on the glass substrate. Use a hot air dryer at 90°C to formally cure (post-baking) Bake) for 60 minutes to obtain a substrate with a cured film for evaluation of development characteristics of Examples 1 to 16 and Comparative Examples 1 to 4.

The following evaluation was performed using the above-mentioned substrate with a cured film for evaluation of development characteristics.

[Evaluation of development characteristics]

(Pattern adhesion)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No peeling at all

△: partly peeled off

×: mostly peeled off

(Pattern linearity)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No burrs on the edge of the pattern can be seen

△: Some burrs on the edge of the pattern can be seen

×: The burrs on the edge of the pattern can be seen in most parts

(Pattern fineness)

(evaluation method)

Observe the mask pattern of 10 to 50 μm after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

◎: Form a pattern of 10 to 15 μm

○: Form a pattern of 16 to 24μm

△: Form a pattern of 25 to 50μm

×: No pattern formed

Using the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4, a substrate with a cured film for solvent resistance evaluation was produced.

(Production of substrate with cured film for solvent resistance evaluation)

On the glass substrate, the photosensitive resin composition shown in Tables 1 and 2 was coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and the hot plate was used to pre-baked at 90°C 2 Minutes later, a cured film (coating film) is produced. Then, the above-mentioned hardened film (coating film) is covered with a negative light mask with line width/pitch=20μm/20μm, and an ultra-high pressure mercury lamp with an i-ray illuminance of 30mW/cm ² is irradiated with ultraviolet light of 50mJ/cm ² for photohardening reaction.

Then, the exposed cured film (coating film) was developed with a shower pressure of 1 kgf/cm ² at 25° C., 0.05% potassium hydroxide solution, and then sprayed and washed with 5 kgf/cm ² for 60 seconds. The unexposed parts of the above-mentioned cured film (coating film) were removed to form a cured film pattern on the glass substrate, which was cured (post-baked) at 90°C using a hot air dryer for 60 minutes to obtain related examples 1 to 16, and comparison Examples 1 to 4 of the substrate with a cured film for solvent resistance evaluation.

The following evaluations were performed using the above-mentioned substrate with a cured film for solvent resistance evaluation.

〔Evaluation of solvent resistance〕

(evaluation method)

The surface of the cured film (coating film) made on the glass substrate is immersed in the wafer of PGMEA and wiped back and forth 20 times continuously. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: There is no dissolution or damage on the surface of the cured film (coating film)

△: Only a part of the surface of the cured film (coating film) can be seen to dissolve, and only a part is damaged

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

[Evaluation of penetration rate]

(evaluation method)

Using an ultraviolet-visible-near-infrared spectrophotometer "UH4150" (manufactured by Hitachi HIGH TECHSCIENCE Co., Ltd.), the transmittance of the above-mentioned substrate with a cured film in the visible light region (380 nm to 780 nm) was measured. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: The penetration rate is more than 70%

△: The penetration rate is more than 60% and less than 70%

×: The penetration rate is less than 60%

[Evaluation of light scattering]

The above-mentioned substrate with a cured film was irradiated with white light vertically, and the transmitted scattered light was measured using a Goniophotometer "GP-1" (manufactured by NIKKA Densei Co., Ltd.). In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: To evaluate the intensity of scattered light at 5° and 60° at the angle of direct light traveling in a straight line as 0°, the light scattering intensity at 60° is more than 20% relative to the light scattering intensity at 5° By.

△: The angle of direct light traveling in a straight line is evaluated as the intensity of the scattered light at 0° at 5° and 60°. Compared with the light scattering intensity at 5°, the light scattering intensity at 60° exceeds 10%. And less than 20%.

×: To evaluate the intensity of scattered light at 5° and 60° at 0° with the angle of the direct penetrating light traveling in a straight line. Relative to the light scattering intensity at 5°, the light scattering intensity at 60° is less than 10% By.

Table 3 shows the evaluation results of the above-mentioned items for the substrates with cured films formed by curing the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4 obtained above.

It is clear from the results of Examples 1 to 16 and Comparative Examples 1 to 4 that by using a photosensitive resin composition containing the alkali-soluble resin represented by the general formula (1) of the present invention and TiO ₂ , light scattering can be produced A substrate with a cured film that can form a fine pattern with excellent performance.

[Example 2]

The photosensitive resin composition using the titanium dioxide dispersion liquid as the component (D) was prepared as Examples 17-30 and Comparative Examples 5-9. The blending components are shown in Tables 4 and 5. The numerical values in Tables 4 and 5 all represent mass%. In addition, (B)-3 is the amount of dendrimer without solvent.

[Assessment]

Using the photosensitive resin compositions of Examples 17 to 30 and Comparative Examples 5 to 9, production of a substrate with a cured film for evaluation of development characteristics was performed.

(Production of substrate with cured film for evaluation of development characteristics)

On the glass substrate, the photosensitive resin composition shown in Tables 4 and 5 was coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and prebaked at 90°C using a hot plate 2 Minutes later, a cured film (coating film) is produced. Then, adjust the exposure interval to 100μm, and coat the above-mentioned cured film (coating film) with a negative light mask of 10 to 50μm (per 5μm scale), and irradiate 50mJ/cm with an ultra-high pressure mercury lamp with an i-ray illuminance of 30mW/cm ^{2 2} UV light, the light curing reaction.

Then, the exposed cured film (coating film) is developed by 25°C, 0.04% potassium hydroxide solution at a shower pressure of 1kgf/cm ² from the developing time (BREAK TIME=BT) when the pattern begins to appear After treatment for 20 seconds, spray water washing at 5kgf/cm ^{2 to} remove the unexposed part of the cured film (coating film) to form a cured film pattern on the glass substrate, and use a hot air dryer at 230°C to formally cure (post-baking) Bake) for 30 minutes to obtain substrates with cured films for evaluation of development characteristics of Examples 17 to 30 and Comparative Examples 5 to 9.

The following evaluation was performed using the above-mentioned substrate with a cured film for evaluation of development characteristics.

[Evaluation of development characteristics]

(Pattern adhesion)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No peeling off

△: partly peeled off

×: mostly peeled off

(Pattern linearity)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No burrs on the edge of the pattern can be seen

△: Some burrs on the edge of the pattern can be seen

×: The burrs on the edge of the pattern can be seen in most parts

(Pattern fineness)

(evaluation method)

Observe the mask pattern of 10 to 50 μm after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

◎: Form a pattern of 10 to 15 μm

○: Form a pattern of 16 to 24μm

△: Form a pattern of 25 to 50μm

×: No pattern formed

[Evaluation of penetration rate]

(evaluation method)

Use the ultraviolet-visible-near-infrared spectrophotometer "UH4150" to measure the transmittance in the visible light range (380nm to 780nm) of the above-mentioned substrate with a hardened film. In addition, ○ or more is regarded as a pass.

(Assessment criteria)

○: The penetration rate is more than 70%

△: The penetration rate is more than 60% and less than 70%

×: The penetration rate is less than 60%

Using the photosensitive resin compositions of Examples 17 to 30 and Comparative Examples 5 to 9, the production of a substrate with a cured film for light scattering evaluation was performed.

(Production of base material with hardened film for light scattering evaluation)

On the glass substrate, the photosensitive resin composition shown in Tables 4 and 5 was coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and prebaked at 90°C using a hot plate 2 Minutes later, a cured film (coating film) is produced. Then, without covering the negative light mask, an ultra-high pressure mercury lamp with an i-ray illuminance of 30 mW/cm ² was irradiated with ultraviolet light of 50 mJ/cm ^{2 to} perform a photohardening reaction.

Then, the exposed cured film (coating film) is developed by 25°C, 0.05% potassium hydroxide solution at a shower pressure of 1kgf/cm ² from the developing time (BREAK TIME=BT) when the pattern starts to appear After treatment for 20 seconds, perform 5kgf/cm ² spray water washing to remove the unexposed part of the cured film (coating film) to form a cured film pattern on the glass substrate, and use a hot air dryer at 230°C to formally cure (post-baking) Bake) for 30 minutes to obtain a substrate with a cured film for evaluating the light scattering properties of Examples 17 to 30 and Comparative Examples 5 to 9.

The following evaluation was performed using the above-mentioned substrate with a cured film for the evaluation of light scattering properties.

(evaluation method)

The above-mentioned substrate with a cured film was irradiated with white light vertically, and the transmitted scattered light was measured using a variable angle photometer "GP-1". In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: To evaluate the intensity of scattered light at 5° and 60° at the angle of direct light traveling in a straight line as 0°, the light scattering intensity at 60° is more than 20% relative to the light scattering intensity at 5° By.

△: The angle of direct light traveling in a straight line is evaluated as the intensity of the scattered light at 0° at 5° and 60°. Compared with the light scattering intensity at 5°, the light scattering intensity at 60° exceeds 10%. And less than 20%.

×: To evaluate the intensity of scattered light at 5° and 60° at 0° with the angle of the direct penetrating light traveling in a straight line. Relative to the light scattering intensity at 5°, the light scattering intensity at 60° is less than 10% By.

Regarding the substrates with cured films obtained by curing the photosensitive resin compositions of Examples 17 to 30 and Comparative Examples 5 to 9 obtained above, the results of the evaluation of the above items are shown in Table 6.

From the results of Examples 17 to 30 and Comparative Examples 5 to 9, it is obvious that by using a photosensitive resin composition containing the alkali-soluble resin represented by the general formula (1) of the present invention and TiO ₂ , light scattering can be produced A substrate with a cured film that can form a fine pattern with excellent performance.

[Example 3]

The photosensitive resin composition using the ZnO dispersion liquid and the ZrO ₂ dispersion liquid as the component (D) was prepared as 31 to 45 and Comparative Examples 10 to 12. The blending components are shown in Tables 7 and 8. The numerical values in Tables 7 and 8 all represent mass%. In addition, (B)-3 is the amount of dendrimer without solvent.

[Assessment]

Using the photosensitive resin compositions of Examples 31 to 45 and Comparative Examples 10 to 12, a substrate with a cured film for evaluation of development characteristics was produced.

(Production of substrate with cured film for evaluation of development characteristics)

On the glass substrate, the photosensitive resin composition shown in Tables 7 and 8 was coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and prebaked at 90°C using a hot plate 2 Minutes later, a cured film (coating film) is produced. Then, the above-mentioned hardened film (coating film) is covered with a negative light mask with line width/pitch=20μm/20μm, and an ultra-high pressure mercury lamp with an i-ray illuminance of 30mW/cm ² is irradiated with ultraviolet light of 50mJ/cm ² for photohardening reaction.

Then, the exposed cured film (coating film) is developed by 25°C, 0.04% potassium hydroxide solution at a shower pressure of 1kgf/cm ² from the developing time (BREAK TIME=BT) when the pattern begins to appear After treatment for 20 seconds, spray water washing at 5kgf/cm ^{2 to} remove the unexposed part of the cured film (coating film) to form a cured film pattern on the glass substrate. Use a hot air dryer at 90°C to formally cure (post-baking) Bake) for 60 minutes to obtain substrates with cured films for evaluation of development characteristics of Examples 31 to 45 and Comparative Examples 10 to 12.

The following evaluation was performed using the above-mentioned substrate with a cured film for evaluation of development characteristics.

[Evaluation of development characteristics]

(Pattern adhesion)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No peeling off

△: partly peeled off

×: mostly peeled off

(Pattern linearity)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No burrs on the edge of the pattern can be seen

△: Some burrs on the edge of the pattern can be seen

×: The burrs on the edge of the pattern can be seen in most parts

(Pattern fineness)

(evaluation method)

Observe the mask pattern of 10 to 50 μm after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

◎: Form a pattern of 10 to 15 μm

○: Form a pattern of 16 to 24μm

△: Form a pattern of 25 to 50μm

×: No pattern formed

Using the photosensitive resin compositions of Examples 31 to 45 and Comparative Examples 10 to 12, the production of a substrate with a cured film for solvent resistance evaluation was performed.

(Production of substrate with cured film for solvent resistance evaluation)

On the glass substrate, the photosensitive resin composition shown in Tables 7 and 8 was coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and prebaked at 90°C using a hot plate 2 Minutes later, a cured film (coating film) is produced. Then, the above-mentioned hardened film (coating film) is covered with a negative light mask with line width/pitch=20μm/20μm, and an ultra-high pressure mercury lamp with an i-ray illuminance of 30mW/cm ² is irradiated with ultraviolet light of 50mJ/cm ² for photohardening reaction.

Then, the exposed cured film (coating film) was developed with a shower pressure of 1 kgf/cm ² at 25° C., 0.05% potassium hydroxide solution, and then sprayed and washed with 5 kgf/cm ² for 60 seconds. The unexposed parts of the above-mentioned cured film (coating film) were removed to form a cured film pattern on a glass substrate, and a hot-air dryer was used to formally cure (post-bake) at 90°C for 60 minutes to obtain related examples 31 to 45 and comparisons The substrate with a cured film for solvent resistance evaluation of Examples 10-12.

The following evaluations were performed using the above-mentioned substrate with a cured film for solvent resistance evaluation.

〔Evaluation of solvent resistance〕

(evaluation method)

The surface of the cured film (coating film) made on the glass substrate was immersed in the PGMEA wafer and wiped continuously 20 times. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: There is no dissolution or damage on the surface of the cured film (coating film)

△: Only a part of the surface of the cured film (coating film) can be seen to dissolve, and only a part is damaged

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

[Evaluation of penetration rate]

(evaluation method)

Measure the transmittance of the visible light region (380nm to 780nm) of the above-mentioned substrate with a hardened film using a UV-visible near-infrared spectrophotometer "UH4150". In addition, △ or more was regarded as a pass. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: The penetration rate is above 80%

△: The penetration rate is more than 70% and less than 80%

×: The penetration rate is less than 70%

[Evaluation of light scattering]

The above-mentioned substrate with a cured film was irradiated with white light vertically, and the transmitted scattered light was measured using a variable angle photometer "GP-1". In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: The angle of direct light traveling in a straight line is evaluated as the intensity of scattered light at 0° at 5° and 45°. Compared with the light scattering intensity at 5°, the light scattering intensity at 45° exceeds 15%. By.

△: The angle of direct light traveling in a straight line is evaluated as the intensity of scattered light at 0° at 5° and 45°. Compared with the light scattering intensity at 5°, the light scattering intensity at 45° is more than 10%. And 15% or less.

×: The angle of direct light traveling in a straight line is evaluated as the intensity of the scattered light at 0° at 5° and 45°. The light scattering intensity at 45° is less than 10% relative to the light scattering intensity at 5° By.

Table 9 shows the evaluation results of the above-mentioned items for the substrates with cured films formed by curing the photosensitive resin compositions of Examples 31 to 45 and Comparative Examples 10 to 12 obtained above.

From the results of the foregoing Examples 31 to 45 and Comparative Examples 10 to 12, it is obvious that by using the unsaturated group-containing alkali-soluble resin and metal oxides (ZnO, ZrO) represented by the general formula (1) of the present invention ₂ ) The photosensitive resin composition can produce a cured film with excellent light scattering and fine pattern formation.

[Example 4]

The photosensitive resin composition using the ZnO dispersion liquid and the ZrO ₂ dispersion liquid as the (D) component was prepared as Examples 46-60 and Comparative Examples 13-15. The blending components are shown in Tables 10 and 11. The numerical values in Tables 10 and 11 all represent mass%. In addition, (B)-3 is the amount of dendrimer without solvent.

[Assessment]

The photosensitive resin compositions of Examples 46 to 60 and Comparative Examples 13 to 15 were used to produce a substrate with a cured film for evaluation of development characteristics.

(Production of substrate with cured film for evaluation of development characteristics)

On the glass substrate, the photosensitive resin composition shown in Tables 10 and 11 was coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and prebaked at 90°C using a hot plate 2 Minutes later, a cured film (coating film) is produced. Then, adjust the exposure interval to 100μm, and coat the above-mentioned cured film (coating film) with a negative light mask of 10 to 50μm (per 5μm scale), and irradiate 50mJ/cm with an ultra-high pressure mercury lamp with an i-ray illuminance of 30mW/cm ^{2 2} UV light, the light curing reaction.

Then, the exposed cured film (coating film) is developed by 25°C, 0.04% potassium hydroxide solution at a shower pressure of 1kgf/cm ² from the developing time (BREAK TIME=BT) when the pattern begins to appear After treatment for 20 seconds, spray water washing at 5kgf/cm ^{2 to} remove the unexposed part of the cured film (coating film) to form a cured film pattern on the glass substrate, and use a hot air dryer at 230°C to formally cure (post-baking) Bake) for 30 minutes to obtain substrates with cured films for evaluation of development characteristics of Examples 46 to 60 and Comparative Examples 13 to 15.

The following evaluation was performed using the above-mentioned substrate with a cured film for evaluation of development characteristics.

[Evaluation of development characteristics]

(Pattern adhesion)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No peeling off

△: partly peeled off

×: mostly peeled off

(Pattern linearity)

(evaluation method)

Observe the 20μm mask pattern after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: No burrs on the edge of the pattern can be seen

△: Some burrs on the edge of the pattern can be seen

×: The burrs on the edge of the pattern can be seen in most parts

(Pattern fineness)

(evaluation method)

Observe the mask pattern of 10 to 50 μm after hardening (post-baking) with an optical microscope. In addition, △ or more was regarded as a pass.

(Assessment criteria)

◎: Form a pattern of 10 to 15 μm

○: Form a pattern of 16 to 24μm

△: Form a pattern of 25 to 50μm

×: No pattern formed

[Evaluation of penetration rate]

(evaluation method)

Measure the transmittance of the visible light region (380nm to 780nm) of the above-mentioned substrate with a hardened film using an ultraviolet-visible-near-infrared spectrophotometer "UH4150". In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: The penetration rate is above 80%

△: The penetration rate is more than 70% and less than 80%

×: The penetration rate is less than 70%

The photosensitive resin compositions of Examples 46 to 60 and Comparative Examples 13 to 15 were used to produce a substrate with a cured film for light scattering evaluation.

(Production of substrate with hardened film for light scattering evaluation)

On the glass substrate, the photosensitive resin composition shown in Tables 10 and 11 was coated with a spin coater so that the film thickness after the heat curing treatment became 2.0 μm, and prebaked at 90°C using a hot plate 2 Minutes later, a cured film (coating film) is produced. Then, without covering the negative light mask, an ultra-high pressure mercury lamp with an i-ray illuminance of 30 mW/cm ² was irradiated with ultraviolet light of 50 mJ/cm ^{2 to} perform a photohardening reaction.

Then, the exposed cured film (coating film) is developed by 25°C, 0.05% potassium hydroxide solution at a shower pressure of 1kgf/cm ² from the developing time (BREAK TIME=BT) when the pattern starts to appear After treatment for 20 seconds, spray water washing at 5kgf/cm ^{2 to} remove the unexposed part of the cured film (coating film) to form a cured film pattern on the glass substrate, and use a hot air dryer at 230°C to formally cure (post-baking) Bake) for 30 minutes to obtain a substrate with a cured film for evaluating the light scattering properties of Examples 46 to 60 and Comparative Examples 13 to 15.

The following evaluations were performed using the above-mentioned substrate with a cured film for evaluation of light scattering properties.

[Evaluation of light scattering]

(evaluation method)

The cured film (coating film) was the same cured film (coating film) as the one produced for solvent resistance evaluation, and white light was irradiated vertically, and the transmitted scattered light was measured with a variable angle photometer. In addition, △ or more was regarded as a pass.

(Assessment criteria)

○: The angle of direct light traveling in a straight line is evaluated as the intensity of scattered light at 0° at 5° and 45°. Compared with the light scattering intensity at 5°, the light scattering intensity at 45° exceeds 15%. By.

△: The angle of direct light traveling in a straight line is evaluated as the intensity of scattered light at 5° and 45° at 0°. Compared with the light scattering intensity at 5°, the light scattering intensity at 45° is more than 10%. And 15% or less.

×: The angle of direct light traveling in a straight line is evaluated as the intensity of the scattered light at 0° at 5° and 45°. The light scattering intensity at 45° is less than 10% relative to the light scattering intensity at 5° By.

The results of the evaluation of the above-mentioned items are shown in Table 12 for the substrates with cured films obtained by curing the photosensitive resin compositions of Examples 46 to 60 and Comparative Examples 13 to 15 obtained above.

From the results of the foregoing Examples 46 to 60 and Comparative Examples 13 to 15, it is obvious that by using the unsaturated group-containing alkali-soluble resin and metal oxides (ZnO, ZrO) represented by the general formula (1) of the present invention ₂ ) The photosensitive resin composition can produce a cured film with excellent light scattering and fine pattern formation.

[Possibility of industrial use]

According to the method of manufacturing a substrate with a cured film of the present invention, a substrate with a cured film having excellent light scattering properties can be obtained. Therefore, for example, it can be used in a display device or the like. That is, the pattern can be formed by photolithography etching, so it has the advantage that it can be formed by a known photolithography etching step. In addition, film strength can be obtained even at low temperatures, so it is suitable for the production of touch panels and color filters using substrates with low heat resistance.

Claims (13)

A method for manufacturing a substrate with a hardened film is to form a light-scattering hardened film pattern on the substrate to produce a substrate with a hardened film. The manufacturing method uses photosensitive inorganic particles with an average particle size of 100 to 700 nm. The resin composition is applied on a substrate, exposed through a light mask, and unexposed portions are removed by development, and heated to form a predetermined cured film pattern. A substrate with a hardened film, manufactured by the manufacturing method described in item 1 of the scope of the patent application, and the transmittance of the visible light region of the substrate with a hardened film is more than 70%, which is perpendicular to the aforementioned substrate with a hardened film When irradiated with white light, the angle of direct light traveling in a straight line is set to the intensity of scattered light at 0°, compared to the intensity of scattered light when the angle of direct light is set to 5°, It is more than 20%. A substrate with a hardened film, manufactured by the manufacturing method described in item 1 of the scope of the patent application, and the visible light region of the substrate with a hardened film has a transmittance of 80% or more, which is perpendicular to the aforementioned substrate with a hardened film When irradiating white light, the angle of direct light traveling in a straight line is set to the intensity of scattered light at 0° at 45°, compared to the intensity of scattered light at the aforementioned angle of direct light at 5°. It is more than 15%. A photosensitive resin composition for the user when manufacturing the substrate with a cured film described in item 2 of the scope of patent application, the photosensitive resin composition comprising: (A) Alkali-soluble resins containing unsaturated groups, (B) A photopolymerizable monomer with at least 2 ethylenically unsaturated bonds, (C) Epoxy compound, (D)TiO ₂ , (E) photopolymerization initiator, and (F) Solvent; The content of component (D) is 1% by mass or more and less than 20% by mass relative to the total mass of solid components. A photosensitive resin composition for the user when manufacturing the substrate with a cured film described in item 3 of the scope of patent application, the photosensitive resin composition comprising: (A) Alkali-soluble resins containing unsaturated groups, (B) A photopolymerizable monomer with at least 2 ethylenically unsaturated bonds, (C) Epoxy compound, (D) Metal oxide particles, (E) photopolymerization initiator, and (F) Solvent; The refractive index of (D) component is 1.9 to 2.3. The photosensitive resin composition according to item 4 or 5 of the scope of patent application, wherein the unsaturated group-containing alkali-soluble resin of component (A) is represented by the general formula (1) Resin

In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group with 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-, 茀-9,9 -Diyl or direct bonding, Y is a tetravalent carboxylic acid residue, Z is each independently a hydrogen atom or a substituent represented by the general formula (2), but one or more of Z is the general formula (2) For the substituents shown in (2), n is an integer from 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 item 4 or 5 of the scope of patent application, wherein the mass of component (A) is 20 to 70% by mass relative to the total mass of solid content, and ( The mass of the component B) is 5 to 40% by mass, and the mass of the component (C) is 8 to 24% by mass relative to the total mass of the solid content. The photosensitive resin composition as described in item 4 or 5 of the scope of patent application, which contains (G) epoxy compound hardener and/or hardening accelerator, relative to the total mass of solid content, (C) component and (G) The total mass of components is 15 to 35% by mass. The photosensitive resin composition as described in claim 4 or 5, wherein the epoxy equivalent of the epoxy compound of the component (C) is 100 to 300 g/eq. The photosensitive resin composition described in claim 8, wherein the curing agent and/or curing accelerator of the component (G) contains acid anhydride. A cured film formed by curing the photosensitive resin composition described in any one of items 4 to 10 in the scope of the patent application. A display device is provided with the hardened film described in item 11 of the scope of patent application or a substrate with hardened film described in item 2 or 3 of the scope of patent application. A method for manufacturing a substrate with a hardened film is to form a hardened film pattern with light scattering properties on a substrate with a heat-resistant temperature of 150°C or less to manufacture a substrate with a hardened film. The manufacturing method is the fourth to tenth patent application. The photosensitive resin composition of any one of the items The material is applied on the substrate, exposed through a light mask, and the unexposed part is removed by development, and heated at 150°C or less to form a predetermined cured film pattern.