JP2020166255A - Method for manufacturing substrate with cured film, substrate with cured film, photosensitive resin composition, cured film formed by curing photosensitive resin composition, and display device having cured film or substrate with cured film - Google Patents

Abstract

To provide a method for manufacturing a substrate with a cured film.SOLUTION: The method for manufacturing a substrate with a cured film of the present invention is a method for manufacturing a substrate with a cured film by forming a cured film pattern having a light-scattering property on a substrate. In the method, a photosensitive resin composition containing inorganic particles having an average particle diameter of 100 to 700 nm is applied on a substrate, exposed through a photomask, developed to remove an unexposed portion, and heated to form a predetermined cured film pattern.SELECTED DRAWING: None

Description

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 obtained 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 highly heat-resistant substrates such as glass substrates and silicon wafers that can be used at high temperatures of 200 ° C or higher, but also PET (polyethylene terephthalate) with low heat resistance has been used for the purpose of making devices flexible and one-chip. A pattern using a photosensitive resin composition having a light scattering function is formed on a plastic substrate (plastic film, resin film) such as PEN (polyethylene terephthalate), or a substrate with an organic device such as an organic EL device or an organic TFT. It is being considered to form.

Here, if a photosensitive resin composition for forming a pattern by high-temperature firing is subjected to low-temperature firing in accordance with the heat resistance of the substrate, the film strength of the pattern formed on the plastic substrate and the substrate with an organic device becomes insufficient. In the subsequent steps (for example, solvent resistance during resist application, alkali resistance during alkaline development, etc.), there is a problem that the film of the coating film is easily reduced, the surface is roughened, the pattern is peeled off, and the like.

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

For example, Patent Document 1 describes photosensitive for forming a pattern having a light scattering function, which is composed of a TiO ₂ filler, a photopolymerizable (meth) acrylic monomer, an alkali-soluble resin, a photopolymerization initiator, and an organic solvent. The sex composition is disclosed. It is said that the photosensitive composition has photolithography characteristics suitable for use in a display device, and also has a light scattering property that scatters blue light at a wider angle than the incident angle by the TiO ₂ filler.

Further, Patent Document 2 includes at least one kind of resin (A) as a binder material, contains fluorine as light scattering particles (B), and includes ZrO ₂ and TiO ₂ as metal oxide fine particles (C). A resin composition for a light scattering layer containing at least one selected metal oxide fine particles is disclosed. It is said that the resin composition for a light scattering layer can provide a resin composition for a light scattering layer that has a small wavelength dependence of the light extraction efficiency improvement rate and can be used in a wide wavelength range.

Japanese Unexamined Patent Publication No. 2013-156304 Japanese Unexamined Patent Publication No. 2015-022794

However, according to the findings of the present inventors, the photosensitive composition described in Patent Document 1 has low solvent resistance, and the resin composition for a light scattering layer described in Patent Document 2 has a pattern having desired light scattering properties. Could not be obtained. Further, neither the photosensitive composition described in Patent Document 1 nor the resin composition for a light scattering layer described in Patent Document 2 sufficiently satisfies the adhesion and linear reproducibility of the cured film.

The present invention has been made in view of the above points, and has a light scattering function directly on the substrate regardless of the method for manufacturing the substrate with the cured film, the substrate with the cured film, and the heat resistant temperature of the substrate, and has adhesiveness and straightness. To provide a display device having a photosensitive resin composition capable of forming a cured film having excellent properties, solvent resistance, etc., a cured film obtained by curing the photosensitive resin composition, and a cured film and a substrate with a cured film. The purpose.

The method for producing a substrate with a cured film of the present invention is a method for producing a substrate with a cured film by forming a cured film pattern having photoscattering property on the substrate, and is an inorganic particle having an average particle size of 100 to 700 nm. A photosensitive resin composition containing the above-mentioned material is applied onto a substrate, exposed through a photomask, unexposed areas are removed by development, and heated to form a predetermined cured film pattern.

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

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

The display device of the present invention has the cured film or the substrate with the cured film.

The method for producing a substrate with a cured film of the present invention is a method for producing a substrate with a cured film by forming a cured film pattern having photoscattering property on a substrate having a heat resistant temperature of 150 ° C. or lower, and the above-mentioned photosensitive resin. The composition is applied onto a substrate, exposed through a photomask, unexposed portions are removed by development, and heated at 150 ° C. or lower to form a predetermined cured film pattern.

According to the present invention, regardless of the method for manufacturing a substrate with a cured film, the substrate with a cured film, and the heat resistant temperature of the substrate, the substrate has a light scattering function directly and is excellent in adhesion, linearity, solvent resistance, and the like. It is possible to provide a display device having a photosensitive resin composition capable of forming a cured film, a cured film obtained by curing the photosensitive resin composition, and a cured film and a substrate with a cured film.

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

The photosensitive resin composition of the present invention contains (A) an unsaturated group-containing alkali-soluble resin. Any resin having an acid value for imparting alkali developability and capable of having appropriate photocurability in combination with the photopolymerizable monomer of the component (B) can be used without particular limitation. Among these resins, resins having a highly aromatic skeleton generally tend to have a higher specific gravity than aliphatic resins, and when solutions having the same resin concentration are used, the specific gravity of the resin solution is increased. Can be made larger. It is presumed that this makes it possible to increase the dispersion stability of the metal oxide fine particles having a higher specific gravity than the resin. Therefore, by using the resin represented by the general formula (1), a photosensitive resin composition having sufficient dispersion stability of the metal oxide fine particles can be obtained. Among them, when an unsaturated group-containing alkali-soluble resin (cardo resin) having a polycyclic aromatic skeleton, wherein X represented by the general formula (1) is a fluorene-9,9-diyl group, is used. Since the effect is increased, it is expected that the dispersion stability of the metal oxide fine particles is improved in the cardo resin. As a result, the light scattering property of the cured film obtained by curing the photosensitive resin composition of the present invention can be enhanced. In addition, the cardo resin has a property of excellent adhesion during development when a pattern is formed by photolithography, and this property can be effectively utilized even when a filler of metal oxide fine particles coexists. It is presumed to be.

The mass of the component (A) in the photosensitive resin composition of the present invention is preferably 20 to 70% by mass with respect 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 lower, the content of the component (A) is 20 to 60% by mass with respect to the total mass of the solid content. Is more preferable, and when a cardo resin is used, it is more preferably 35 to 55% by mass. Further, when a resin such as an acrylic copolymer is used, it is more preferably 20 to 50% by mass. When the mass of the component (A) is 20% by mass or more with respect to the total mass of the solid content, the dissolution development can stably form a pattern during the alkaline development even if the metal oxide fine particles are contained. It is possible to design the composition of the photosensitive resin composition in order to obtain a desired pattern without residue, and when the mass of the component (A) is 60% by mass or less with respect to the total mass of the solid content, the hardness of the cured film is fine. The sex can be improved. In addition, the suitability of the production process during alkaline development is improved, and the photocurability can be sufficiently ensured.

When the photosensitive resin composition of the present invention is a composition that is fired at a high temperature of more than 150 ° C., the content of the component (A) is 35 to 70% by mass with respect to the total mass of the solid content. When a cardo resin is used, it is more preferably 45 to 60% by mass. When a resin such as an acrylic copolymer system is used, it is preferably 35 to 55% by mass or less. When the content of the component (A) is 35% by mass or more, even if the metal oxide fine particles are contained, dissolution development occurs during alkaline development, and a desired pattern can be obtained without residue, and the content of the component (A) is high. When it is 70% by mass or less, the fineness of the cured film can be improved. In addition, the suitability of the production process during alkaline development is improved, and the photocurability can be sufficiently ensured.

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

(In the formula (1), R ₁ , R _2, R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an atomic or methyl group, where X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, and Z is independently represented by a hydrogen atom or the general formula (2). However, one or more of Z are substituents represented by the general formula (2), and n is an integer of 1 to 20.)

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

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

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

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

The epoxy compound (a-1) 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 raw materials for the epoxy compound (a-1) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4-hydroxy-). 3,5-Dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) Hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, Bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-) Dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane , 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) Propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) ) Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) ) Fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5) -Dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, Includes 3,3'-biphenol and the like. Only one of these may be used alone, or two or more thereof may be used in combination.

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

A known method can be used for the reaction between the epoxy compound (a-1) represented by the general formula (3) and (meth) acrylic acid. For example, Japanese Patent Application Laid-Open No. 4-355450 describes a diol containing a polymerizable unsaturated group by using about 2 mol (meth) acrylic acid with respect to 1 mol of an epoxy compound having two epoxy groups. It is stated that it can be obtained. In the present invention, the compound obtained by the above reaction is a diol containing a polymerizable unsaturated group, and is a diol (d) containing a polymerizable unsaturated group represented by the general formula (4) (hereinafter, simply ". It is also referred to as "diol (d)" represented by the general formula (4)).

(In the formula (4), R ₁ , R _2, R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an atom or a methyl group, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond.)

Synthesis of diol (d) represented by general formula (4), subsequent addition reaction of polyvalent carboxylic acid or its anhydride, and monofunctional epoxy having a polymerizable unsaturated group having reactivity with a carboxy group. In the production of the alkali-soluble resin represented by the general formula (1) by reacting a compound or the like, the reaction is usually carried out in a solvent using a catalyst as needed.

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

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

Next, the diol (d) represented by the general formula (4) obtained by the reaction of the epoxy compound (a-1) represented by the general formula (3) with the (meth) acrylic acid, and the dicarboxylic acid or tricarboxylic acid. Acids or their acid anhydrides (b) and tetracarboxylic acids or their acid dianhydrides (c) are reacted to form a carboxy group and polymerizable unsaturated in one molecule represented by the general formula (1). An alkali-soluble resin having a group can be obtained.

(In the formula (1), R ₁ , R _2, R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an atomic or methyl group, where X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, and Z is independently represented by a hydrogen atom or the general formula (2). However, one or more of Z are substituents represented by the general formula (2), and n is an integer of 1 to 20.)

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

The acid component used for synthesizing the alkali-soluble resin represented by the general formula (1) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by the general formula (4). Therefore, it is necessary to use dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) in combination with tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, these carboxylic acid residues may contain a bond containing a hetero element such as -O-, -S-, and a carbonyl group.

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

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

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

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

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

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

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

Here, the diol (d) represented by the formula (4), a dicarboxylic acid or a tricarboxylic acid or their acid monoanhydride (b), a tetracarboxylic acid or an acid dianhydride thereof is used so that the terminal of the compound becomes a carboxy group. It is preferable to react so that the molar ratio with the anhydride (c) is (d) :( b) :( c) = 1: 0.01 to 1.0: 0.2 to 1.0.

For example, when the acid monoanhydride (b) and the acid dianhydride (c) are used, the amount of the acid component with respect to the diol (d) represented by the formula (4) [(b) / 2 + (c)]. It is preferable to react so that the molar ratio [(d) / [(b) / 2+ (c)]] of the above is 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of the diol containing an unreacted polymerizable unsaturated group is not increased, so that the stability over time of the alkali-soluble resin composition is enhanced. Can be done. On the other hand, when the molar ratio exceeds 0.5, the terminal of the alkali-soluble resin represented by the formula (1) does not become an acid anhydride, so that the increase in the content of the unreacted acid dianhydride is suppressed. As a result, the stability of the alkali-soluble resin composition over time can be improved. For the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the formula (1), the molar ratios of the components (d), (b) and (c) are arbitrarily changed within the above range. can do.

The acid value of the alkali-soluble resin represented by the general formula (1) is preferably in the range of 20 to 180 mgKOH / g, more preferably 40 mgKOH / g or more and 140 mgKOH / g or less, and more preferably 80 mgKOH / g. More preferably, it is 120 mgKOH / g or less. When the acid value is 20 mgKOH / g or more, the residue is less likely to remain during alkaline development, and when the acid value is 180 mgKOH / g or less, the penetration of the alkaline developer does not become too fast, so peeling development should be suppressed. Can be done. The acid value can be determined by titrating with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

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

The photosensitive resin composition (B) of the present invention contains a photopolymerizable monomer having at least two ethylenically unsaturated bonds. The component (B) makes the adhesion of the cured film higher, and also makes the exposed portion more soluble in the alkaline developer to make the linear reproducibility of the cured product higher. However, in order to make the cured film less brittle, suppress the decrease in the acid value of the composition, improve the solubility of the unexposed portion in the alkaline developer, and improve the linear reproducibility of the cured product. , (B) It is preferable that the amount of the component is not too large.

Here, when the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150 ° C. or lower, the content of the component (B) is 5 to 40% by mass with respect to the total mass of the solid content. Is preferable. When a cardo resin is used as the component (A), the mass of the component (B) is preferably 5 to 20% by mass with respect to the total mass of the solid content. When another acrylic copolymer resin or the like is used as the component (A), the mass of the component (B) is preferably 10 to 35% by mass with respect to the total mass of the solid content.

When the photosensitive resin composition of the present invention is a composition that is fired at a high temperature of more than 150 ° C., the mass of the component (B) is 10 to 40% by mass with respect to the total mass of the solid content. When a cardo resin is used as the component (A), the mass of the component (B) is preferably 10 to 35% by mass with respect to the total mass of the solid content. When another acrylic copolymer resin or the like is used as the component (A), the mass of the component (B) is preferably 20 to 40% by mass with respect to the total mass of the solid content.

By setting the mass of the component (B) to 5 to 40% by mass with respect to the total mass of the solid content, it is possible to design the composition of the photosensitive resin composition having desired characteristics, for example, the photosensitive of the present invention. The linearity and fineness of the cured film obtained by curing the resin composition can be improved.

(B) Examples of photopolymerizable monomers having at least two ethylenically unsaturated bonds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol. Di (meth) acrylate, tetramethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethyl propantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa. It has (meth) acrylic acid esters such as (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and an ethylenic double bond. Examples of the compound include a dendritic polymer having a (meth) acryloyl group and the like. It should be noted that these may be used alone or in combination of two or more.

In the example of the dendritic polymer having a (meth) acryloyl group as the compound having an ethylenic double bond, a part of the carbon-carbon double bond in the (meth) acryloyl group of the polyfunctional (meth) acrylate is used. It contains a dendritic polymer obtained by adding a polyvalent mercapto compound. Specifically, it is obtained by reacting the (meth) acryloyl group of the polyfunctional (meth) acrylate represented by the general formula (5) with the thiol group of the polyvalent mercapto compound represented by the general formula (6). There are dendritic polymers.

(In formula (5), R ₆ is a hydrogen atom or a methyl group, and R ₇ is the remainder of donating l hydroxyl groups out of k hydroxyl groups of R ₉ (OH) _k to the ester bond in the formula. A preferred R ₉ (OH) _k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or multiple molecules of the polyvalent alcohol. Are polyhydric alcohol ethers linked via ether bonds by dehydration condensation of alcohols, or esters of these polyhydric alcohols or polyhydric alcohol ethers with hydroxy acids. K and l are 2 independently. It is an integer of ~ 20 and k ≧ l.)

In formula (6), R ₈ is a single bond or a 2 to 6 valent C1 to C6 hydrocarbon group, p is 2 when R ₈ is a single bond, and R ₈ is 2 to 6 valent. When it is the group of, it is an integer of 2 to 6.)

Examples of the polyfunctional (meth) acrylate represented by the general formula (5) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and tetraethylene glycol di (meth). ) Acrylic, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolethanetri ( Meta) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (Meta) acrylate, tripentaerythritol hepta (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, epichlorohydrin-modified hexahydrophthal Acid di (meth) acrylate, hydroxypentaerythritol neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) Acrylic, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, alkoxy-modified tri Includes (meth) acrylic acid esters such as trimethylolpropane tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

Examples of the polyvalent mercapto compound represented by the general formula (6) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, and trimethylol. Propanetri (mercaptoacetate), trimethylpropantri (mercaptopropionate), pentaerythritoltetra (mercaptoacetate), pentaerythritoltri (mercaptoacetate), pentaerythritoltetra (mercaptopropionate), dipentaerythritol hexa (mercapto) Acetate), dipentaerythritol hexa (mercaptopropionate), etc. are included. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

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

The photosensitive resin composition of the present invention contains (C) an epoxy compound. The content of the component (C) is preferably 8 to 24% by mass with respect to the solid content. When the photosensitive resin composition contains a sufficient amount of the component (C), the solvent resistance of the cured product can be sufficiently enhanced. However, in order to sufficiently improve the adhesion and linear reproducibility of the cured product, it is preferable that the amount of the component (C) is not too large.

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 lower, the photosensitive resin composition preferably contains a larger amount of the component (C). The mass of the component (C) at this time is preferably 8 to 24% by mass with respect to the solid content, and more preferably 12 to 24% by mass with respect to the solid content.

Further, when the photosensitive resin composition of the present invention is a composition that is fired at a high temperature of more than 150 ° C., the component (C) is easily sufficiently cured, so that the photosensitive resin composition contains a smaller amount of the component (C). Is preferably included. The mass of the component (C) at this time is preferably 8 to 20% by mass with respect to the solid content, and more preferably 8 to 18% by mass with respect to the solid content.

Examples of the epoxy compound (C) include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol fluorene type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a phenol aralkyl type epoxy compound, and a naphthalene skeleton. Phenol novolak compound (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compound, trisphenol methane type epoxy compound, tetrakisphenol ethane type epoxy compound, polyhydric alcohol glycidyl ether, polyhydric carboxylic acid A copolymer of a monomer having a (meth) acrylic group containing glycidyl (meth) acrylate as a unit represented by a glycidyl ester or a copolymer of methacrylic acid and glycidyl methacrylate, 3', 4'-epoxycyclohexylmethyl 3 , 4-Epoxycyclohexanecarboxylate-type alicyclic epoxy compound, Polyfunctional epoxy compound having a dicyclopentadiene skeleton (for example, HP7200 series: manufactured by DIC Co., Ltd.), 2,2-Bis (hydroxymethyl) -1 -Butanol 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct (eg, EHPE3150: manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (eg, NISSO-PB / JP-100: manufactured by Nippon Soda Co., Ltd.) , Epoxy compounds having a silicone skeleton and the like are included.

The epoxy equivalent of the epoxy compound of the component (C) is preferably 100 to 300 g / eq, and more preferably 100 to 200 g / eq. The number average molecular weight (Mn) of the epoxy compound of the component (C) is preferably 100 to 5000. As these compounds, only one kind of compound may be used, or two or more kinds thereof may be used in combination.

For the epoxy equivalent of the epoxy compound of the component (C), a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) was used by adding an acetic acid solution of tetraethylammonium bromide after dissolving the resin solution in dioxane. It can be obtained by titrating with a 1 / 10N-perchloric acid solution. Further, the number average molecular weight (Mn) of the epoxy compound of the component (C) can be determined in terms of polystyrene by using gel permeation chromatography (GPC) measurement (HLC-8220 GPC, manufactured by Tosoh Corporation).

The photosensitive resin composition of the present invention preferably contains metal oxide fine particles as the component (D). The metal oxide fine particles are preferably inorganic particles having an average particle size of 100 to 700 nm, and more preferably TIO ₂ having an average particle size of 100 to 700 nm.

The particle size and shape of the TiO ₂ are not particularly limited as long as the formed cured film (coating film) can exhibit a light scattering function. The average particle size of TiO ₂ is 100 to 700 nm, more preferably 200 to 600 nm. When the average particle size of TiO ₂ is 100 nm or more, the light scattering property of the cured product can be sufficiently enhanced, and when the average particle size of TiO ₂ is 700 nm or less, the adhesion and linear reproducibility of the cured product are sufficiently improved. Can be enhanced.

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

Further, as the component (D), metal oxide fine particles having a refractive index of 1.9 to 2.3 may be contained instead of TiO ₂ having an average particle size of 100 to 700 nm. The particle size and shape of 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 exert 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 a metal oxide, the higher the light scattering property, but on the other hand, if the light scattering property is too strong, the transmittance of straight light decreases. The refractive index of the metal oxide fine particles can be measured with an Abbe refractive index meter using light having a wavelength of 589 nm.

The average particle size of ZnO and ZrO ₂ is preferably 150 to 500 nm, and more preferably 150 to 400 nm. When the average particle size of the metal oxide is 150 nm or more, the light scattering property by the cured film can be sufficiently enhanced, and when the average particle size of the metal oxide is 500 nm or less, the adhesion and linear reproducibility of the cured film can be improved. Can be sufficiently enhanced.

The average particle size of the metal oxide fine particles can be determined by the cumulant method using a particle size distribution meter "particle size analyzer FPAR-1000" of a dynamic light scattering method.

The component (D) can enhance the light scattering property of the cured film. However, if the amount of the 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 are deteriorated, and the light transmission of the transmission film is reduced. The sex 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 content.

When the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150 ° C. or lower, the content of the component (D) is 1% by mass or more and 35% by mass with respect to the total mass of the solid content. It is preferably less than%, more preferably 2% by mass or more and less than 25% by mass, and further 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 to be calcined at a high temperature of more than 150 ° C., the content of the component (D) is 1% by mass or more 35 based on the total mass of the solid content. It is preferably less than mass%, and more preferably 2% by mass or more and less than 25% by mass.

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

Examples of the component (E) include acetophenones, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone and other acetophenones; benzophenone. , 2-Chlorobenzophenone, p, p'-bisdimethylaminobenzophenone and other benzophenones; benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2- (o-chlorophenyl) -4 , 5-Phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o) −methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds; 2-trichloromethyl-5-styryl-1,3,4-oxadiazol, Halos such as 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methyldiazole compounds; 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- Phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4) −methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) Halomethyl-s-triazine compounds such as -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine; 1,2- Octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-phenylsulfanylphenyl) pig N-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanyl) O-acyloxime compounds such as phenyl) butane-1-onoxime-O-acetate; benzyldimethylketal, thioxanthone, 2-chlorothioxanone, 2,4-diethylthioxanone, 2-methylthioxanone, 2 -Sulfur compounds such as isopropylthioxanson; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone; azobisisobutyronitrile, benzoyl peroxide, cumemper Organic peroxides such as oxides; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; tertiary amines such as triethanolamine and triethylamine are included. As these photopolymerization initiators, only one of them may be used alone, or two or more of them may be used in combination.

In particular, when the amount of metal oxide added is large, when the amount of photopolymerization initiator added is small, or when the heat curing process at a high temperature of 150 ° C. cannot be performed and photocuring is desired to be performed more effectively. When a sensitive photopolymerization initiator is required, it is preferable to use O-acyloxime compounds (including ketooxime). Among them, the compound group represented by the general formula (7) and the general formula (8) can be applied as a more sensitive photopolymerization initiator. Among them, when it is desired to carry out photocuring more effectively in response to low temperature curing, it is more preferable to use an O-acyloxime-based photopolymerization initiator having a molar extinction coefficient at 365 nm of 10000 L / mol · cm or more. The term "photopolymerization initiator" as used in the present invention is used to include a sensitizer.

In formula (7), R ₁₀ and R ₁₁ independently have an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, or an aryl alkyl group having 4 to 20 carbon atoms. It represents 12 heterocyclic groups, where R ₁₂ represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, wherein the alkyl group and the aryl group represent. It may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene moiety may be an unsaturated bond, an ether bond, a thioether bond, or the like. It may contain an ester bond, and the alkyl group may be a linear, branched, or cyclic alkyl group.)

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

Here, the mass of the component (E) is preferably 0.1 to 30% by mass, preferably 1 to 25% by mass, based on the total mass of the components (A) and (B). When the mass of the component (E) is 0.1% by mass or more with respect to the total mass of the components (A) and (B), the photopolymerization rate is appropriate, so that the decrease in sensitivity is suppressed. it can. Further, when the mass of the component (E) is 30% by mass or less with respect to the total mass of the components (A) and (B), the sensitivity of the composition to exposure is not too high, so that the mask is used. The faithful line width can be reproduced and the pattern edge can be sharpened.

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

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

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

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

Examples of the curing agent for the epoxy compound as the component (G) include amine compounds, polyvalent carboxylic acid compounds, phenol resins, amino resins, dicyandiamides, Lewis acid complex compounds and the like. In the present invention, a polyvalent carboxylic acid compound can be preferably used.

Examples of polyvalent carboxylic acid compounds include polyvalent carboxylic acids, anhydrides of polyvalent carboxylic acids, and pyrolytic esters of polyvalent carboxylic acids. A polyvalent carboxylic acid is a compound having two or more carboxy groups in one molecule, for example, succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-. 4,5-dicarboxylic acid, norbornan-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic 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 and the like are included. Examples of polyvalent carboxylic acid anhydrides include acid anhydrides of the above compounds. This may be an intermolecular acid anhydride, but generally an intramolecularly ring-closed acid anhydride is used. Examples of thermally decomposable esters of polyvalent carboxylic acids include t-butyl esters, 1- (alkyloxy) ethyl esters, and 1- (alkylsulfanyl) ethyl esters of the above compounds (where alkyl has 1 to 20 carbon atoms. It is a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may have a branched structure or a ring structure, or may be substituted with an arbitrary substituent) and the like. Further, as the polyvalent carboxylic acid compound, a polymer or a copolymer having two or more carboxy groups can also be used, and the carboxy group may be an anhydride or a pyrolytic ester.

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, and tetracarboxylic acid dianhydride. It contains compounds in which an acid anhydride is ring-opened by reacting with a diamine or a diol. Of these, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and benzene-1,2,4-tricarboxylic acid anhydrides can be used. preferable. When the polyvalent carboxylic acid compound is used as a curing agent for the epoxy compound, the compounding ratio is such that the carboxy group of the polyvalent carboxylic acid compound is 0.5 to 1.5 mol with respect to 1 mol of the epoxy group of the epoxy compound. More preferably, it is blended so as to be 0.6 to 1.2 mol.

As the curing accelerator of the epoxy compound as the component (G), a known compound known as a curing accelerator of the epoxy compound, a curing catalyst, a latent curing agent, or the like can be used. Examples of curing accelerators for epoxy compounds include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organic metal compounds, imidazoles and the like. Among the above curing accelerators, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene, or salts thereof. Is preferable.

The amount of the curing 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. When the amount of the curing accelerator added is 0.05 parts by mass or more, the amount added can be adjusted depending on the state of development of chemical resistance of the resin film pattern after heat curing. Further, when the amount of the curing accelerator added is 2 parts by mass or less, the curing rate of the epoxy compound can be in an appropriate range.

When the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150 ° C. or lower, the total mass of the components (C) and (G) is 15% by mass with respect to the total mass of the solid content. Above 35. It is preferably 20% by mass or less, and more preferably 20% by mass or more and 30% by mass or less. When the total mass of the component (C) and the component (G) is 15% by mass or more with respect to the total mass of the solid content, the curability when cured at a low temperature of 150 ° C. or lower is sufficiently ensured. Further, if the total mass of the component (C) and the component (G) is 35% by mass or less with respect to the total mass of the solid content, the patterning property, linearity and solvent resistance during alkaline development may be adversely affected. It is possible to improve the curability.

When the photosensitive resin composition of the present invention is a composition that is fired at a high temperature of more than 150 ° C., the component (G) may be absent, and the total mass of the components (C) and (G) is solid. It is preferably 8 to 25% by mass with respect to the total mass of the minute.

Next, a method for manufacturing a plurality of substrates with a cured film of the present invention will be described. The cured film (coating film) of the present invention can be formed by a photolithography method using the photosensitive resin composition of the present invention.

In the method for producing a substrate with a cured film by forming a light-scattering cured film pattern on the substrate of the present invention, a photosensitive resin composition containing inorganic particles having an average particle size of 100 to 700 nm is formed on the substrate. This is a manufacturing method in which an unexposed portion is removed by development and heated to form a predetermined cured film pattern.

In the method of forming a cured film pattern having light scattering property on a substrate having a heat resistant temperature of 150 ° C. or less to produce a substrate with a cured film, the above-mentioned photosensitive resin composition is applied onto the substrate and photomasked. This is a manufacturing method in which exposure is performed through a mask, an unexposed portion is removed by development, and heating is performed at 150 ° C. or lower to form a predetermined cured film pattern.

The method of the present invention for producing a substrate with a cured film by forming a cured film pattern having light scattering property on a substrate having a heat resistant temperature of more than 150 ° C. is to apply the above-mentioned photosensitive resin composition on the substrate and take a photo. This is a manufacturing method in which exposure is performed through a mask, an unexposed portion is removed by development, and heating is performed at a temperature of more than 150 ° C. to form a predetermined cured film pattern.

The method of applying the photosensitive resin composition of the present invention on a substrate is any method such as a known solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coater machine, a spinner machine, or the like. Can also be adopted. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (prebaking). Pre-baking is performed by heating in an oven, a hot plate, or the like. The heating temperature and heating time in the prebake are appropriately selected according to the solvent used, and are performed at a temperature of, for example, 60 to 110 ° C. (set so as not to exceed the heat resistant temperature of the substrate) for 1 to 3 minutes.

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

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

Alkaline development after exposure is performed for the purpose of removing the resist in the unexposed portion, and this development forms a desired pattern. Examples of the developing solution suitable for this alkaline development include an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like, and in particular, sodium carbonate, potassium carbonate, and lithium carbonate. It is preferable to develop at a temperature of 23 to 28 ° C. using a weak alkaline aqueous solution containing 0.05 to 3.0% by mass of carbonate such as, and it is fine using a commercially available developer, an ultrasonic cleaner or the like. The image can be formed precisely.

When a cured film pattern having light scattering property is formed on a substrate having a heat resistant temperature of 150 ° C. or lower, the temperature is 80 to 140 ° C. (set so as not to exceed the heat resistant temperature of the substrate) and 20 after development. The heat treatment (post-baking) is preferably performed under the conditions of ~ 90 minutes, and more preferably performed under the conditions of a temperature of 90 to 120 ° C. and a heating time of 30 to 60 minutes. The post-baking is performed for the purpose of enhancing the adhesion between the patterned cured film and the substrate. This is done by heating in an oven, hot plate, etc., similar to prebaking. The patterned cured film of the present invention is formed through each step by the above photolithography method.

When a cured film pattern having light scattering property is formed on a substrate having a heat resistant temperature of more than 150 ° C., the temperature is 80 to 250 ° C. (set so as not to exceed the heat resistant temperature of the substrate) and 20 after development. The heat treatment (post-baking) is preferably performed under the conditions of ~ 90 minutes, and more preferably performed under the conditions of a temperature of 180 to 230 ° C. and a heating time of 30 to 60 minutes. The post-baking is performed for the purpose of enhancing the adhesion between the patterned cured film and the substrate. This is done by heating in an oven, hot plate, etc., similar to prebaking. The patterned cured film of the present invention is formed through each step by the above photolithography method.

By the above method, a cured film obtained by curing a photosensitive resin composition containing TiO ₂ having an average particle size of 100 to 700 nm as the component (D) described above, and a transmittance in the visible light region of 70% or more. When white light is irradiated perpendicularly to the substrate with a cured film, the intensity of scattered light at 60 ° is 5 ° when the angle of directly transmitted light traveling straight without scattering is 0 °. It is possible to obtain a substrate with a cured film which is 20% or more of the amount. Therefore, it can be suitably used for a display device for a light scattering layer.

A cured film obtained by curing a photosensitive resin composition containing a metal oxide (ZnO, ZrO ₂ ) having a refractive index of 1.9 to 2.3 as the component (D) described above by the above method, and a visible light region. When the angle at which the transmittance of 80% is 80 ° is 0 °, a substrate with a cured film can be obtained in which the intensity of scattered light at 45 ° is 15% or more with respect to the intensity of scattered light at 5 °. Therefore, it can be suitably used for a display device for a light scattering layer.

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

First, the synthesis examples of the alkali-soluble resin represented by the general formula (1) will be described. Unless otherwise specified, the evaluation of the resins in these synthesis examples was carried out as follows. When the same model is used for various measuring devices, the device manufacturer name is omitted from the second place. Further, in Examples 1 and 2, the glass substrates used for producing the substrate with the cured film for measurement are all glass substrates subjected to the same treatment.

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

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

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600".

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

[Average particle size]
It was determined by the cumulant method using a particle size distribution meter "particle size analyzer FPAR-1000" of a dynamic light scattering method.

The abbreviations used in the synthesis example are as follows.
DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid SA: Succinic anhydride BPFE: Bisphenol fluorene type epoxy compound (9,9-bis (4-hydroxyphenyl) fluorene reaction with chloromethyloxylane object)
BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride PTMA: Pentaerythritol tetra (mercaptoacetate)
DPHA: Mix of dipentaerythritol pentaacrylate and hexaacrylate TEAB: Tetraethylammonium bromide AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine BzDMA: benzyldimethylamine PGMEA: Propylene glycol monomethyl Ether acetate

[Synthesis Example 1]
BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g) and TEAB (0.48 g) were charged in a 500 ml four-necked flask equipped with a return condenser. The reaction was carried out by stirring at 100 to 105 ° C. for 20 hours. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged in a flask, and the mixture was stirred at 120 to 125 ° C. for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin. (A) -1 was obtained. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (in terms of solid content) was 103 mgKOH / g, and the weight average molecular weight (Mw) by GPC analysis was 3600.

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

Then, after replacing the inside of the flask system with air, AA (24.0 g (95% of glycidyl group)), TDAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution. , 120 ° C. for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. Further, SA (30.0 g (90% of the number of moles added with AA)) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution and reacted at 120 ° C. for 4 hours to polymerize. An unsaturated group-containing alkali-soluble copolymer resin solution (A) -2 was obtained. The solid content concentration of the resin solution was 41.7% by mass, the acid value (solid content equivalent) was 76 mgKOH / g, and the weight average molecular weight (Mw) by GPC analysis was 5300.

[Synthesis Example 3]
In a 1 L four-necked flask, PTMA (20 g, 0.19 mol of mercapto group), DPHA (212 g, 2.12 mol of acrylic group), PGMEA (58 g), HQ (0.1 g), and BzDMA (0. 01 g) was added and reacted at 60 ° C. for 12 hours to obtain a dendritic polymer solution (B) -3 (solid content concentration: 80% by mass). The disappearance of the thiol group of the obtained dendritic polymer was confirmed by the iodometry method. 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 group)
(A) -1: Resin solution obtained in Synthesis Example 1 (solid content concentration 56.1% by mass)
(A) -2: Resin solution obtained in Synthesis Example 2 (solid content concentration 41.7% by mass)

(Photopolymerizable monomer)
(B) -1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA (acrylic equivalent 96-115), manufactured by Nippon Kayaku Co., Ltd.)
(B) -2: Mixture of pentaerythritol triacrylate and tetraacrylate (M-450 (acrylic equivalent 88), manufactured by Toa Synthetic Co., Ltd.)
(B) -3: Dendrite polymer obtained in Synthetic Example 3 above

(Epoxy compound)
(C) -1: 3,4-Epoxycyclohexanecarboxylic acid (3', 4'-epoxycyclohexyl) methyl (celloxide 2021P (epoxy equivalent 135), manufactured by Daicel Corporation)
(C) -2: 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct (EHPE3150 (epoxy equivalent 180), manufactured by Daicel Co., Ltd.)
(C) -3: Tetra butanetetracarboxylate (3,4-epoxycyclohexylmethyl) modified ε-caprolactone (Epolide GT401 (epoxy equivalent 220), manufactured by Daicel Corporation)

[Metal oxide dispersion]
(Titania dispersion)
(D) -1: Titania dispersion (average particle size 50 nm) concentration 75% by mass, propylene glycol monomethyl ether acetate solvent titania dispersion (D) -2: Titania dispersion (average particle size 120 nm) concentration 75% by mass, Titania dispersion of propylene glycol monomethyl ether acetate solvent (D) -3: Titania dispersion (average particle size 270 nm) concentration 75% by mass, titania dispersion of propylene glycol monomethyl ether acetate solvent (D) -4: Titania dispersion (Titania dispersion) (Average particle size 410 nm) concentration 75% by mass, propylene glycol monomethyl ether acetate solvent titania dispersion (D) -5: Titania dispersion (average particle size 620 nm) concentration 75% by mass, propylene glycol monomethyl ether acetate solvent titania dispersion (D) -6: Titania dispersion (average particle size 970 nm) concentration 75% by mass, titania dispersion of propylene glycol monomethyl ether acetate solvent

(ZnO dispersion and ZrO ₂ dispersion)
(D) -7: ZnO dispersion (average particle size 200 nm, refractive index 2.0) concentration 20% by mass, ZnO dispersion of propylene glycol monomethyl ether acetate solvent (D) -8: ZnO dispersion (average particle size 350 nm) , Refractive index 2.0) Concentration 20% by mass, ZnO dispersion of propylene glycol monomethyl ether acetate solvent (D) -9: ZrO ₂ dispersion (average particle size 170 nm, refractive index 2.2) Concentration 20% by mass, propylene ZrO ₂ dispersion of glycol monomethyl ether acetate solvent (D) -10: ZrO ₂ dispersion (average particle size 240 nm, refractive index 2.2) concentration 20% by mass, ZrO ₂ dispersion of propylene glycol monomethyl ether acetate solvent (D) ) -11: TiO ₂ dispersion (average particle size 400 nm, refractive index 2.5) concentration 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 of propylene glycol monomethyl ether acetate solvent

(Photopolymerization initiator)
(E): 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (IrgacureOXE-01, manufactured by BASF, "Irgacure" is a registered trademark of the company)

(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)

(Curing agent and curing accelerator)
(G) -1: Benzene 1,2,4-tricarboxylic acid-1,2-anhydride (G) -2: 1,8-diazabicyclo [5.4.0] Undec-7-ene (DBU (R)) ) PGMEA solution containing 2.0% by mass, manufactured by Sun Appro Co., Ltd.)

(Other additives)
(H) -1: Surfactant (Mega Fuck F-447, manufactured by DIC Corporation, "Mega Fuck" is a registered trademark of the company)
(H) -2: Surfactant (DOWNSIL SH3775, manufactured by Dow, "DOWNSIL" is a registered trademark of the company)
(H) -3: Antioxidant (pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Irganox 1010, manufactured by BASF, "Irganox" is a registered trademark of the same company)
(H) -4: Coupling agent (3-glycidoxypropyltrimethoxysilane)

[Example 1]
Photosensitive resin compositions using a titania dispersion as a component (D) were prepared as Examples 1 to 16 and Comparative Examples 1 to 4. The ingredients are shown in Tables 1 and 2. The numerical values in Tables 1 and 2 all represent mass%. In addition, (B) -3 is the amount of the dendritic polymer containing no solvent.

[Evaluation]
Using the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4, a substrate with a cured film for evaluating development characteristics was produced.

(Preparation of substrate with cured film for developing development characteristics)
The surface of the photosensitive resin composition shown in Tables 1 and 2 was washed by irradiating the surface with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm ² in advance with a low-pressure mercury lamp, and the surface of the photosensitive resin composition was cleaned. (Manufactured) (hereinafter referred to as "glass substrate"), coated with a spin coater so that the film thickness after heat curing treatment is 2.0 μm, and prebaked at 90 ° C. for 2 minutes using a hot plate. A cured film (coating film) was prepared. Next, a negative photomask having a line / space of 20 μm / 20 μm was placed on the cured film (coating film), and an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW / cm ² was used to irradiate ultraviolet rays of 50 mJ / cm ² . A photocuring reaction was carried out.

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.04% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, a spray water wash of 5 kgf / cm ² was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 90 using a hot air dryer. This curing (post-baking) was performed at ° C. for 60 minutes to obtain a substrate with a cured film for evaluating development characteristics according to Examples 1 to 16 and Comparative Examples 1 to 4.

The following evaluation was performed using the substrate with a cured film for evaluating the development characteristics.

[Development characteristic evaluation]
(Pattern adhesion)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Not peeled at all Δ: Partly peeled ×: Mostly peeled

(Pattern linearity)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

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

(Pattern definition)
(Evaluation method)
The 10 to 50 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
⊚: A pattern of 10 to 15 μm is formed ◯: A pattern of 16 to 24 μm is formed Δ: A pattern of 25 to 50 μm is formed ×: A pattern is not 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.

(Preparation of substrate with cured film for solvent resistance evaluation)
The photosensitive resin compositions shown in Tables 1 and 2 are applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and at 90 ° C. using a hot plate. A cured film (coating film) was prepared by prebaking for 2 minutes. Next, a negative photomask having a line / space of 20 μm / 20 μm was placed on the cured film (coating film), and an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW / cm ² was used to irradiate ultraviolet rays of 50 mJ / cm ² . A photocuring reaction was carried out.

Next, the exposed cured film (coating film) was developed with a 0.05% potassium hydroxide solution at 25 ° C. at a shower pressure of 1 kgf / cm ² for 60 seconds, and then washed with a spray of 5 kgf / cm ² . To remove the unexposed portion of the cured film (coating film) to form a cured film pattern on a glass substrate, and main cure (post-bake) at 90 ° C. for 60 minutes using a hot air dryer. Substrates with a cured film for evaluating solvent resistance according to Examples 1 to 16 and Comparative Examples 1 to 4 were obtained.

The following evaluation was performed using the substrate with a cured film for solvent resistance evaluation.

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

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

[Evaluation of transmittance]
(Evaluation method)
The transmittance of the visible light region (380 nm to 780 nm) of the substrate with the cured film was measured using an ultraviolet-visible near-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation). In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Transmittance is 70% or more Δ: Transmittance is 60% or more and less than 70% ×: Transmittance is less than 60%

[Evaluation of light scattering]
The substrate with the cured film was vertically irradiated with white light, and the transmitted scattered light was measured using a goniophotometer "GP-1" (manufactured by Nikka Densoku Co., Ltd.). In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was more than 20% of the light scattering intensity at 5 °. Item Δ: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was more than 10% of the light scattering intensity at 5 °. 20% or less ×: The intensity of scattered light at 5 ° and 60 ° when the angle of the directly transmitted light traveling straight is 0 ° is evaluated, and the light scattering intensity at 60 ° becomes the light scattering intensity at 5 °. 10% or less

Table 3 shows the results of evaluation of the above items with respect to the substrate with a cured film obtained by curing the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4 obtained above.

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

[Example 2]
Photosensitive resin compositions using a titania dispersion as a component (D) were prepared as Examples 17 to 30 and Comparative Examples 5 to 9. The ingredients 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 the dendritic polymer containing no solvent.

[Evaluation]
Using the photosensitive resin compositions of Examples 17 to 30 and Comparative Examples 5 to 9, a substrate with a cured film for evaluating development characteristics was produced.

(Preparation of substrate with cured film for developing development characteristics)
The photosensitive resin compositions shown in Tables 4 and 5 are applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and at 90 ° C. using a hot plate. A cured film (coating film) was prepared by prebaking for 2 minutes. Next, the exposure gap was adjusted to 100 μm, the cured film (coating film) was covered with a negative photomask of 10 to 50 μm (in 5 μm increments), and an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm ² was used to cover 50 mJ / cm. ^The photocuring reaction was carried out by irradiating with the ultraviolet rays of ² .

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.04% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, a spray water wash of 5 kgf / cm ² was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 230 using a hot air dryer. This curing (post-baking) was performed at ° C. for 30 minutes to obtain a substrate with a cured film for evaluating development characteristics according to Examples 17 to 30 and Comparative Examples 5 to 9.

The following evaluation was performed using the substrate with a cured film for evaluating the development characteristics.

[Development characteristic evaluation]
(Pattern adhesion)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Not peeled at all Δ: Partly peeled ×: Mostly peeled

(Pattern linearity)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

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

(Pattern definition)
(Evaluation method)
The 10 to 50 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
⊚: A pattern of 10 to 15 μm is formed ◯: A pattern of 16 to 24 μm is formed Δ: A pattern of 25 to 50 μm is formed ×: A pattern is not formed

[Evaluation of transmittance]
(Evaluation method)
Using an ultraviolet-visible near-infrared spectrophotometer "UH4150", the transmittance in the visible light region (380 nm to 780 nm) of the substrate with the cured film was measured. In addition, ○ or more was accepted.

(Evaluation criteria)
◯: Transmittance is 70% or more Δ: Transmittance is 60% or more and less than 70% ×: Transmittance is less than 60%

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

(Preparation of base material with cured film for light scattering evaluation)
The photosensitive resin compositions shown in Tables 4 and 5 are applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and at 90 ° C. using a hot plate. A cured film (coating film) was prepared by prebaking for 2 minutes. Next, a photocuring reaction was carried out by irradiating ultraviolet rays of 50 mJ / cm ² with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW / cm ² without covering with a negative photomask.

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.05% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, a spray water wash of 5 kgf / cm ² was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 230 using a hot air dryer. This curing (post-baking) was performed at ° C. for 30 minutes to obtain a substrate with a cured film for light scattering evaluation according to Examples 17 to 30 and Comparative Examples 5 to 9.

The following evaluation was performed using the substrate with a cured film for light scattering evaluation.

(Evaluation method)
The substrate with the cured film was vertically irradiated with white light, and the transmitted scattered light was measured using a goniometer "GP-1". In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was more than 20% of the light scattering intensity at 5 °. Item Δ: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was more than 10% of the light scattering intensity at 5 °. 20% or less ×: The intensity of scattered light at 5 ° and 60 ° when the angle of the directly transmitted light traveling straight is 0 ° is evaluated, and the light scattering intensity at 60 ° becomes the light scattering intensity at 5 °. 10% or less

Table 6 shows the results of evaluation of the above items with respect to the substrates with a cured film obtained by curing the photosensitive resin compositions of Examples 17 to 30 and Comparative Examples 5 to 9 obtained above.

As is clear from the results of Examples 17 to 30 and Comparative Examples 5 to 9, the photosensitive resin composition containing the alkali-soluble resin represented by the formula (1) of the present invention and TiO ₂ is used. It was found that a substrate with a cured film capable of forming a fine pattern as well as having excellent light scattering properties can be produced.

[Example 3]
As the component (D), the photosensitive resin composition using the ZnO dispersion and ZrO ₂ dispersion Example 31 to 45 were prepared as Comparative Examples 10 to 12. The ingredients 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 the dendritic polymer containing no solvent.

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

(Preparation of substrate with cured film for developing development characteristics)
The photosensitive resin compositions shown in Tables 7 and 8 are applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and at 90 ° C. using a hot plate. A cured film (coating film) was prepared by prebaking for 2 minutes. Next, a negative photomask having a line / space of 20 μm / 20 μm was placed on the cured film (coating film), and an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW / cm ² was used to irradiate ultraviolet rays of 50 mJ / cm ² . A photocuring reaction was carried out.

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.04% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, a spray water wash of 5 kgf / cm ² was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 90 using a hot air dryer. This curing (post-baking) was performed at ° C. for 60 minutes to obtain a substrate with a cured film for evaluating development characteristics according to Examples 31 to 45 and Comparative Examples 10 to 12.

The following evaluation was performed using the substrate with a cured film for evaluating the development characteristics.

[Development characteristic evaluation]
(Pattern adhesion)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Not peeled at all Δ: Partly peeled ×: Mostly peeled

(Pattern linearity)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

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

(Pattern definition)
(Evaluation method)
The 10 to 50 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
⊚: A pattern of 10 to 15 μm is formed ◯: A pattern of 16 to 24 μm is formed Δ: A pattern of 25 to 50 μm is formed ×: A pattern is not formed

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

(Preparation of substrate with cured film for solvent resistance evaluation)
The photosensitive resin compositions shown in Tables 7 and 8 are applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and at 90 ° C. using a hot plate. A cured film (coating film) was prepared by prebaking for 2 minutes. Next, a negative photomask having a line / space of 20 μm / 20 μm was placed on the cured film (coating film), and an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW / cm ² was used to irradiate ultraviolet rays of 50 mJ / cm ² . A photocuring reaction was carried out.

Next, the exposed cured film (coating film) was developed with a 0.05% potassium hydroxide solution at 25 ° C. at a shower pressure of 1 kgf / cm ² for 60 seconds, and then washed with a spray of 5 kgf / cm ² . To remove the unexposed portion of the cured film (coating film) to form a cured film pattern on a glass substrate, and main cure (post-bake) at 90 ° C. for 60 minutes using a hot air dryer. Substrates with a cured film for evaluating solvent resistance according to Examples 31 to 45 and Comparative Examples 10 to 12 were obtained.

The following evaluation was performed using the substrate with a cured film for solvent resistance evaluation.

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

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

[Evaluation of transmittance]
(Evaluation method)
Using an ultraviolet-visible near-infrared spectrophotometer "UH4150", the transmittance in the visible light region (380 nm to 780 nm) of the substrate with the cured film was measured. In addition, △ or more was regarded as passing. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Transmittance is 80% or more Δ: Transmittance is 70% or more and less than 80% ×: Transmittance is less than 70%

[Evaluation of light scattering]
The substrate with the cured film was vertically irradiated with white light, and the transmitted scattered light was measured using a goniometer "GP-1". In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: The intensity of scattered light at 5 ° and 45 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 45 ° was more than 15% of the light scattering intensity at 5 °. △: The intensity of scattered light at 5 ° and 45 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 45 ° was more than 10% of the light scattering intensity at 5 °. 15% or less ×: The intensity of scattered light at 5 ° and 45 ° when the angle of the directly transmitted light traveling straight is 0 ° is evaluated, and the light scattering intensity at 45 ° becomes the light scattering intensity at 5 °. 10% or less

Table 9 shows the results of evaluation of the above items with respect to the substrates with a cured film obtained by curing the photosensitive resin compositions of Examples 31 to 45 and Comparative Examples 10 to 12 obtained above.

As is clear from the results of Examples 31 to 45 and Comparative Examples 10 to 12, the photosensitive group-containing alkali-soluble resin and metal oxide (ZnO, ZrO ₂ ) of the general formula (1) of the present invention are contained. It was found that by using the sex resin composition, it is possible to produce a cured film having excellent light scattering properties and capable of forming a fine pattern.

[Example 4]
As the component (D), the photosensitive resin composition using the ZnO dispersion and ZrO ₂ dispersion Example 46-60 were prepared as comparative examples 13 to 15. The compounding 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 the dendritic polymer containing no solvent.

[Evaluation]
Using the photosensitive resin compositions of Examples 46 to 60 and Comparative Examples 13 to 15, a substrate with a cured film for evaluating development characteristics was produced.

(Preparation of substrate with cured film for developing development characteristics)
The photosensitive resin compositions shown in Tables 10 and 11 are applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and at 90 ° C. using a hot plate. A cured film (coating film) was prepared by prebaking for 2 minutes. Next, the exposure gap was adjusted to 100 μm, the cured film (coating film) was covered with a negative photomask of 10 to 50 μm (in 5 μm increments), and an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm ² was used to cover 50 mJ / cm. ^The photocuring reaction was carried out by irradiating with the ultraviolet rays of ² .

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.04% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, a spray water wash of 5 kgf / cm ² was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 230 using a hot air dryer. This curing (post-baking) was performed at ° C. for 30 minutes to obtain a substrate with a cured film for evaluating development characteristics according to Examples 46 to 60 and Comparative Examples 13 to 15.

The following evaluation was performed using the substrate with a cured film for evaluating the development characteristics.

[Development characteristic evaluation]
(Pattern adhesion)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Not peeled at all Δ: Partly peeled ×: Mostly peeled

(Pattern linearity)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

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

(Pattern definition)
(Evaluation method)
The 10 to 50 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
⊚: A pattern of 10 to 15 μm is formed ◯: A pattern of 16 to 24 μm is formed Δ: A pattern of 25 to 50 μm is formed ×: A pattern is not formed

[Evaluation of transmittance]
(Evaluation method)
Using an ultraviolet-visible near-infrared spectrophotometer "UH4150", the transmittance in the visible light region (380 nm to 780 nm) of the substrate with the cured film was measured. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Transmittance is 80% or more Δ: Transmittance is 70% or more and less than 80% ×: Transmittance is less than 70%

Using the photosensitive resin compositions of Examples 46 to 60 and Comparative Examples 13 to 15, a substrate with a cured film for light scattering evaluation was produced.

(Preparation of substrate with cured film for light scattering evaluation)
The photosensitive resin compositions shown in Tables 10 and 11 are applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and at 90 ° C. using a hot plate. A cured film (coating film) was prepared by prebaking for 2 minutes. Next, a photocuring reaction was carried out by irradiating ultraviolet rays of 50 mJ / cm ² with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW / cm ² without covering with a negative photomask.

Next, the exposed cured film (coating film) was subjected to a shower pressure of 1 kgf / cm ² with a 0.05% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, a spray water wash of 5 kgf / cm ² was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 230 using a hot air dryer. This curing (post-baking) was performed at ° C. for 30 minutes to obtain a substrate with a cured film for evaluating light scattering properties according to Examples 46 to 60 and Comparative Examples 13 to 15.

The following evaluation was performed using the substrate with a cured film for light scattering evaluation.

[Evaluation of light scattering]
(Evaluation method)
White light was vertically irradiated to a cured film (coating film) similar to the cured film (coating film) prepared for solvent resistance evaluation, and transmitted scattered light was measured using a goniophotometer. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: The intensity of scattered light at 5 ° and 45 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 45 ° was more than 15% of the light scattering intensity at 5 °. △: The intensity of scattered light at 5 ° and 45 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 45 ° was more than 10% of the light scattering intensity at 5 °. 15% or less ×: The intensity of scattered light at 5 ° and 45 ° when the angle of the directly transmitted light traveling straight is 0 ° is evaluated, and the light scattering intensity at 45 ° becomes the light scattering intensity at 5 °. 10% or less

Table 12 shows the results of evaluation of the above items with respect to the substrates with a cured film obtained by curing the photosensitive resin compositions of Examples 46 to 60 and Comparative Examples 13 to 15 obtained above.

As is clear from the results of Examples 46 to 60 and Comparative Examples 13 to 15, the unsaturated group-containing alkali-soluble resin and metal oxide (ZnO, ZrO ₂ ) of the general formula (1) of the present invention are used. It was found that by using the photosensitive resin composition containing the mixture, it is possible to produce a cured film having excellent light scattering properties and capable of forming a fine pattern.

According to the method for producing 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, it is useful for, for example, a display device. That is, since the pattern can be formed by photolithography, there is an advantage that it can be formed by the existing photolithography process. Further, since the film strength can be obtained even at a low temperature, it is suitable for manufacturing a touch panel and a color filter using a substrate having low heat resistance.

Claims (13)

A method for producing a substrate with a cured film by forming a light-scattering cured film pattern on the substrate, wherein a photosensitive resin composition containing inorganic particles having an average particle size of 100 to 700 nm is placed on the substrate. A method for producing a substrate with a cured film, which comprises applying, exposing through a photomask, removing an unexposed portion by development, and heating to form a predetermined cured film pattern. A substrate with a cured film manufactured by the method according to claim 1, which has a transmittance of 70% or more in the visible light region and travels straight when white light is irradiated perpendicularly to the substrate with the cured film. With a cured film, the intensity of scattered light at 60 ° when the angle of the directly transmitted light is 0 ° is 20% or more of the intensity of the scattered light when the angle of the directly transmitted light is 5 °. substrate. A substrate with a cured film manufactured by the method according to claim 1, which has a transmittance of 80% or more in the visible light region and travels straight when white light is irradiated perpendicularly to the substrate with the cured film. With a cured film, the intensity of scattered light at 45 ° when the angle of the directly transmitted light is 0 ° is 15% or more of the intensity of the scattered light when the angle of the directly transmitted light is 5 °. substrate. A photosensitive resin composition used for producing the substrate with a cured film according to claim 2.
(A) Unsaturated group-containing alkali-soluble resin and
(B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds,
(C) Epoxy compound and
(D) TiO ₂ and
(E) Photopolymerization initiator and
(F) Solvent and
Including
A photosensitive resin composition in which the content of the component (D) is 1% by mass or more and less than 20% by mass with respect to the total mass of the solid content. A photosensitive resin composition used for producing the substrate with a cured film according to claim 3.
(A) Unsaturated group-containing alkali-soluble resin and
(B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds,
(C) Epoxy compound and
(D) Metal oxide fine particles and
(E) Photopolymerization initiator and
(F) Solvent and
Including
A photosensitive resin composition having a refractive index of the component (D) of 1.9 to 2.3. The photosensitive resin composition according to claim 4 or 5.
A photosensitive resin composition in which the unsaturated group-containing alkali-soluble resin of the component (A) is an unsaturated group-containing alkali-soluble resin represented by the general formula (1).

(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, and R ₅ is hydrogen. It is an atomic or methyl group, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, and Z is independently represented by a hydrogen atom or the general formula (2). However, one or more of Z are substituents represented by the general formula (2), and n is an integer of 1 to 20.)

(In formula (2), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.) The photosensitive resin composition according to any one of claims 4 to 6.
The mass of the component (A) is 20 to 70% by mass with respect to the total mass of the solid content, and the mass of the component (B) is 5 to 40% by mass with respect to the total mass of the solid content (C). A photosensitive resin composition in which the mass of the component is 8 to 24% by mass with respect to the total mass of the solid content.
The photosensitive resin composition according to any one of claims 4 to 7.
A photosensitive resin containing a curing agent and / or a curing accelerator of an epoxy compound (G), and the total mass of the components (C) and (G) is 15 to 35% by mass with respect to the total mass of the solid content. Composition. The photosensitive resin composition according to any one of claims 4 to 8, wherein the epoxy equivalent of the epoxy compound of the component (C) is 100 to 300 g / eq. The photosensitive resin composition according to claim 8, wherein the curing agent and / or curing accelerator of the component (G) contains an acid anhydride. A cured film obtained by curing the photosensitive resin composition according to any one of claims 4 to 10. A display device having the cured film according to claim 11 or the substrate with the cured film according to claim 2 or 3. The photosensitive resin according to any one of claims 4 to 10, which is a method for producing a substrate with a cured film by forming a cured film pattern having light scattering property on a substrate having a heat resistant temperature of 150 ° C. or less. A method for producing a substrate with a cured film, wherein the composition is applied onto a substrate, exposed through a photomask, an unexposed portion is removed by development, and heated at 150 ° C. or lower to form a predetermined cured film pattern. ..