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.

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

[Technical Field]

[0001] 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 a photosensitive resin composition, and a display device having a cured film or a substrate with a cured film. [Background technology]

[0002] In recent years, studies have been conducted to form patterns using photosensitive resin compositions with light-scattering properties on plastic substrates (plastic films, resin films) such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate), or on substrates with organic devices such as organic EL devices and organic TFTs, for the purpose of making devices more flexible and integrated into a single chip.

[0003] In this case, when a low-temperature firing method is used to form a pattern using a photosensitive resin composition that is fired at high temperatures, in accordance with the heat resistance of the substrate, the film strength of the pattern formed on plastic substrates and substrates with organic devices becomes insufficient. This leads to problems such as film thinning, surface roughness, and pattern peeling in subsequent processes (for example, solvent resistance during resist coating and alkali resistance during alkaline development).

[0004] Therefore, there is a need for a photosensitive resin composition that has light-scattering properties and can be used for both high-temperature and low-temperature firing.

[0005] For example, Patent Document 1 discloses a photosensitive composition for forming a pattern having a light-scattering function, comprising a TiO2 filler, a photopolymerizable (meth)acrylic monomer, an alkali-soluble resin, a photopolymerization initiator, and an organic solvent. The above photosensitive composition is said to have photolithography properties suitable for use in display devices, and to have light-scattering properties that scatter blue light over an angle wider than the angle of incidence by the TiO2 filler.

[0006] In addition, Patent Document 2 discloses a resin composition for a light-scattering layer that contains at least one resin (A) as a binder material, contains fluorine as light-scattering particles (B), and contains at least one metal-oxide fine particle selected from the group consisting of ZrO2 and TiO2 as metal-oxide fine particles (C). The above resin composition for a light-scattering layer is said to be capable of providing 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 region.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] 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 could not obtain a pattern having desired light-scattering properties. In addition, neither the photosensitive composition described in Patent Document 1 nor the resin composition for a light-scattering layer described in Patent Document 2 sufficiently satisfied the adhesion and linear reproducibility of the cured film. <​​​​​​​​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 light scattering properties on a substrate, comprising applying a photosensitive resin composition containing inorganic particles with an average particle size of 100 to 700 nm on the substrate, exposing through a photomask, removing unexposed portions by development, and heating to form a predetermined cured film pattern.

[0011] The cured film of the present invention is obtained by curing the above photosensitive resin composition.

[0012] The substrate with a cured film of the present invention has the above cured film.

[0013] The display device of the present invention has the above cured film or the above substrate with a cured film.

[0014] 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 light scattering properties on a substrate with a heat resistance temperature of 150°C or lower, comprising applying the above photosensitive resin composition on the substrate, exposing through a photomask, removing unexposed portions by development, and heating at 150°C or lower to form a predetermined cured film pattern.

Effects of the Invention

[0015] According to the present invention, it is possible to provide a method for manufacturing a substrate with a cured film, a substrate with a cured film, a photosensitive resin composition capable of directly forming a cured film having a light scattering function on a substrate and excellent in adhesion, linearity, solvent resistance, etc. regardless of the heat resistance temperature of the substrate, a cured film obtained by curing the photosensitive resin composition, and a display device having the cured film and the substrate with a cured film.

Modes for Carrying Out the Invention

[0016] 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 content of each component has a first decimal place of 0, the notation after the decimal point may be omitted.

[0017] The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin containing an unsaturated group. Any resin that has an acid value for imparting alkali developability and can be combined with the photopolymerizable monomer of component (B) to achieve appropriate photocurability can be used without particular limitation. Among these resins, resins with a highly aromatic skeleton generally tend to have a higher specific gravity than aliphatic resins, and when prepared as a solution of the same resin concentration, the specific gravity of the resin solution can be increased. This is presumed to increase the dispersion stability of metal oxide fine particles, which have a higher specific gravity than the resin. Therefore, by using the resin represented by general formula (1), a photosensitive resin composition with sufficient dispersion stability of metal oxide fine particles can be obtained. Among these, the effect is greater when using an alkali-soluble resin containing an unsaturated group (cardio resin) having a polycyclic aromatic skeleton in which X in general formula (1) is a fluorene-9,9-diyl group, and it is considered that the dispersion stability of metal oxide fine particles is improved in the cardiac resin. As a result, the light scattering properties of the cured film obtained by curing the photosensitive resin composition of the present invention can be increased. Furthermore, when pattern formation is performed by photolithography, Cardo resin has excellent adhesion properties during development, and it is presumed that this property can be effectively utilized even when metal oxide fine particle fillers are used in its coexistence.

[0018] In the photosensitive resin composition of the present invention, the mass of component (A) is preferably 20 to 70% by mass of the total mass of solids.

[0019] Here, if the photosensitive resin composition of the present invention is a composition fired at a low temperature of 150°C or lower, the content of component (A) is more preferably 20 to 60% by mass relative to the total mass of solids, and more preferably 35 to 55% by mass when using cardo resin. Furthermore, if other resins such as acrylic copolymers are used, it is more preferably 20 to 50% by mass. If the mass of component (A) is 20% by mass or more relative to the total mass of solids, it becomes possible to stably form a pattern during alkaline development even if metal oxide fine particles are included, and it becomes possible to design the formulation of the photosensitive resin composition to obtain the desired pattern without residue. If the mass of component (A) is 60% by mass or less relative to the total mass of solids, the fineness of the cured film can be improved. In addition, the suitability of the production process during alkaline development is improved and photocurability can be sufficiently ensured.

[0020] Furthermore, when the photosensitive resin composition of the present invention is a composition fired at a high temperature exceeding 150°C, the content of component (A) is preferably 35 to 70% by mass relative to the total mass of solids, and more preferably 45 to 60% by mass when using cardo resin. When using other resins such as acrylic copolymers, it is preferably 35 to 55% by mass or less. When the content of component (A) is 35% by mass or more, even if metal oxide fine particles are included, they will dissolve during alkaline development and the desired pattern can be obtained without residue, and when the content of component (A) 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 photocurability can be sufficiently ensured.

[0021] The alkali-soluble resin (A) represented by general formula (1) of the present invention, which has a carboxyl group and a polymerizable unsaturated group in one molecule, is obtained by reacting a reaction product of an epoxy compound (a-1) having two epoxy groups in one molecule with an unsaturated group-containing monocarboxylic acid, with a dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), and a tetracarboxylic acid or its acid dianhydride (c).

[0022] [ka]

[0023] (In formula (1), R1, R 2、 R3 and R4 are independently a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group; R5 is a hydrogen atom or a methyl group; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; Y is a tetravalent carboxylic acid residue; and Z is independently a hydrogen atom or a substituent represented by general formula (2). However, at least one of the Zs must be a substituent represented by general formula (2), and n is an integer from 1 to 20.

[0024] [ka]

[0025] (However, W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0026] A method for producing an alkali-soluble resin represented by general formula (1), which has a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter also simply referred to as "alkali-soluble resin represented by general formula (1)") will be described in detail.

[0027] First, an epoxy compound (a-1) having two epoxy groups in one molecule, represented by general formula (3) (hereinafter also simply referred to as "epoxy compound (a-1) represented by general formula (3)") is reacted with an unsaturated group-containing monocarboxylic acid (for example, (meth)acrylic acid) to obtain epoxy (meth)acrylate.

[0028] [ka]

[0029] (In formula (3), R1, R 2、R3 and R4 are independently a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group, and X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond.

[0030] The epoxy compound (a-1) represented by general formula (3) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin.

[0031] Examples of bisphenols used as raw materials for epoxy compounds (a-1) include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, and bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane. Ropane, 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-dimeth Bis(4-hydroxyphenyl)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-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl) This includes 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, 3,3'-biphenol, etc.These may be used individually or in combination of two or more types.

[0032] Examples of the above-mentioned unsaturated group-containing monocarboxylic acid compounds include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with acid monoanhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride.

[0033] The reaction between the epoxy compound (a-1) represented by general formula (3) and (meth)acrylic acid can be carried out using known methods. For example, Japanese Patent Publication No. 4-355450 describes that a diol containing polymerizable unsaturated groups can be obtained by using about 2 moles of (meth)acrylic acid for 1 mole of epoxy compound having two epoxy groups. In the present invention, the compound obtained by the above reaction is a diol containing polymerizable unsaturated groups, and is a diol (d) containing polymerizable unsaturated groups represented by general formula (4) (hereinafter also simply referred to as "diol (d) represented by general formula (4)").

[0034] [ka]

[0035] (In formula (4), R1, R 2、 R3 and R4 are independently a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group; R5 is a hydrogen atom or a methyl group; and X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond.

[0036] In the synthesis of diol (d) represented by general formula (4), followed by the addition reaction of a polycarboxylic acid or its anhydride, and further reacting with a monofunctional epoxy compound having a polymerizable unsaturated group that reacts with a carboxyl group, the reaction is usually carried out in a solvent with a catalyst as needed.

[0037] Examples of solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling-point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone solvents such as cyclohexanone and diisobutyl ketone. There are no particular restrictions on the reaction conditions, such as the solvent and catalyst used, but it is preferable to use a solvent that does not contain hydroxyl groups and has a boiling point higher than the reaction temperature as the reaction solvent.

[0038] Furthermore, it is preferable to use a catalyst in the reaction between a carboxyl group and an epoxy group, and Japanese Patent Publication No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0039] Next, a diol (d) represented by general formula (4), obtained by the reaction of epoxy compound (a-1) represented by general formula (3) with (meth)acrylic acid, is reacted with a dicarboxylic acid or tricarboxylic acid or their acid anhydride (b), and a tetracarboxylic acid or its acid dianhydride (c) to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule, represented by general formula (1).

[0040] [ka]

[0041] (In formula (1), R1, R 2、R3 and R4 are independently a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group; R5 is a hydrogen atom or a methyl group; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; Y is a tetravalent carboxylic acid residue; and Z is independently a hydrogen atom or a substituent represented by general formula (2). However, at least one of the Zs must be a substituent represented by general formula (2), and n is an integer from 1 to 20.

[0042] [ka]

[0043] (In formula (2), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0044] The acid component used to synthesize the alkali-soluble resin represented by general formula (1) is a polyvalent acid component that can react with the hydroxyl group in the diol (d) molecule represented by general formula (4), and it is necessary to use a combination of a dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) and a tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the above acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, these carboxylic acid residues may contain bonds containing heteroatoms such as -O-, -S-, and carbonyl groups.

[0045] As the dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), chain-type hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or their acid monoanhydrides can be used.

[0046] Examples of acid monoanhydrides of chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids with any substituent introduced. Examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrotrimellitic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids with any substituent introduced. Furthermore, examples of acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid, and trimellitic acid, as well as acid monoanhydrides of dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced.

[0047] Among the acid monoanhydrides of dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, with succinic acid, itaconic acid, and tetrahydrophthalic acid being more preferred. Furthermore, in the case of dicarboxylic acids or tricarboxylic acids, it is preferable to use their acid monoanhydrides. The above-mentioned acid monoanhydrides of dicarboxylic acids or tricarboxylic acids may be used individually or in combination of two or more.

[0048] Furthermore, as the tetracarboxylic acid or its acid dianhydride (c), chain-type hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or their acid dianhydrides can be used.

[0049] Examples of chain-type hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain-type hydrocarbon tetracarboxylic acids to which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups have been introduced. Examples of the above alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and alicyclic tetracarboxylic acids to which substituents such as chain-type hydrocarbon groups and unsaturated hydrocarbon groups have been introduced. Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid.

[0050] Among tetracarboxylic acids or their acid dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenyl ethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenyl ethertetracarboxylic acid are more preferred. Furthermore, when using a tetracarboxylic acid or its acid dianhydride, it is preferable to use the acid dianhydride. Note that the above-mentioned tetracarboxylic acids or their acid dianhydrides may be used individually or in combination of two or more.

[0051] The reaction between the diol (d) represented by general formula (4) and the acid components (b) and (c) is not particularly limited, and known methods can be employed. For example, Japanese Patent Publication No. 9-325494 describes a method for reacting epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0052] Here, it is preferable to react the compound such that the terminal end of the compound becomes a carboxyl group, with the diol (d), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), tetracarboxylic acid or its acid dianhydride (c) represented by formula (4) in a molar ratio of (d):(b):(c) = 1:0.01 to 1.0:0.2 to 1.0.

[0053] For example, when using acid monoanhydride (b) and acid dianhydride (c), it is preferable to react them so that the molar ratio of the amount of acid component [(b) / 2+(c)] to the diol (d) represented by formula (4) [(d) / [(b) / 2+(c)]] is 0.5 to 1.0. Here, if the molar ratio is 1.0 or less, the content of the diol containing unreacted polymerizable unsaturated groups will not increase, thus improving the long-term stability of the alkali-soluble resin composition. On the other hand, if the molar ratio exceeds 0.5, the end of the alkali-soluble resin represented by formula (1) will not become an acid anhydride, so the increase in the content of unreacted acid dianhydride can be suppressed, thus improving the long-term stability of the alkali-soluble resin composition. Note that the molar ratios of each component (d), (b), and (c) can be arbitrarily changed within the above range in order to adjust the acid value and molecular weight of the alkali-soluble resin represented by formula (1).

[0054] Furthermore, the preferred range for the acid value of the alkali-soluble resin represented by general formula (1) is preferably 20 to 180 mgKOH / g, more preferably 40 mgKOH / g to 140 mgKOH / g, and even more preferably 80 mgKOH / g to 120 mgKOH / g. When the acid value is 20 mgKOH / g or higher, residue is less likely to remain during alkaline development, and when it is 180 mgKOH / g or lower, the penetration of the alkaline developer does not become too fast, thus suppressing peeling development. The acid value can be determined by titration with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0055] The weight-average molecular weight (Mw) of the alkali-soluble resin represented by general formula (1), measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation), is typically 1,000 to 100,000, preferably 2,000 to 20,000, and more preferably 2,000 to 6,000. When the weight-average molecular weight is 1,000 or higher, the decrease in pattern adhesion during alkaline development can be suppressed. Furthermore, when the weight-average molecular weight is less than 100,000, it is easier to adjust the solution viscosity of the photosensitive resin composition to a level suitable for coating, and alkaline development does not take too long.

[0056] The photosensitive resin composition (B) of the present invention contains a photopolymerizable monomer having at least two ethylenically unsaturated bonds. Component (B) improves the adhesion of the cured film and the solubility of the exposed areas in the alkaline developer, thereby improving the linear reproducibility of the cured product. However, in order to prevent the cured film from becoming brittle and to suppress the decrease in the acid value of the composition, thereby improving the solubility of the unexposed areas in the alkaline developer and further improving the linear reproducibility of the cured product, it is preferable that the amount of component (B) is not too large.

[0057] Here, if 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 component (B) is preferably 5 to 40% by mass with respect to the total mass of solids. If a cardo resin is used as component (A), the mass of component (B) is preferably 5 to 20% by mass with respect to the total mass of solids. Furthermore, if other acrylic copolymer resins, etc., are used as component (A), the mass of component (B) is preferably 10 to 35% by mass with respect to the total mass of solids.

[0058] Furthermore, if the photosensitive resin composition of the present invention is a composition that is fired at a high temperature exceeding 150°C, the mass of component (B) is preferably 10 to 40% by mass of the total mass of solids, and if a cardo resin is used as component (A), the mass of component (B) is preferably 10 to 35% by mass of the total mass of solids. If other acrylic copolymer resins are used as component (A), the mass of component (B) is preferably 20 to 40% by mass of the total mass of solids.

[0059] (B) By setting the mass of component (B) to 5 to 40% by mass relative to the total mass of solids, it becomes possible to design a photosensitive resin composition with desired properties, and for example, the linearity and fineness of the cured film obtained by curing the photosensitive resin composition of the present invention can be improved.

[0060] (B) Examples of photopolymerizable monomers having at least two ethylenically unsaturated bonds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra( This includes (meth)acrylic acid esters such as meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendritic polymers having a (meth)acryloyl group as a compound having an ethylenic double bond. These may be used individually or in combination of two or more.

[0061] Examples of dendritic polymers having a (meth)acryloyl group as compounds having an ethylenic double bond include dendritic polymers obtained by adding a polyvalent mercapto compound to a portion of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, there are dendritic polymers obtained by reacting the (meth)acryloyl group of a polyfunctional (meth)acrylate represented by general formula (5) with the thiol group of a polyvalent mercapto compound represented by general formula (6).

[0062] [ka]

[0063] (In formula (5), R6 is a hydrogen atom or a methyl group, and R7 is R9(OH) k This is the remaining portion after 1 of the k hydroxyl groups have been donated to the ester bond in the formula. Preferred R9(OH) k These are polyhydric alcohols based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or polyhydric alcohol ethers formed by the dehydration condensation of such polyhydric alcohols linked via ether bonds, or esters of these polyhydric alcohols or polyhydric alcohol ethers with hydroxy acids. k and l are independently integers between 2 and 20, and k ≥ l.

[0064] [ka]

[0065] (In formula (6), R8 is a single bond or a C1-C6 hydrocarbon group with 2-6 valent values, and p is 2 when R8 is a single bond, and an integer between 2 and 6 when R8 is a group with 2-6 valent values.)

[0066] Examples of polyfunctional (meth)acrylates represented by general formula (5) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, and propylene oxide-modified trimethylolpropane tri(meth)acrylate. Trimethylol ethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified Pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, epichlorohydrin-modified hexahydrophthalate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified trimethylolpropane This includes (meth)acrylic acid esters such as tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate (meth)acrylate, tris((meth)acryloxyethyl) isocyanurate, alkoxy-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. These compounds may be used individually or in combination of two or more.

[0067] Examples of polyvalent mercapto compounds represented by general formula (6) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bis-dimercaptoethanethiol, trimethylolpropanetri(mercaptoacetate), trimethylolpropanetri(mercaptopropionate), pentaerythritoltetra(mercaptoacetate), pentaerythritoltri(mercaptoacetate), pentaerythritoltetra(mercaptopropionate), dipentaerythritolhexa(mercaptoacetate), and dipentaerythritolhexa(mercaptopropionate). These compounds may be used individually or in combination of two or more.

[0068] Furthermore, polymerization inhibitors may be added as needed during the synthesis of the above-mentioned dendritic polymers. Examples of polymerization inhibitors include hydroquinone compounds and phenolic compounds. Specific examples include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, and 2,4,6-tri-tert-butylphenol (BHT).

[0069] The photosensitive resin composition of the present invention contains (C) an epoxy compound. The content of component (C) is preferably 8 to 24% by mass relative to the solid content. When the photosensitive resin composition contains a sufficient amount of component (C), the solvent resistance of the cured product can be sufficiently improved. However, in order to sufficiently improve the adhesion and linearity of the cured product, it is preferable that the amount of component (C) is not too high.

[0070] 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, it is preferable that the photosensitive resin composition contains a larger amount of component (C). In this case, the mass of component (C) is preferably 8 to 24% by mass relative to the solid content, and more preferably 12 to 24% by mass relative to the solid content.

[0071] Furthermore, when the photosensitive resin composition of the present invention is a composition that is fired at a high temperature exceeding 150°C, it is preferable that the photosensitive resin composition contains a smaller amount of component (C) because component (C) hardens sufficiently easily. In this case, the mass of component (C) is preferably 8 to 20% by mass relative to the solid content, and more preferably 8 to 18% by mass relative to the solid content.

[0072] (C) Examples of epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds, tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, and copolymers of methacrylic acid and glycidyl methacrylate (meth) This includes copolymers of monomers having (meth)acrylic groups containing glycidyl acrylate as a unit, alicyclic epoxy compounds represented by 3',4'-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate, polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton.

[0073] The epoxy equivalent of the epoxy compound in component (C) is preferably 100 to 300 g / eq, and more preferably 100 to 200 g / eq. Furthermore, the number-average molecular weight (Mn) of the epoxy compound in component (C) is preferably 100 to 5000. Note that these compounds may be used individually or in combination of two or more.

[0074] The epoxy equivalent of component (C) of the epoxy compound can be determined by dissolving the resin solution in dioxane, adding an acetic acid solution of tetraethylammonium bromide, and titrating with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). The number-average molecular weight (Mn) of component (C) of the epoxy compound can be determined in polystyrene equivalent using gel permeation chromatography (GPC) measurement (HLC-8220GPC, manufactured by Tosoh Corporation).

[0075] The photosensitive resin composition of the present invention preferably contains metal oxide fine particles as component (D). The metal oxide fine particles are preferably inorganic particles with an average particle size of 100 to 700 nm, and more preferably TiO2 with an average particle size of 100 to 700 nm.

[0076] The TiO2 particles described above are not particularly limited in terms of particle size or shape, as long as the formed cured film (coating) can exhibit light scattering functionality. The average particle size of the TiO2 particles is 100 to 700 nm, and more preferably 200 to 600 nm. If the average particle size of the TiO2 particles is 100 nm or more, the light scattering properties of the cured product can be sufficiently enhanced, and if the average particle size of the TiO2 particles is 700 nm or less, the adhesion and linearity of the cured product can be sufficiently enhanced.

[0077] The average particle size of the TiO2 can be determined using the cumulant method with the "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.), a particle size distribution analyzer that uses dynamic light scattering.

[0078] Furthermore, instead of TiO2 with an average particle size of 100 to 700 nm, component (D) may include metal oxide fine particles with a refractive index of 1.9 to 2.3. The particle size and shape of the metal oxide fine particles with a refractive index of 1.9 to 2.3 are not particularly limited, as long as the formed cured film (coating) can exhibit light scattering functionality.

[0079] Examples of metal oxide nanoparticles with refractive indices of 1.9 to 2.3 include ZnO and ZrO2. Generally, the higher the refractive index of a metal oxide, the higher its light scattering properties. However, if the light scattering properties are too strong, the transmittance of directional light decreases. The refractive index of the above metal oxide nanoparticles can be measured using an Abbe refractometer with light at a wavelength of 589 nm.

[0080] The average particle size of ZnO and ZrO2 is preferably 150 to 500 nm, and more preferably 150 to 400 nm. If the average particle size of the metal oxide is 150 nm or more, the light scattering properties of the cured film can be sufficiently enhanced, and if the average particle size of the metal oxide is 500 nm or less, the adhesion and linearity of the cured film can be sufficiently enhanced.

[0081] The average particle size of the above-mentioned metal oxide nanoparticles can be determined by the cumulant method using the "Particle Size Analyzer FPAR-1000" dynamic light scattering particle size distribution analyzer.

[0082] Component (D) can enhance the light scattering properties of the cured film. However, if the amount of component (D) in the photosensitive resin composition of the present invention is too large, the adhesion, linearity, fineness, and solvent resistance of the cured film will decrease, and the light transmittance of the transparent film will also decrease. For this reason, the mass of component (D) is preferably 1% by mass or more and 35% by mass or less of the total mass of solids.

[0083] Furthermore, if 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 component (D) is preferably 1% by mass or more and less than 35% by mass, more preferably 2% by mass or more and less than 25% by mass, and even more preferably 2% by mass or more and less than 20% by mass, based on the total mass of solids.

[0084] On the other hand, if 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 component (D) is preferably 1% by mass or more and less than 35% by mass, and more preferably 2% by mass or more and less than 25% by mass, based on the total mass of solids.

[0085] The photosensitive resin composition of the present invention comprises (E) a photopolymerization initiator.

[0086] Examples of component (E) include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; and benzoin such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. In ethers; biimidazole compounds such as 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazol, 2-trichloromethyl-5-(p-cyanostyryl)- Halomethyldiazole compounds such as 1,3,4-oxadiazole and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxyphenyl) Halomethyl-s-triazine compounds such as -4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine;O-acyloxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, and 1-(4-methylsulfanylphenyl)butane-1-one oxime-O-acetate; benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone These include sulfur compounds such as 2-methylthioxanthone and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used individually or in combination of two or more.

[0087] In particular, when a high-sensitivity photopolymerization initiator is required, such as when a large amount of metal oxide is added, when it is desired to reduce the amount of photopolymerization initiator added, or when a high-temperature heat curing process such as 150°C cannot be performed and more effective photocuring is desired, it is preferable to use O-acyloxime compounds (including ketoximes). Among these, the group of compounds represented by general formula (7) and general formula (8) can be applied as more highly sensitive photopolymerization initiators. Among these, when it is desired to perform photocuring more effectively in response to low-temperature curing, it is even more preferable to use an O-acyloxime photopolymerization initiator having a molar extinction coefficient at 365 nm of 10,000 L / mol·cm or more. In this invention, "photopolymerization initiator" is used to include sensitizers.

[0088] [ka]

[0089] (In formula (7), R 10 and R 11 each independently represent an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R 12 represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group 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 contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Further, the alkyl group may be a linear, branched, or cyclic alkyl group.)

[0090]

Chemical Structure

[0091] (In formula (8), R 13 and R 14 each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group or an alkylcycloalkyl group, or a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms. R 15 independently represents a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and a part of the -CH2- groups in the alkyl group or alkenyl group may be substituted with an -O- group. Further, a part of the hydrogen atoms in these R 13 to R 15 groups may be substituted with halogen atoms.)

[0092] Here, the mass of component (E) is preferably 0.1 to 30% by mass, and more preferably 1 to 25% by mass, relative to the total mass of components (A) and (B). When the mass of component (E) is 0.1% by mass or more relative to the total mass of components (A) and (B), it has an appropriate photopolymerization rate, so a decrease in sensitivity can be suppressed. Also, when the mass of component (E) is 30% by mass or less relative to the total mass of components (A) and (B), the sensitivity of the composition to exposure is not too high, so the line width can be faithfully reproduced for the mask and the pattern edges can be made sharp.

[0093] The photosensitive resin composition of the present invention contains (F) a solvent.

[0094] (F) Examples of solvents contained in the photosensitive resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, and propylene This includes glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing these, a homogeneous solution-like composition can be obtained. These solvents may be used individually or in combination of two or more to achieve the necessary properties such as applicability.

[0095] The content of component (F) varies depending on the target viscosity, but it is preferably 60 to 90% by mass in the photosensitive resin composition solution.

[0096] The photosensitive resin composition of the present invention may contain (G) an epoxy compound curing agent and / or curing accelerator. When the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150°C or lower, the curing of component (C) tends to be insufficient, so it is preferable that the photosensitive resin composition contains component (G) in order to sufficiently cure component (C).

[0097] Examples of curing agents for the epoxy compound component (G) include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamides, Lewis acid complex compounds, and the like. Polycarboxylic acid compounds are preferably used in the present invention.

[0098] Examples of polycarboxylic acid compounds include polycarboxylic acids, polycarboxylic acid anhydrides, and pyrolytic esters of polycarboxylic acids. A polycarboxylic acid is a compound having two or more carboxyl groups in one molecule, and examples include succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-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, and butane-1,2,3,4-tetracarboxylic acid. Examples of polycarboxylic acid anhydrides include acid anhydrides of the above compounds. These may be intermolecular acid anhydrides, but generally intramolecularly cyclized acid anhydrides are used. Examples of pyrolytic esters of polycarboxylic acids include t-butyl esters, 1-(alkyloxy)ethyl esters, and 1-(alkylsulfanyl)ethyl esters of the above compounds (wherein alkyl is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a branched or cyclic structure, and may be substituted with any substituent). In addition, polymers or copolymers having two or more carboxyl groups can be used as polycarboxylic acid compounds, and the carboxyl groups may be anhydrides or pyrolytic esters.

[0099] Furthermore, examples of the polymers or copolymers mentioned above include polymers or copolymers containing (meth)acrylic acid as a component, copolymers containing maleic anhydride as a component, and compounds obtained by reacting tetracarboxylic dianhydride with diamine or diol to open the ring of an acid anhydride. Of these, it is preferable to use phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and benzene-1,2,4-tricarboxylic acid anhydrides. When using polycarboxylic acid compounds as curing agents for epoxy compounds, the blending ratio should be such that the carboxyl groups of the polycarboxylic acid compound are 0.5 to 1.5 moles, more preferably 0.6 to 1.2 moles, per mole of epoxy groups of the epoxy compound.

[0100] As the curing accelerator for the epoxy compound (G), known compounds known as epoxy compound curing accelerators, curing catalysts, latent curing agents, etc., can be used. Examples of epoxy compound curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, etc. Among the above curing accelerators, 1,8-diazabicyclo[5.4.0]undeca-7-ene or 1,5-diazabicyclo[4.3.0]nona-5-ene or salts thereof are preferred.

[0101] The amount of curing accelerator added is preferably 0.05 parts by mass or more and 2 parts by mass or less per 100 parts by mass of epoxy compound. If the amount of curing accelerator is 0.05 parts by mass or more, the amount can be adjusted depending on the chemical resistance of the resin film pattern after heat curing. Furthermore, if the amount of curing accelerator is 2 parts by mass or less, the curing rate of the epoxy compound can be kept within an appropriate range.

[0102] 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 component (C) and component (G) is preferably 15% by mass or more and 35% by mass or less, and more preferably 20% by mass or more and 30% by mass or less, relative to the total mass of solids. When the total mass of component (C) and component (G) is 15% by mass or more relative to the total mass of solids, sufficient curability is ensured when cured at a low temperature of 150°C or lower. Furthermore, when the total mass of component (C) and component (G) is 35% by mass or less relative to the total mass of solids, curability can be improved without adversely affecting patternability, linearity, and solvent resistance during alkaline development.

[0103] If the photosensitive resin composition of the present invention is a composition that is fired at a high temperature of more than 150°C, component (G) may be omitted, and the total mass of component (C) and component (G) is preferably 8 to 25% by mass of the total mass of solids.

[0104] Next, a method for manufacturing multiple substrates with cured films according to the present invention will be described. The cured film (coating film) of the present invention can be formed by photolithography using the photosensitive resin composition of the present invention.

[0105] The present invention provides a method for manufacturing a substrate with a cured film by forming a light-scattering cured film pattern on the substrate, which involves applying a photosensitive resin composition containing inorganic particles with an average particle size of 100 to 700 nm onto the substrate, exposing it through a photomask, removing unexposed areas by development, and heating to form a predetermined cured film pattern.

[0106] The present invention provides a method for manufacturing a substrate with a cured film by forming a light-scattering cured film pattern on a substrate with a heat resistance temperature of 150°C or lower. This method involves applying the above-mentioned photosensitive resin composition to the substrate, exposing it through a photomask, removing unexposed areas by development, and heating it at 150°C or lower to form a predetermined cured film pattern.

[0107] The present invention provides a method for manufacturing a substrate with a cured film by forming a light-scattering cured film pattern on a substrate with a heat resistance temperature exceeding 150°C. This method involves applying the above-mentioned photosensitive resin composition to the substrate, exposing it through a photomask, removing unexposed areas by development, and heating it at a temperature exceeding 150°C to form a predetermined cured film pattern.

[0108] The method for applying the photosensitive resin composition of the present invention onto a substrate can be any known method, including the solution immersion method, the spray method, or methods using a roller coater, land coater, slit coater, or spinner machine. After applying the composition to the desired thickness using these methods, a film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating using an oven, hot plate, or the like. The heating temperature and time during pre-baking are appropriately selected depending on the solvent used, for example, at a temperature of 60 to 110°C (set so as not to exceed the heat resistance temperature of the substrate) for 1 to 3 minutes.

[0109] The exposure performed after pre-baking is carried out using an ultraviolet exposure apparatus, and by exposing the resist only to the parts corresponding to the pattern through a photomask, only the resist is exposed. The exposure apparatus and exposure irradiation conditions are appropriately selected, and exposure is performed using light sources such as ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and far-ultraviolet lamps to photocur the photosensitive resin composition in the coating film. Preferably, photocuring is performed by irradiating with a constant amount of light with a wavelength of 365 nm.

[0110] For exposure, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc., can be used, but the wavelength range of the radiation is preferably 250 to 450 nm. Suitable developers for this alkaline development include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be appropriately selected according to the characteristics of the resin layer, and surfactants may be added as needed. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using commercially available developers or ultrasonic cleaners. After alkaline development, the image is usually washed with water. As for development methods, shower development, spray development, dip development, paddle development, etc., can be applied.

[0111] Alkaline development after exposure is performed to remove the resist from the unexposed areas, and this development forms the desired pattern. Suitable developers for this alkaline development include, for example, aqueous solutions of alkali metal or alkaline earth metal carbonates, and aqueous solutions of alkali metal hydroxides. In particular, it is preferable to develop at a temperature of 23 to 28°C using a weakly alkaline aqueous solution containing 0.05 to 3.0% by mass of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, and fine images can be precisely formed using commercially available developing machines or ultrasonic cleaners.

[0112] When a light-scattering cured film pattern is formed on a substrate with a heat resistance temperature of 150°C or lower, it is preferable to perform heat treatment (post-bake) after development at a temperature of 80-140°C (set so as not to exceed the heat resistance temperature of the substrate) for 20-90 minutes, and more preferably at a temperature of 90-120°C for 30-60 minutes. The above post-bake is performed for purposes such as improving the adhesion between the patterned cured film and the substrate. This is done by heating with an oven, hot plate, etc., similar to pre-bake. The patterned cured film of the present invention is formed through the above steps of the photolithography method.

[0113] When a light-scattering cured film pattern is formed on a substrate with a heat resistance temperature exceeding 150°C, it is preferable to perform heat treatment (post-bake) after development at a temperature of 80-250°C (set so as not to exceed the heat resistance temperature of the substrate) for 20-90 minutes, and more preferably at a temperature of 180-230°C for 30-60 minutes. The above post-bake is performed for purposes such as improving the adhesion between the patterned cured film and the substrate. This is done by heating with an oven, hot plate, etc., similar to pre-bake. The patterned cured film of the present invention is formed through the above steps of the photolithography method.

[0114] By the above method, a cured film can be obtained obtained by curing a photosensitive resin composition containing TiO2 with an average particle size of 100 to 700 nm as component (D) as described above, and a substrate with a cured film having a transmittance of 70% or more in the visible light region, and when white light is irradiated perpendicularly to the substrate with the cured film, if the angle of directly transmitted light that travels in a straight line without scattering is taken as 0°, the intensity of scattered light at 60° is 20% or more of the intensity of scattered light at 5°. Therefore, it can be suitably used as a light scattering layer in a display device.

[0115] By the above method, a cured film can be obtained by curing a photosensitive resin composition containing a metal oxide (ZnO, ZrO2) with a refractive index of 1.9 to 2.3 as component (D) as described above, and a substrate with a cured film in which, when the angle at which the transmittance in the visible light region is 80% is set to 0°, the intensity of scattered light at 45° is 15% or more of the intensity of scattered light at 5°. Therefore, it can be suitably used as a light scattering layer in a display device. [Examples]

[0116] The embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto.

[0117] First, we will explain examples of the synthesis of alkali-soluble resins represented by general formula (1). Unless otherwise noted, the evaluation of the resins in these synthesis examples was performed as follows. For various measuring instruments, the manufacturer's name is omitted from the second instance onward when the same model was used. In addition, in Examples 1 and 2, the glass substrates used to prepare the cured film substrates for measurement were all glass substrates that had undergone the same treatment.

[0118] [Solid content concentration] The weight of 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)]. After heating at 160°C for 2 hours, the weight [W2 (g)] was obtained and calculated using the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0119] [Epoxy equivalent] The resin solution was dissolved in dioxane, then an acetic acid solution of tetraethylammonium bromide was added, and the result was obtained by titrating with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0120] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" to determine the result.

[0121] [Molecular weight] The molecular weight was measured using gel permeation chromatography (GPC) "HLC-8220GPC" (solvent: tetrahydrofuran, columns: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuperH-5000 (1) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was determined as a value converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0122] [Average particle size] The particle size distribution was determined using the cumulant method with the "Particle Size Analyzer FPAR-1000" dynamic light scattering particle size analyzer.

[0123] The abbreviations used in the synthesis examples are as follows: DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid SA: Succinic anhydride BPFE: Bisphenol fluorene type epoxy compound (reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane) BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride THPA: Tetrahydrophthalic anhydride PTMA: Pentaerythritol tetra (mercaptoacetate) DPHA: A mixture of dipentaerythritol pentaacrylate and hexaacrylate. TEAB: Tetraethylammonium bromide AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine BzDMA: Benzyldimethylamine PGMEA: Propylene glycol monomethyl ether acetate

[0124] [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 into a 500 ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 100-105°C for 20 hours to allow it to react. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask, and the mixture was stirred at 120-125°C for 6 hours to obtain polymerizable unsaturated group-containing alkali-soluble resin (A)-1. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (based on solid content) was 103 mg KOH / g, and the weight-average molecular weight (Mw) determined by GPC analysis was 3600.

[0125] [Synthesis Example 2] 300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the flask system was purged with nitrogen before being heated to 120°C. 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 which AIBN (10 g) was dissolved was added dropwise to this flask from a dropping funnel over 2 hours, and the mixture was stirred at 120°C for another 2 hours to obtain a copolymer solution.

[0126] Next, after replacing the flask system with air, AA (24.0 g (95% of glycidyl groups)), TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 120°C for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. Furthermore, SA (30.0 g (90% of the moles of AA added)) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution, and the mixture was reacted at 120°C for 4 hours to obtain polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A)-2. The solid content concentration of the resin solution was 41.7% by mass, the acid value (based on solid content) was 76 mgKOH / g, and the weight-average molecular weight (Mw) determined by GPC analysis was 5300.

[0127] [Synthesis Example 3] In a 1 L four-necked flask, PTMA (20 g, 0.19 mol mercapto groups), DPHA (212 g, 2.12 mol acrylic groups), PGMEA (58 g), HQ (0.1 g), and BzDMA (0.01 g) were added and reacted at 60°C for 12 hours to obtain dendritic polymer solution (B)-3 (solid content concentration: 80% by mass). The disappearance of thiol groups from the obtained dendritic polymer was confirmed by iodometry. The weight-average molecular weight (Mw) of the obtained dendritic polymer was 10,000.

[0128] The abbreviations shown in Tables 1, 2, 4, 5, 7, 8, 10, and 11 are as follows:

[0129] (Alkali-soluble resin containing polymerizable unsaturated groups) (A)-1: Resin solution obtained in Synthesis Example 1 above (solid content concentration 56.1% by mass) (A)-2: Resin solution obtained in Synthesis Example 2 above (solid content concentration 41.7% by mass)

[0130] (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 Toagosei Co., Ltd.) (B)-3: Dendritic polymer obtained in Synthesis Example 3 above

[0131] (Epoxy compound) (C)-1:3,4-Epoxycyclohexanecarboxylic acid (3',4'-epoxycyclohexyl)methyl (Celoxide 2021P (epoxy equivalent 135), manufactured by Daicel Corporation) (C)-2: 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 (epoxy equivalent 180), manufactured by Daicel Corporation) (C)-3: Butanetetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (Epolid GT401 (epoxy equivalent 220), manufactured by Daicel Corporation)

[0132] [Dispersion of metal oxides] (Titania dispersion) (D)-1: Titania dispersion (average particle size 50 nm), concentration 75% by mass, titania dispersion in propylene glycol monomethyl ether acetate solvent. (D)-2: Titania dispersion (average particle size 120 nm), concentration 75% by mass, titania dispersion in propylene glycol monomethyl ether acetate solvent. (D)-3: Titania dispersion (average particle size 270 nm), concentration 75% by mass, titania dispersion in propylene glycol monomethyl ether acetate solvent. (D)-4: Titania dispersion (average particle size 410 nm), concentration 75% by mass, titania dispersion in propylene glycol monomethyl ether acetate solvent. (D)-5: Titania dispersion (average particle size 620 nm), concentration 75% by mass, titania dispersion in propylene glycol monomethyl ether acetate solvent. (D)-6: Titania dispersion (average particle size 970 nm), concentration 75% by mass, titania dispersion in propylene glycol monomethyl ether acetate solvent.

[0133] (ZnO dispersion and ZrO2 dispersion) (D)-7: ZnO dispersion (average particle size 200 nm, refractive index 2.0), concentration 20% by mass, ZnO dispersion in 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 in propylene glycol monomethyl ether acetate solvent. (D)-9: ZrO2 dispersion (average particle size 170 nm, refractive index 2.2), concentration 20% by mass, ZrO2 dispersion in propylene glycol monomethyl ether acetate solvent. (D)-10: ZrO2 dispersion (average particle size 240 nm, refractive index 2.2), concentration 20% by mass, ZrO2 dispersion in propylene glycol monomethyl ether acetate solvent. (D)-11: TiO2 dispersion (average particle size 400 nm, refractive index 2.5), concentration 75% by mass, TiO2 dispersion in propylene glycol monomethyl ether acetate solvent. (D)-12: Al2O3 dispersion (average particle size 300 nm, refractive index 1.77), concentration 20% by mass, Al2O3 dispersion in propylene glycol monomethyl ether acetate solvent.

[0134] (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)

[0135] (solvent) (F)-1: Propylene glycol monomethyl ether acetate (PGMEA) (F)-2: Diethylene glycol ethyl methyl ether (EDM) (F)-3:3-Methoxy-3-methyl-1-butylacetate (MMBA) (F)-4:3-Methyl methoxypropionate (MMP) (F)-5: Cyclohexanone (ANON)

[0136] (Hardening agent and curing accelerator) (G)-1: Benzene 1,2,4-tricarboxylic acid-1,2-anhydride (G)-2: A PGMEA solution containing 2.0% by mass of 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU(R)), manufactured by Sunapro Co., Ltd.

[0137] (Other additives) (H)-1: Surfactant (Megafac F-447, manufactured by DIC Corporation; "Megafac" is a registered trademark of the company) (H)-2: Surfactant (DOWSIL SH3775, manufactured by Dow Corporation; DOWSIL 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 company) (H)-4: Coupling agent (3-glycidoxypropyltrimethoxysilane)

[0138] [Example 1] Photosensitive resin compositions using a titania dispersion as component (D) were prepared as Examples 1 to 16 and Comparative Examples 1 to 4. Their constituent components are shown in Tables 1 and 2. All values ​​in Tables 1 and 2 represent mass percent. Note that (B)-3 is the amount of dendritic polymer without solvent.

[0139] [Table 1]

[0140] [Table 2]

[0141] [evaluation] Using the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-4, substrates with cured films for evaluating development characteristics were prepared.

[0142] (Preparation of substrates with cured films for development characteristic evaluation) The photosensitive resin compositions shown in Tables 1 and 2 were pre-treated with a low-pressure mercury lamp at a wavelength of 254 nm and an illuminance of 1000 mJ / cm². 2A 125mm x 125mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate"), whose surface had been cleaned by irradiation with ultraviolet light, was coated using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A cured film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Next, a negative photomask with a line / space of 20 μm / 20 μm was placed over the cured film (coating) and the i-line irradiance was 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0143] Next, the exposed cured film (coating) was subjected to a 1 kgf / cm² treatment with a 0.04% potassium hydroxide solution at 25°C. 2 After developing for 20 seconds from the development time (break time = BT) when the pattern begins to appear, using a shower pressure of 5 kgf / cm², the development process is performed. 2 The cured film (coating) was then sprayed with water to remove the unexposed portion and form a cured film pattern on the glass substrate. The substrate was then fully cured (post-bake) using a hot air dryer at 90°C for 60 minutes to obtain substrates with cured films for evaluating development characteristics according to Examples 1 to 16 and Comparative Examples 1 to 4.

[0144] The following evaluations were performed using the cured film-coated substrate described above for evaluating development characteristics.

[0145] [Development characteristics evaluation] (Pattern adhesion) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable.

[0146] (Evaluation Criteria) ○: Not peeling off at all △: Partially peeled off ×: Mostly peeled off

[0147] (Pattern linearity) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable.

[0148] (Evaluation Criteria) ○: No jaggedness is observed in the pattern edges. △: Some jaggedness is observed in the pattern edges. ×: Jagged edges are visible in most of the pattern.

[0149] (Pattern resolution) (Evaluation method) The 10-50 μm mask patterns after final curing (post-bake) were observed under an optical microscope. A result of △ or higher was considered acceptable.

[0150] (Evaluation Criteria) ◎: A pattern of 10-15 μm is formed. ○: A pattern of 16-24 μm is formed. △: A pattern of 25-50 μm is formed. ×: No pattern has been formed.

[0151] Cured substrates for solvent resistance evaluation were prepared using the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-4.

[0152] (Preparation of substrates with cured films for solvent resistance evaluation) The photosensitive resin compositions shown in Tables 1 and 2 were applied to a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A cured film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Next, a negative-type photomask with a line / space of 20 μm / 20 μm was placed over the cured film (coating) and the i-line illuminance was 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0153] Next, the exposed cured film (coating) was subjected to a 1 kgf / cm² treatment with a 0.05% potassium hydroxide solution at 25°C. 2After developing with a shower pressure of 5 kgf / cm² for 60 seconds, the treatment is performed. 2 The cured film (coating) was then sprayed with water to remove the unexposed portion and form a cured film pattern on the glass substrate. The substrate was then fully cured (post-bake) using a hot air dryer at 90°C for 60 minutes to obtain substrates with cured films for solvent resistance evaluation according to Examples 1 to 16 and Comparative Examples 1 to 4.

[0154] The following evaluations were performed using the substrate with the cured film used for solvent resistance evaluation described above.

[0155] [Solvent resistance evaluation] (Evaluation method) The surface of the cured film (coating) fabricated on the glass substrate was rubbed back and forth 20 times continuously with a cloth soaked in PGMEA. A result of △ or higher was considered acceptable.

[0156] (Evaluation Criteria) ○: No dissolution is observed on the surface of the hardened film (coating), and there are no scratches. △: Dissolution is observed in a very small area of ​​the surface of the hardened film (coating), and there are also scratches in a very small area. ×: The surface of the hardened film (coating) has softened and is scratched in most areas.

[0157] [Evaluation of Transmittance] (Evaluation method) The transmittance in the visible light region (380nm to 780nm) of the above-mentioned cured film-coated substrate was measured using the UH4150 ultraviolet-visible-near-infrared spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd.). A result of △ or higher was considered acceptable.

[0158] (Evaluation Criteria) ○: Transmittance of 70% or higher △: Transmittance is between 60% and 70% ×: Transmittance less than 60%

[0159] [Evaluation of light scattering properties] The above-mentioned substrate with the cured film was irradiated perpendicularly with white light, and the transmitted and scattered light was measured using a goniophotometer "GP-1" (manufactured by Nikka Densoku Co., Ltd.). A score of △ or higher was considered acceptable.

[0160] (Evaluation Criteria) ○: Evaluate the intensity of scattered light at angles of 5° and 60°, with the angle of directly transmitted light traveling in a straight line being set to 0°, and select those where the light scattering intensity at 60° is more than 20% of the light scattering intensity at 5°. △: Evaluate the intensity of scattered light at angles of 5° and 60°, with the angle of directly transmitted light traveling in a straight line being set to 0°. The light scattering intensity at 60° is greater than 10% but less than or equal to 20% of the light scattering intensity at 5°. ×: Evaluate the intensity of scattered light at 5° and 60° angles, with the angle of directly transmitted light traveling in a straight line being set to 0°, and the light scattering intensity at 60° is 10% or less of the light scattering intensity at 5°.

[0161] Table 3 shows the results of evaluating the above items for substrates with cured films obtained by curing the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4.

[0162] [Table 3]

[0163] As is clear from the results of Examples 1 to 16 and Comparative Examples 1 to 4 above, it has been found that by using a photosensitive resin composition containing the alkali-soluble resin represented by the general formula (1) of the present invention and TiO2, it is possible to produce a cured film substrate that exhibits excellent light scattering properties and can form fine patterns.

[0164] [Example 2] Photosensitive resin compositions using a titania dispersion as component (D) were prepared as Examples 17-30 and Comparative Examples 5-9. Their compositional components are shown in Tables 4 and 5. All values ​​in Tables 4 and 5 represent mass percent. Note that (B)-3 is the amount of dendritic polymer without solvent.

[0165] [Table 4]

[0166] [Table 5]

[0167] [evaluation] Cured substrates for evaluating development characteristics were prepared using the photosensitive resin compositions of Examples 17-30 and Comparative Examples 5-9.

[0168] (Preparation of substrates with cured films for development characteristic evaluation) The photosensitive resin compositions shown in Tables 4 and 5 were applied to a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A cured film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Next, the exposure gap was adjusted to 100 μm, and a negative-type photomask of 10 to 50 μm (in 5 μm increments) was placed over the cured film (coating) with an i-line illuminance of 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0169] Next, the exposed cured film (coating) was subjected to a 1 kgf / cm² treatment with a 0.04% potassium hydroxide solution at 25°C. 2 After developing for 20 seconds from the development time (break time = BT) when the pattern begins to appear, using a shower pressure of 5 kgf / cm², the development process is performed. 2 The cured film (coating) was then sprayed with water to remove the unexposed portion and form a cured film pattern on the glass substrate. The substrate was then fully cured (post-bake) using a hot air dryer at 230°C for 30 minutes to obtain substrates with cured films for evaluating development characteristics according to Examples 17-30 and Comparative Examples 5-9.

[0170] The following evaluations were performed using the cured film-coated substrate described above for evaluating development characteristics.

[0171] [Development characteristics evaluation] (Pattern adhesion) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable.

[0172] (Evaluation Criteria) ○: Not peeling off at all △: Partially peeled off ×: Mostly peeled off

[0173] (Pattern linearity) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed under an optical microscope. A result of △ or higher was considered acceptable.

[0174] (Evaluation Criteria) ○: No jaggedness is observed in the pattern edges. △: Some jaggedness is observed in the pattern edges. ×: Jagged edges are visible in most of the pattern.

[0175] (Pattern resolution) (Evaluation method) The 10-50 μm mask patterns after final curing (post-bake) were observed under an optical microscope. A result of △ or higher was considered acceptable.

[0176] (Evaluation Criteria) ◎: A pattern of 10-15 μm is formed. ○: A pattern of 16-24 μm is formed. △: A pattern of 25-50 μm is formed. ×: No pattern has been formed.

[0177] [Evaluation of Transmittance] (Evaluation method) The transmittance in the visible light region (380nm to 780nm) of the substrate with the cured film was measured using the UV-Vis-Near-Infrared Spectrophotometer "UH4150". A result of ○ or higher was considered acceptable.

[0178] (Evaluation Criteria) ○: Transmittance of 70% or higher △: Transmittance is between 60% and 70% ×: Transmittance less than 60%

[0179] Using the photosensitive resin compositions of Examples 17-30 and Comparative Examples 5-9, substrates with cured films for light scattering evaluation were prepared.

[0180] (Preparation of substrates with cured films for light scattering evaluation) The photosensitive resin compositions shown in Tables 4 and 5 were applied to a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A cured film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Subsequently, without covering with a negative-type photomask, the i-line illuminance was 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0181] Next, the exposed cured film (coating) was subjected to a 1 kgf / cm² treatment with a 0.05% potassium hydroxide solution at 25°C. 2 After developing for 20 seconds from the development time (break time = BT) when the pattern begins to appear, using a shower pressure of 5 kgf / cm², the development process is performed. 2 The cured film (coating) was then sprayed with water to remove the unexposed portion and form a cured film pattern on the glass substrate. The substrate was then fully cured (post-bake) using a hot air dryer at 230°C for 30 minutes to obtain substrates with cured films for light scattering evaluation according to Examples 17-30 and Comparative Examples 5-9.

[0182] The following evaluations were performed using the cured film-coated substrate described above for light scattering evaluation.

[0183] (Evaluation method) The above-mentioned substrate with the cured film was irradiated perpendicularly with white light, and the transmitted and scattered light was measured using a goniophotometer "GP-1". A result of △ or higher was considered acceptable.

[0184] (Evaluation Criteria) ○: Evaluate the intensity of scattered light at angles of 5° and 60°, with the angle of directly transmitted light traveling in a straight line being set to 0°, and select those where the light scattering intensity at 60° is more than 20% of the light scattering intensity at 5°. △: Evaluate the intensity of scattered light at angles of 5° and 60°, with the angle of directly transmitted light traveling in a straight line being set to 0°. The light scattering intensity at 60° is greater than 10% but less than or equal to 20% of the light scattering intensity at 5°. ×: Evaluate the intensity of scattered light at 5° and 60° angles, with the angle of directly transmitted light traveling in a straight line being set to 0°, and the light scattering intensity at 60° is 10% or less of the light scattering intensity at 5°.

[0185] Table 6 shows the results of evaluating the above items for substrates with cured films obtained by curing the photosensitive resin compositions of Examples 17-30 and Comparative Examples 5-9.

[0186] [Table 6]

[0187] As is clear from the results of Examples 17-30 and Comparative Examples 5-9 above, it has been found that by using a photosensitive resin composition containing the alkali-soluble resin represented by formula (1) of the present invention and TiO2, it is possible to produce a cured film substrate that exhibits excellent light scattering properties and can form fine patterns.

[0188] [Example 3] Photosensitive resin compositions using ZnO dispersions and ZrO2 dispersions as component (D) were prepared as Examples 31-45 and Comparative Examples 10-12. Their compositional components are shown in Tables 7 and 8. All values ​​in Tables 7 and 8 represent mass percent. Note that (B)-3 is the amount of dendritic polymer without solvent.

[0189] [Table 7]

[0190] [Table 8]

[0191] [evaluation] Cured substrates for evaluating development characteristics were prepared using the photosensitive resin compositions of Examples 31-45 and Comparative Examples 10-12.

[0192] (Preparation of substrates with cured films for development characteristic evaluation) The photosensitive resin compositions shown in Tables 7 and 8 were applied to a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A cured film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Next, a negative-type photomask with a line / space of 20 μm / 20 μm was placed over the cured film (coating) and the i-line illuminance was 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0193] Next, the exposed cured film (coating) was subjected to a 1 kgf / cm² treatment with a 0.04% potassium hydroxide solution at 25°C. 2 After developing for 20 seconds from the development time (break time = BT) when the pattern begins to appear, using a shower pressure of 5 kgf / cm², the development process is performed. 2 The cured film (coating) was then sprayed with water to remove the unexposed portion and form a cured film pattern on the glass substrate. The substrate was then fully cured (post-bake) at 90°C for 60 minutes using a hot air dryer to obtain substrates with cured films for evaluating the development characteristics of Examples 31-45 and Comparative Examples 10-12.

[0194] The following evaluations were performed using the cured film-coated substrate described above for evaluating development characteristics.

[0195] [Development characteristics evaluation] (Pattern adhesion) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable.

[0196] (Evaluation Criteria) ○: Not peeling off at all △: Partially peeled off ×: Mostly peeled off

[0197] (Pattern linearity) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable.

[0198] (Evaluation Criteria) ○: No jaggedness is observed in the pattern edges. △: Some jaggedness is observed in the pattern edges. ×: Jagged edges are visible in most of the pattern.

[0199] (Pattern resolution) (Evaluation method) The 10-50 μm mask patterns after final curing (post-bake) were observed under an optical microscope. A result of △ or higher was considered acceptable.

[0200] (Evaluation Criteria) ◎: A pattern of 10-15 μm is formed. ○: A pattern of 16-24 μm is formed. △: A pattern of 25-50 μm is formed. ×: No pattern has been formed.

[0201] Cured substrates for solvent resistance evaluation were prepared using the photosensitive resin compositions of Examples 31-45 and Comparative Examples 10-12.

[0202] (Preparation of substrates with cured films for solvent resistance evaluation) The photosensitive resin compositions shown in Tables 7 and 8 were applied to a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A cured film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Next, a negative-type photomask with a line / space of 20 μm / 20 μm was placed over the cured film (coating) and the i-line illuminance was 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0203] Next, the exposed cured film (coating film) was developed for 60 seconds at a shower pressure of 1 kgf / cm² with a 0.05% potassium hydroxide solution at 25°C, and then spray rinsed at 5 kgf / cm² to remove the unexposed portion of the cured film (coating film) and form a cured film pattern on the glass substrate. The film was then post baked at 90°C for 60 minutes using a hot air dryer to obtain substrates with cured films for solvent resistance evaluation according to Examples 31 to 45 and Comparative Examples 10 to 12. 2 of shower pressure for 60 seconds, and then spray rinsed at 5 kgf / cm² 2 to remove the unexposed portion of the cured film (coating film) and form a cured film pattern on the glass substrate. The film was then post baked at 90°C for 60 minutes using a hot air dryer to obtain substrates with cured films for solvent resistance evaluation according to Examples 31 to 45 and Comparative Examples 10 to 12.

[0204] The following evaluations were performed using the substrates with cured films for solvent resistance evaluation.

[0205] [Solvent Resistance Evaluation] (Evaluation Method) The surface of the cured film (coating film) formed on the glass substrate was continuously rubbed 20 times back and forth with a wipe soaked in PGMEA. A result of △ or better was considered a pass.

[0206] (Evaluation Criteria) ○: No dissolution was observed on the surface of the cured film (coating film), and no scratches were found. △: Dissolution was observed in a very small part of the surface of the cured film (coating film), and a very small part was scratched. ×: The surface of the cured film (coating film) was softened and mostly scratched.

[0207] [Transmittance Evaluation] (Evaluation Method) Using an ultraviolet-visible-near infrared spectrophotometer "UH4150", the transmittance of the substrate with the cured film in the visible light range (380 nm to 780 nm) was measured. A result of △ or better was considered a pass.

[0208] (Evaluation Criteria) ○: Transmittance is 80% or more. △: Transmittance is 70% or more and less than 80%. ×: Transmittance is less than 70%.

[0209] [Light Scattering Evaluation] The above-mentioned substrate with the cured film was irradiated perpendicularly with white light, and the transmitted and scattered light was measured using a goniophotometer "GP-1". A result of △ or higher was considered acceptable.

[0210] (Evaluation Criteria) ○: Evaluate the intensity of scattered light at angles of 5° and 45°, with the angle of directly transmitted light traveling in a straight line being set to 0°, and select those where the light scattering intensity at 45° is more than 15% of the light scattering intensity at 5°. △: Evaluate the intensity of scattered light at angles of 5° and 45°, with the angle of directly transmitted light traveling in a straight line being set to 0°. The light scattering intensity at 45° is greater than 10% but less than or equal to 15% of the light scattering intensity at 5°. ×: Evaluate the intensity of scattered light at angles of 5° and 45°, with the angle of directly transmitted light traveling in a straight line being set to 0°, and the light scattering intensity at 45° is 10% or less of the light scattering intensity at 5°.

[0211] Table 9 shows the results of evaluating the above items for substrates with cured films obtained by curing the photosensitive resin compositions of Examples 31 to 45 and Comparative Examples 10 to 12.

[0212] [Table 9]

[0213] As is clear from the results of Examples 31-45 and Comparative Examples 10-12, it has been found that by using the alkali-soluble resin containing an unsaturated group of the general formula (1) of the present invention and a photosensitive resin composition containing a metal oxide (ZnO, ZrO2), it is possible to produce a cured film that exhibits excellent light scattering properties and can form fine patterns.

[0214] [Example 4] Photosensitive resin compositions using ZnO dispersions and ZrO2 dispersions as component (D) were prepared as Examples 46-60 and Comparative Examples 13-15. Their compositional components are shown in Tables 10 and 11. All values ​​in Tables 10 and 11 represent mass percent. Note that (B)-3 is the amount of dendritic polymer without solvent.

[0215]

Table 10

[0216]

Table 11

[0217] [Evaluation] Substrates with cured films for developing property evaluation were prepared using the photosensitive resin compositions of Examples 46 to 60 and Comparative Examples 13 to 15.

[0218] (Preparation of Substrates with Cured Films for Developing Property Evaluation) The photosensitive resin compositions shown in Tables 10 and 11 were applied onto a glass substrate using a spin coater so that the film thickness after heat curing treatment would be 2.0 μm, and pre-baked at 90 °C for 2 minutes using a hot plate to form a cured film (coating film). Next, the exposure gap was adjusted to 100 μm, a negative-type photomask of 10 to 50 μm (in 5-μm increments) was placed over the above-mentioned cured film (coating film), and ultraviolet light of 50 mJ / cm 2 was irradiated using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm 2 to perform a photocuring reaction.

[0219] Next, the exposed cured film (coating film) was developed at a shower pressure of 1 kgf / cm 2 with a 0.04% potassium hydroxide solution at 25 °C for 20 seconds starting from the development time (break time = BT) when the pattern began to appear, and then spray rinsed with water at 5 kgf / cm 2 to remove the unexposed portion of the above-mentioned cured film (coating film) and form a cured film pattern on the glass substrate. Then, it was post-cured (post baked) at 230 °C for 30 minutes using a hot air dryer to obtain substrates with cured films for developing property evaluation according to Examples 46 to 60 and Comparative Examples 13 to 15.

[0220] The following evaluations were performed using the substrates with cured films for developing property evaluation.

[0221] [Development characteristics evaluation] (Pattern adhesion) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable.

[0222] (Evaluation Criteria) ○: Not peeling off at all △: Partially peeled off ×: Mostly peeled off

[0223] (Pattern linearity) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed under an optical microscope. A result of △ or higher was considered acceptable.

[0224] (Evaluation Criteria) ○: No jaggedness is observed in the pattern edges. △: Some jaggedness is observed in the pattern edges. ×: Jagged edges are visible in most of the pattern.

[0225] (Pattern resolution) (Evaluation method) The 10-50 μm mask patterns after final curing (post-bake) were observed under an optical microscope. A result of △ or higher was considered acceptable.

[0226] (Evaluation Criteria) ◎: A pattern of 10-15 μm is formed. ○: A pattern of 16-24 μm is formed. △: A pattern of 25-50 μm is formed. ×: No pattern has been formed.

[0227] [Evaluation of Transmittance] (Evaluation method) The transmittance in the visible light region (380nm to 780nm) of the substrate with the cured film was measured using the UV-Vis-Near-Infrared Spectrophotometer "UH4150". A result of △ or higher was considered acceptable.

[0228] (Evaluation Criteria) ○: Transmittance of 80% or higher △: Transmittance is between 70% and 80% ×: Transmittance less than 70%

[0229] Using the photosensitive resin compositions of Examples 46-60 and Comparative Examples 13-15, substrates with cured films for light scattering evaluation were prepared.

[0230] (Preparation of substrates with cured films for light scattering evaluation) The photosensitive resin compositions shown in Tables 10 and 11 were applied to a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. A cured film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Subsequently, without covering with a negative-type photomask, the i-line illuminance was 30 mW / cm². 2 50 mJ / cm² with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0231] Next, the exposed cured film (coating) was subjected to a 1 kgf / cm² treatment with a 0.05% potassium hydroxide solution at 25°C. 2 After developing for 20 seconds from the development time (break time = BT) when the pattern begins to appear, using a shower pressure of 5 kgf / cm², the development process is performed. 2 The cured film (coating) was then sprayed with water to remove the unexposed portion and form a cured film pattern on the glass substrate. The substrate was then fully cured (post-bake) using a hot air dryer at 230°C for 30 minutes to obtain substrates with cured films for light scattering evaluation according to Examples 46-60 and Comparative Examples 13-15.

[0232] The following evaluations were performed using the cured film-coated substrate described above for light scattering evaluation.

[0233] [Evaluation of light scattering properties] (Evaluation method) For the solvent resistance evaluation, a cured film (coating) similar to the one prepared was irradiated perpendicularly with white light, and the transmitted and scattered light was measured using a goniophotometer. A result of △ or higher was considered acceptable.

[0234] (Evaluation Criteria) ○: Evaluate the intensity of scattered light at angles of 5° and 45°, with the angle of directly transmitted light traveling in a straight line being set to 0°, and select those where the light scattering intensity at 45° is more than 15% of the light scattering intensity at 5°. △: Evaluate the intensity of scattered light at angles of 5° and 45°, with the angle of directly transmitted light traveling in a straight line being set to 0°. The light scattering intensity at 45° is greater than 10% but less than or equal to 15% of the light scattering intensity at 5°. ×: Evaluate the intensity of scattered light at angles of 5° and 45°, with the angle of directly transmitted light traveling in a straight line being set to 0°, and the light scattering intensity at 45° is 10% or less of the light scattering intensity at 5°.

[0235] Table 12 shows the results of evaluating the above items for substrates with cured films obtained by curing the photosensitive resin compositions of Examples 46-60 and Comparative Examples 13-15.

[0236] [Table 12]

[0237] As is clear from the results of Examples 46-60 and Comparative Examples 13-15, it has been found that by using the alkali-soluble resin containing an unsaturated group of the general formula (1) of the present invention and a photosensitive resin composition containing a metal oxide (ZnO, ZrO2), it is possible to produce a cured film that exhibits excellent light scattering properties and can form fine patterns. [Industrial applicability]

[0238] The present invention provides a method for manufacturing a cured film-coated substrate, which allows for the production of a cured film-coated substrate with excellent light scattering properties. Therefore, it is useful for applications such as display devices. Specifically, since the pattern can be formed using photolithography, it has the advantage of being usable in existing photolithography processes. Furthermore, because film strength can be obtained even at low temperatures, it is suitable for the production of touch panels and color filters using substrates with low heat resistance.

Claims

1. A method for manufacturing a substrate with a cured film by forming a light-scattering cured film pattern on a substrate, ZnO particles or ZrO₂ particles with an average particle size of 100 to 700 nm, An alkali-soluble resin containing an unsaturated group represented by general formula (1), A method for manufacturing a substrate with a cured film, comprising applying a photosensitive resin composition containing a certain substance onto a substrate, exposing it through a photomask, removing unexposed areas by development, and heating to form a predetermined cured film pattern. 【Chemistry 1】 (In formula (1), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ５ is a hydrogen atom or a methyl group, X is -CO-, -SO ２ -, -C(CF ３ )([[]] ２ -, -Si(CH ３ )([[]] ２ -, -CH ２ -, -C(CH ３ )([[]] ２ -, -O-, a fluorene-9,9-diyl group or a direct bond, Y is a tetravalent carboxylic acid residue, and Z is each independently a hydrogen atom or a substituent represented by general formula (2). However, one or more of Z are substituents represented by general formula (2), and n is an integer of 1 to 20.)​​​ 【Chemistry 2】 (In formula (2), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

2. A substrate with a cured film manufactured by the method of claim 1, wherein the transmittance in the visible light region is 80% or more, and the intensity of scattered light at 45° when the angle of directly transmitted light that travels in a straight line is taken as 0° when white light is irradiated perpendicularly to the substrate with the cured film is 15% or more of the intensity of scattered light when the angle of directly transmitted light is taken as 5°.

3. A photosensitive resin composition used in manufacturing a substrate with a cured film according to claim 2, (A) An alkali-soluble resin containing an unsaturated group represented by general formula (1), (B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) Epoxy compound and (D) ZnO particles or ZrO2 particles, (E) Photopolymerization initiator, (F) Solvent and Includes, A photosensitive resin composition in which the refractive index of component (D) is 1.9 to 2.

3.

4. A photosensitive resin composition according to claim 3, A photosensitive resin composition in which the mass of component (A) is 20 to 70% by mass of the total mass of solids, the mass of component (B) is 5 to 40% by mass of the total mass of solids, and the mass of component (C) is 8 to 24% by mass of the total mass of solids.

5. A photosensitive resin composition according to claim 3 or 4, A photosensitive resin composition comprising (G) a curing agent and / or curing accelerator for an epoxy compound, wherein the total mass of component (C) and component (G) is 15 to 35% by mass of the total mass of solids.

6. The photosensitive resin composition according to any one of claims 3 to 5, wherein the epoxy equivalent of the epoxy compound of component (C) is 100 to 300 g / eq.

7. The photosensitive resin composition according to claim 5, wherein the curing agent and / or curing accelerator of component (G) comprises an acid anhydride.

8. A cured film obtained by curing the photosensitive resin composition according to any one of claims 3 to 7.

9. A display device having the cured film described in claim 8 or the substrate with the cured film described in claim 2.

10. A method for manufacturing a substrate with a cured film, comprising forming a light-scattering cured film pattern on a substrate with a heat resistance temperature of 150°C or lower, wherein the photosensitive resin composition according to any one of claims 3 to 7 is applied to the substrate, exposed through a photomask, unexposed areas are removed by development, and a predetermined cured film pattern is formed by heating at 150°C or lower.

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