KR20240064539A - Photosensitive resin composition for black resist, light-shielding film cured thereof, color filter and touch panel having that film, and display device having them - Google Patents

Abstract

[Problem] To provide a photosensitive resin composition for black resist that can obtain a cured film with high light-shielding properties and reduced reflectance on both the glass surface side and the film surface side.
[Solution] Contains (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a light-shielding component, (E) silica particles, (F) a dispersant, and (G) a solvent. , (F) the dispersant has an acid value and an amine value of 10 to 80 mgKOH/g or less, (E) the mass ratio of the (F) dispersant to the silica particles is 0.02 to 0.60, and the (G) solvent is propylene glycol monomethyl ether. A photosensitive resin composition for black resists containing acetate and a solvent (excluding the solvent represented by General Formula (1)) whose vapor pressure at 20°C is less than 250 Pa.
RO-(CH ₂ CH ₂ O)nR···(1)
(R represents an alkyl group or aryl group that may have a substituent, and n is an integer of 2 to 5.)

Description

Photosensitive resin composition for black resist, light shielding film, color filter, touch panel and display device

The present invention relates to a photosensitive resin composition for black resist, a light-shielding film formed by curing the same, a color filter and a touch panel having the light-shielding film, and a display device having the color filter or the touch panel.

Recently, with the development of mobile terminals, the number of display devices having a touch panel or liquid crystal panel, etc., used outdoors or in vehicles has been increasing. In the display device, a light-shielding film is installed on the outer frame of the touch panel to block light leakage from the periphery of the liquid crystal panel on the back, and on the liquid crystal panel, for suppressing light leakage from the screen during black display, and adjacent to each other. A light shielding film (black matrix) is installed to suppress color mixing between color resists.

The black matrix is required to have high light blocking properties and low reflectance. For example, Patent Document 1 describes that by using hydrophobic silica fine particles dispersed with a specific urethane-based dispersant, the high light-shielding properties and low reflectivity of the black matrix can be achieved at both times. Additionally, in Patent Document 1, when evaluating low reflectivity, the reflectance from the glass surface of a glass substrate coated with a black photosensitive resin composition and cured is measured.

Japanese Patent Publication No. 2015-161815

As described in Patent Document 1, various photosensitive resin compositions for obtaining a cured film that has high light-shielding properties and reduced reflectance from a glass surface are being studied. On the other hand, according to the knowledge of the present inventors, there is a demand for cured films such as black matrix to reduce not only the reflectance from the glass surface but also the reflectance from the film surface side.

The present invention has been made in view of these points, and provides a photosensitive resin composition for black resist that can obtain a cured film with high light-shielding properties and reduced reflectance on both the glass surface side and the film surface side, a light-shielding film formed by curing the same, and a color filter having the light-shielding film. and a touch panel, and a display device having the color filter or the touch panel.

One form of the present invention for solving the above problems relates to the photosensitive resin composition for black resist described in [1] to [9] below.

[1] (A) a photosensitive resin containing an unsaturated group,

(B) a photopolymerizable compound having at least two or more unsaturated bonds,

(C) a photopolymerization initiator,

(D) at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials,

(E) silica particles,

(F) a dispersant,

(G) contains a solvent;

The (F) dispersant has an acid value and an amine value, and both the acid value and the amine value are 10 mgKOH/g or more and 80 mgKOH/g or less,

The ratio (mF/mE) of the total mass (mF) of the (F) dispersant to the total mass (mE) of the (E) silica particles is 0.02 or more and 0.60 or less,

The solvent (G) is a first solvent that is propylene glycol monomethyl ether acetate, and a second solvent that has a vapor pressure of less than 250 Pa at 20°C (the solvent represented by the following general formula (1) is excluded from the second solvent). A photosensitive resin composition for a black resist, comprising:

RO-(CH ₂ CH ₂ O)nR···(1)

(In General Formula (1), R independently represents an alkyl group or aryl group that may have a substituent, and n is an integer of 2 to 5.)

[2] The photosensitive resin containing an unsaturated group (A) is a polybasic carboxylic acid obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (2) and (meth)acrylic acid. Or the photosensitive resin composition for black resist according to [1], which is a photosensitive resin containing an unsaturated group obtained by further reacting with its anhydride.

(In General Formula (2), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ₂ -, - C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9- represented by general formula (3) d is a diary group or a single bond, and l is an integer between 0 and 10.)

[3] The photosensitive resin composition for black resist according to [1] or [2], wherein the (F) dispersant is a polymer compound having an alkylammonium salt structure.

[4] The solvent (G) includes the 3-1 solvent whose relative dielectric constant at 23°C is 10.0 or more and 30.0 or less (however, excluding the second solvent), or

The second solvent is the black described in [1] to [3], comprising a solvent having a relative dielectric constant at 23°C of less than 10.0 and a 3-2 solvent having a relative dielectric constant at 23°C of 10.0 or more and 30.0 or less. Photosensitive resin composition for resist.

[5] The photosensitive resin composition for black resist according to [4], wherein the solvent (G) contains the solvent 3-1.

[6] The photosensitive resin composition for black resist according to any one of [1] to [5], wherein the (E) silica particles have an average particle diameter of 1 nm or more and 100 nm or less.

[7] Among [1] to [6], wherein the ratio (mE/mD) of the total mass (mE) of the (E) silica particles to the total mass (mD) of the (D) light-shielding component is 0.01 or more and 0.20 or less. The photosensitive resin composition for black resist according to any one of the above.

[8] The photosensitive resin composition for black resist according to any one of [1] to [7], wherein the second solvent is a solvent having a vapor pressure of less than 100 Pa at 20°C.

[9] The second solvent is at least one selected from the group consisting of 3-methoxy-3-methyl-1-butylacetate, 3-methoxy-3-methyl-1-butanol, and propylene glycol diacetate. The photosensitive resin composition according to any one of [1] to [8], containing a solvent.

[10] The photosensitive resin composition for black resist according to any one of [1] to [9], wherein a light-shielding film having a reflectance of 6.5% or less on the film surface side can be obtained by curing the photosensitive resin composition for black resist.

[11] The photosensitive resin composition for black resist according to any one of [1] to [10], wherein a light-shielding film having a reflectance of 5.5% or less on the film surface side can be obtained by curing the photosensitive resin composition for black resist.

Another form of the present invention for solving the above problems relates to the light-shielding film described in [12] below.

[12] A light-shielding film formed by curing the photosensitive resin composition for black resist according to any one of [1] to [11].

Another form of the present invention for solving the above problems relates to a color filter, a touch panel, and a display device as described in [13] to [16] below.

[13] A color filter having the light-shielding film described in [12] as a black matrix.

[14] A touch panel having the light-shielding film described in [12].

[15] A display device having the color filter described in [13].

[16] A display device having the touch panel described in [14].

According to the present invention, a photosensitive resin composition for black resist capable of obtaining a cured film with high light-shielding properties and reduced reflectance on both the glass surface side and the film surface side, a light-shielding film formed by curing the same, a color filter and a touch panel having the light-shielding film, and the above-described light-shielding film. A display device having a color filter or a touch panel is provided.

Hereinafter, the present invention will be described in detail. The photosensitive resin composition for black resist (hereinafter also referred to as “photosensitive resin composition”) of the present invention includes (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable compound having at least two or more unsaturated bonds, and (C) ) A photopolymerization initiator, (D) one type of light-shielding component that is a black pigment, a color mixing pigment, or a light-shielding material, (E) silica particles, (F) a dispersant, and (G) a solvent.

In the present invention, the (F) dispersant has an acid value and an amine value, and both the acid value and the amine value are 10 mgKOH/g or more and 80 mgKOH/g or less. Additionally, the ratio (mF/mE) of the total mass (mF) of the (F) dispersant to the total mass (mE) of the (E) silica particles is 0.02 or more and 0.60 or less. And (G) the solvent is a first solvent which is propylene glycol monomethyl ether acetate, and a second solvent whose vapor pressure at 20°C is less than 250 Pa (the solvent represented by the following general formula (1) is excluded from the second solvent). Includes.

RO-(CH ₂ CH ₂ O)nR···(1)

In General Formula (1), R independently represents an alkyl group or an aryl group which may have a substituent, and n is an integer of 2 to 5.

Hereinafter, components (A) to (G) will be explained.

1. (A) Ingredient

(A) Component is a photosensitive resin containing an unsaturated group. Component (A) preferably contains a polymerizable unsaturated group and an acidic group for developing alkali solubility in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxyl group. There is no particular limitation as long as it is the above resin, and it can be used widely.

Examples of the photosensitive resin containing the unsaturated group include reacting an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth)acrylic acid, and reacting the obtained compound having a hydroxy group with a polybasic carboxylic acid or its anhydride. This includes epoxy (meth)acrylate acid adducts obtained by An epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin, or an equivalent thereof. In addition, “(meth)acrylic acid” is a general term for acrylic acid and methacrylic acid, and means one or both of them.

(A) The component is preferably a bisphenol-type epoxy compound represented by the following general formula (2).

In general formula (2), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-di represented by general formula (3) It is a single bond or a single bond, and l is an integer between 0 and 10.

The bisphenol-type epoxy compound represented by general formula (2) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols and epichlorohydrin. Since this reaction usually involves oligomerization of the diglycidyl ether compound, the bisphenol-type epoxy compound represented by general formula (2) contains an epoxy compound containing two or more bisphenol skeletons.

Examples of bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, and bis(4-hydroxy-3,5-dichlorophenyl). ) Ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hyde) Roxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4- Hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane , bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2 , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy- 3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, Bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9 ,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3 -Fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9 ,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol , 3,3'-biphenol, etc. Among these, bisphenols having a fluorene-9,9-diyl group are preferable.

In addition, examples of the acid monoanhydride of (a) dicarboxylic acid or tricarboxylic acid that is reacted with the hydroxy group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include chain hydrocarbon dicarboxylic acid. Included are acid monoanhydrides of boxylic acids or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids. Examples of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, and oxoglucolic acid. Taric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., and dicarboxylic acids or tricarboxylic acids thereof with arbitrary substituents introduced are included. Examples of alicyclic dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, etc., and optional substituents. These dicarboxylic acids or tricarboxylic acids introduced are included. Examples of aromatic dicarboxylic acids or tricarboxylic acids include phthalic acid, isophthalic acid, trimellitic acid, etc., and dicarboxylic acids or tricarboxylic acids thereof into which arbitrary substituents have been introduced. These dicarboxylic acids or tricarboxylic acids are preferably acid monoanhydrides.

In addition, examples of the acid dianhydride of (b) tetracarboxylic acid to be reacted with the epoxy (meth)acrylate include acid dianhydride of chain hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, or aromatic acid dianhydride of tetracarboxylic acid. The acid dianhydride of tetracarboxylic acid is used. Examples of acid dianhydrides of chain hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., and tetracarboxylic acids into which arbitrary substituents have been introduced. . Examples of acid dianhydrides of alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid. However, these tetracarboxylic acids to which any substituent has been introduced are included. Examples of acid dianhydrides of aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, and tetracarboxylic acids having arbitrary substituents introduced thereto. Contains boxylic acids. These tetracarboxylic acids are preferably acid dianhydrides.

The molar ratio (a)/(b) of (a) acid monoanhydride of dicarboxylic acid or tricarboxylic acid and (b) acid dianhydride of tetracarboxylic acid reacted with epoxy (meth)acrylate is 0.01 or more and 10.0. It is preferable that it is below, and it is more preferable that it is 0.02 or more and less than 3.0. If the molar ratio (a)/(b) is within the above range, the molecular weight of component (A) can be adjusted to improve the patterning properties of the photosensitive resin composition. Additionally, the smaller the molar ratio (a)/(b), the larger the molecular weight is, and the alkali solubility tends to decrease.

In addition, the method of reacting an epoxy compound with (meth)acrylic acid, and the reaction of the epoxy (meth)acrylate obtained from this reaction with a polybasic carboxylic acid or its acid anhydride is not particularly limited, and known methods can be adopted. there is. In addition, the unsaturated group-containing photosensitive resin synthesized through the above reaction preferably has a weight average molecular weight (Mw) of 2,000 or more and 10,000 or less. In addition, the photosensitive resin containing an unsaturated group synthesized through the above reaction preferably has an acid value of 30 mgKOH/g or more and 200 mgKOH/g or less. In addition, the acid value can be obtained by dissolving the resin solution in dioxane and titrating with 1/10 N-KOH aqueous solution using, for example, a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sankyo Co., Ltd.) . In addition, the weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin can be measured, for example, using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation).

Other preferred examples of the component (A) include resins that are copolymers of (meth)acrylic acid, (meth)acrylic acid ester, and the like, and have a (meth)acryloyl group and a carboxyl group. Examples of the above resin include copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, reacting the obtained copolymer with (meth)acrylic acid, and finally dicarboxylic acid or tricarboxylic acid. Alkali-soluble resins containing polymerizable unsaturated groups obtained by reacting acid anhydrides are included. The copolymer contains 20 to 90 mol% of repeating units derived from diesterglycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, as shown in Japanese Patent Application Laid-Open No. 2014-111722, and 1 copolymerizable with this. A copolymer composed of 10 to 80 mol% of repeating units derived from one or more types of polymerizable unsaturated compounds and having a number average molecular weight (Mn) of 2,000 to 20,000 and an acid value of 35 to 120 mgKOH/g, and Japanese Patent Application Laid-Open No. 2018-141968 A weight average molecular weight (Mw) of 3,000 to 50,000, including a unit derived from a (meth)acrylic acid ester compound and a unit having a (meth)acryloyl group and a di- or tricarboxylic acid residue, as shown in the gazette. The alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer of 30 to 200 mg/KOH, can be used as a reference.

(A) One type of component may be used individually, and two or more types may be used together.

The compounding amount of component (A) is preferably 5 mass% or more and 70 mass% or less, more preferably 5 mass% or more and 60 mass% or less, and even more preferably 10 mass% or more and 50 mass% or less, based on the total mass of solid content. do.

2. (B) Ingredient

(B) Component is a photopolymerizable compound having at least two or more unsaturated bonds. (B) Examples of components include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tetramethylene glycol. Di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylol ethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri( Meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylic acids such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. These include esters, compounds having an ethylenic double bond, and dendritic polymers having a (meth)acrylic group. (B) Component may be used individually as one type of these photopolymerizable compounds, or may be used in combination of two or more types. In addition, component (B) can play a role in crosslinking the molecules of component (A), and in order to exert this function, it is preferable to have three or more unsaturated bonds. Additionally, the acrylic equivalent of component (B), which is the molecular weight divided by the number of (meth)acrylic groups in one molecule, is preferably 50 to 300, and more preferably 80 to 200. Additionally, component (B) does not have a free carboxyl group.

(B) Examples of dendritic polymers having a (meth)acryloyl group that can be used as a component include adding a polyvalent mercapto compound to a portion of the carbon-carbon double bond in the (meth)acryloyl group of the polyfunctional (meth)acrylate. Dendritic polymers obtained by addition are included. Specifically, it includes a dendritic polymer obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the following general formula (4) with a polyhydric mercapto compound represented by the following general formula (5). do.

(In the general formula (4), R ₅ is a hydrogen atom or a methyl group, and R ₆ is the remainder of n hydroxy groups among the k hydroxy groups of R ₇ (OH) _k donated to the ester bond in the formula. R ₇ (OH) ) _k is a polyhydric alcohol based on a non-aromatic straight-chain or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyhydric alcohol formed by linking multiple molecules of the above-mentioned polyhydric alcohol through an ether bond through dehydration condensation of the alcohol It is preferable that it is an ether or an ester of these polyhydric alcohols or polyhydric alcohol ethers and hydroxy acids. k and n independently represent an integer of 2 to 20, but k≥n.)

(In General Formula (5), R ₈ is a single bond or a divalent to hexavalent hydrocarbon group with 1 to 6 carbon atoms, and m is 2 when R ₈ is a single bond, and when R ₈ is a divalent to hexavalent In the case of the following groups, it is the same as the mantissa of R _8. )

Examples of polyfunctional (meth)acrylates represented by general formula (4) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ethylene. Oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and (meth)acrylic acid esters such as caprolactone-modified pentaerythritol tri(meth)acrylate. These polyfunctional (meth)acrylates may be used individually or in combination of two or more types.

Examples of polyhydric mercapto compounds represented by general formula (5) include trimethylolpropane tri(mercaptoacetate), trimethylol propane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), and pentaerythritol tetra(mercaptoacetate). Includes erythritol tri (mercaptoacetate), pentaerythritol tetra (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate), etc. These polyvalent mercapto compounds may be used individually, or two or more types may be used in combination.

The mixing ratio of component (A) and component (B) is preferably 30/70 to 90/10 in weight ratio (A)/(B), and more preferably 60/40 to 80/20. If the mixing ratio of component (A) is 30/70 or more, the cured product after photocuring is unlikely to become brittle, and the acid value of the coating film in the unexposed area is unlikely to be lowered, so a decrease in solubility in an alkaline developer can be suppressed. Therefore, it is difficult for defects such as pattern edges to be jagged or not sharp to occur. In addition, if the mixing ratio of component (A) is 90/10 or less, the ratio of photoreactive functional groups in the resin is sufficient, so the desired crosslinked structure can be formed. In addition, since the acidity of the resin component is not too high, it is difficult to increase the solubility in the alkaline developer in the exposed area, so it is possible to suppress the formed pattern from being finer than the target line width and missing patterns. do.

3. (C) Ingredient

(C) Component is a photopolymerization initiator. (C) Examples of components include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Benzophenones such as acetophenones, benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluoro Biimidazole series such as phenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole Compounds; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichlor halomethylthiazole compounds such as lomethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5- Trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1 Halomethyl-S-triazine-based compounds such as ,3,5-triazine; 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, 1-(4-methylsulfanylphenyl)butane-1-oneoxime-O -O-acyloxime compounds such as acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl-O-acetyloxime; Sulfur compounds such as benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; Anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; Organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; These include thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. Among these, O-acyloxime-based compounds are preferred. These photopolymerization initiators may be used individually or in combination of two or more types.

Examples of O-acyloxime-based compounds that can be preferably used include O-acyloxime-based photopolymerization initiators represented by the following general formula (6) and the following general formula (7). Among these compound groups, when using a light-shielding component at a high concentration, it is preferable to use an O-acyloxime-based photopolymerization initiator with a molar extinction coefficient of 10000 or more at 365 nm. In addition, the term "photopolymerization initiator" as used in the present invention is used to include a sensitizer.

(In General Formula (6), R ₉ and R ₁₀ each independently represent an alkyl group with 1 to 15 carbon atoms, an aryl group with 6 to 18 carbon atoms, an arylalkyl group with 7 to 20 carbon atoms, or a heterocyclic group with 4 to 12 carbon atoms, R ₁₁ represents an alkyl group with 1 to 15 carbon atoms, an aryl group with 6 to 18 carbon atoms, and an aryl alkyl group with 7 to 20 carbon atoms. Here, the alkyl group and the aryl group represent an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, and The alkanoyl group of 1 to 10 may be substituted with halogen, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and the alkyl group may be linear, branched, or cyclic. Contribution is also good.)

(In General Formula (7), R ₁₂ and R ₁₃ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, cycloalkylalkyl group or alkyl cycloalkyl group having 4 to 10 carbon atoms, or a 1-carbon alkyl group. R ₁₄ is a phenyl group that may be substituted with an alkyl group of ∼6, and each independently represents a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and a portion of the -CH ₂ -group in the alkyl or alkenyl group is -O. - may be substituted with a group. Additionally, some of the hydrogen atoms in the groups R ₁₂ to R ₁₄ may be substituted with a halogen atom.)

The mixing amount of component (C) is preferably 3 parts by weight or more and 30 parts by weight or less, and more preferably 5 parts by weight or more and 20 parts by weight or less, based on a total of 100 parts by weight of each component (A) and (B). When the compounding amount of component (C) is 3 parts by weight or more, the sensitivity of the photosensitive resin composition becomes good, and the speed of photopolymerization can be sufficiently increased. When the compounding amount of component (C) is 30 parts by weight or less, the sensitivity of the photosensitive resin composition is set to an appropriate range, and it is easy to obtain a cured film having a desired pattern line width and a desired pattern edge shape.

4. (D) Ingredient

(D) The component is a light-shielding component that is a black pigment, a mixed-color organic pigment, or a light-shielding material. As the component (D), known light-shielding components can be used without particular restrictions. In addition, the component (D) is preferably dispersed so that the average particle diameter (average particle diameter measured with a laser diffraction/scattering method particle size distribution meter or a dynamic light scattering method particle size distribution meter) is 1 nm or more and 1000 nm or less.

Examples of the black pigment include perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, etc.

Examples of the above mixed organic pigments include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, trene pigments, perylene pigments, and perylene pigments. Pigments containing a mixture of at least two colors of organic pigments such as paddy pigment, quinophthalone pigment, diketopyrrolopyrrole pigment, and thioindigo pigment are included.

(D) Depending on the function of the intended photosensitive resin composition, only one type of component may be used individually, or two or more types may be used together.

In addition, when using a mixed-color organic pigment as the (D) component, examples of organic pigments that can be used include those with the following numbers in color index names, but are not limited to this.

Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178 , 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272 , 279, etc.

Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129 , 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.

Pigment green 7, 36, 58, etc.

Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.

Pigment Violet 19, 23, 37, etc.

The amount of component (D) can be arbitrarily determined depending on the desired degree of light blocking, but is preferably 20% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 70% by mass or less, based on the total mass of solids in the photosensitive resin composition. desirable. When using an organic pigment such as aniline black, cyanine black, lactam black, or a carbon-based light-shielding component such as carbon black as the light-shielding component of component (D), the mixing amount of component (D) is based on the solid content in the photosensitive resin composition. It is preferable that it is 40 mass% or more and 60 mass% or less. If the compounding amount of the light-shielding component is 20% by mass or more relative to the solid content in the photosensitive resin composition, the light-shielding property of the cured film can be sufficiently improved. If the blending amount of the light-shielding component is 80% by mass or less based on the solid content in the photosensitive resin composition, the content of the photosensitive resin serving as the original binder can be sufficiently increased to obtain desired development characteristics and film-forming ability.

The component (D) is a light-shielding component dispersion dispersed in a solvent and is usually mixed with other components, and a dispersant may be added in that case. As the dispersant, known compounds used for dispersing pigments (light-shielding components) (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular restrictions.

Examples of dispersants for light-shielding components include cationic polymer-based dispersants, anionic polymer-based dispersants, nonionic polymer-based dispersants, and pigment derivative-type dispersants (dispersing aids). In particular, the dispersant has a cationic functional group such as an imidazolyl group, pyrrolyl group, pyridyl group, primary, secondary or tertiary amino group as an adsorption point to the colorant, and has an amine value of 1 mgKOH/g or more and 100 mgKOH/g. Hereinafter, a cationic polymer-based dispersant having a number average molecular weight (Mn) in the range of 1,000 to 100,000 is preferable. The amount of the dispersant for the light-shielding component is preferably 1% by mass or more and 35% by mass or less, and more preferably 2% by mass or more and 25% by mass or less, based on the total mass of the light-shielding component. In addition, high viscosity substances such as resins generally have the effect of stabilizing dispersion, but those that do not have the ability to promote dispersion are not treated as dispersants. However, its use for the purpose of stabilizing dispersion is not limited.

5. (E) Ingredient

(E) The component is silica particles. The manufacturing method, such as gas phase reaction or liquid phase reaction, or the shape (spherical, non-spherical) of the silica particles are not particularly limited.

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

The (E) component can lower the refractive index of the cured film (light-shielding film). As a result, reflection caused by the difference in refractive index of the cured film (light-shielding film), such as the transparent substrate, air, transparent protective film, etc., is suppressed, and the reflectance of the cured film can be lowered.

(E) It is preferable that the average particle diameter of component is 1 nm or more and 100 nm or less, and it is more preferable that it is 10 nm or more and 90 nm or less. Compared to silica particles with a small particle size of several nanometers, silica particles having a size within the above range are thought to be less likely to cause agglomeration between particles. Therefore, if the particle size of component (E) is within the above range, the dispersion stability of component (E) is improved, movement restrictions due to agglomeration of component (E) within the light-shielding film are unlikely to occur, and the amount is sufficient. Since the (E) component can be localized on the film surface side, it is thought that the reflectance on the film surface side can be reduced more sufficiently. In addition, by setting the average particle diameter of component (E) to 100 nm or less, component (E) can be moved to a certain degree in the coating film, making it easier to localize component (E) on the film surface side, and also make it easier to localize component (E) on the film surface side. (E) It is possible to suppress the decrease in linearity and surface smoothness of the cured film due to the component.

The average particle diameter of component (E) can be measured by the cumulant method using a particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) of the dynamic light scattering method.

The refractive index of component (E) is preferably 1.10 or more and 1.47 or less. In addition to using the refractive index of normal silica particles (1.45 to 1.47), by using hollow silica particles with a low refractive index, the refractive index of the light-shielding film can be lowered than that of the light-shielding film containing only normal silica particles.

The refractive index of component (E) can be determined from a transparent mixed solution obtained by mixing the silica particles treated in powder form with a standard refractive solution with a known refractive index. Additionally, the refractive index of the silica particles can be measured using an Abbe refractometer.

(E) The shape of the component may be spherical or elliptical. Among these, a true spherical shape is preferable.

(E) It is preferable that component has a sphericity of 1.0 or more and 1.5 or less. If the sphericity of the silica particles is within this range, the particle shape becomes close to a true sphere. For this reason, it is possible to homogeneously fill a light-shielding film with a thin film thickness in the in-plane direction (direction horizontal to the substrate surface), maintaining the smoothness of the cured film surface, and preventing the silica particles from being exposed to the outside from the cured film surface. A light blocking film can be formed. Therefore, a light-shielding film with a low refractive index and sufficient strength can be obtained.

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

The (E) component can be mixed with other compounding components as a dispersion dispersed in a solvent using the (F) component (dispersant) described later.

It is preferable that the compounding quantity of (E) component is 0.1 mass % or more and 5 mass % or less, and more preferably 0.1 mass % or more and 2 mass % or less with respect to the total mass of the photosensitive resin composition containing a solvent. If the compounding amount of silica particles is within the above range, low reflectivity can be achieved and good optical patterning properties can be ensured.

In addition, the ratio (mE/mD) of the total mass (mE) of the (E) silica particles to the total mass (mD) of the (D) light-shielding component is preferably 0.01 or more and 0.20 or less, and more preferably 0.05 or more and 0.10 or less. do. (D) If the ratio of the total mass (mE) of the silica particles (E) to the total mass (mD) of the light-shielding component is within the above range, it is possible to achieve both high light-shielding and low reflectance.

6. (F) Ingredient

(F) Component is a dispersant. In this embodiment, component (F) has an acid value and an amine value, and both the acid value and the amine value are 10 mgKOH/g or more and 80 mgKOH/g or less. (F) If the amine value of component is 10 mgKOH/g or more, the dispersibility of silica particles can be improved. On the other hand, a dispersant having only an amine value increases the dispersibility of the silica particles, but reduces the solubility of the silica particles in the developing solution, so it remains as a residue at the edge of the pattern and reduces linearity. On the other hand, if the amine value of the dispersant is 10 mgKOH/g or more and the acid value is also 10 mgKOH/g or more, the dispersibility of the silica particles is improved and high-definition pattern formation is possible. On the other hand, by setting both the acid value and the amine value to 80 mgKOH/g or less, the solubility of the silica particles protected with the dispersant in the developing solution does not increase excessively, and a decrease in the fineness of the formed pattern can be suppressed. From the above viewpoint, it is preferable that either the amine value or the acid value of the dispersant is 30 mgKOH/g or more and 80 mgKOH/g or less, and it is more preferable that both are 30 mgKOH/g or more and 80 mgKOH/g or less.

In addition, the acid value of component (F) means the number of mg of KOH required to neutralize 1 g of resin component (solid content), and can be measured based on JIS K 0070 (1992). (F) The amine value of the dispersant as a component means the number of mg of KOH equivalent to the amount of acid (acetic acid, etc.) required to neutralize 1 g of resin component (solid content), and is based on JIS K 7237 (1995). It can be measured.

(F) Examples of the component include alkylammonium salts and alkylolammonium salts of acidic polymers, alkylammonium salts and alkylolammonium salts of polymer copolymers having an acid group, neutralized salts of polymers having an alkylamino group, and phosphoric acid ester salts of polymer copolymers, etc. This is included. Among these, polymer compounds having an alkylammonium salt structure are preferable, and alkylammonium salts of acidic polymers and alkylammonium salts of polymer copolymers having an acid group are more preferable. By using a polymer compound having an alkylammonium salt structure as a dispersant, the generation of aggregated foreign matter derived from silica particles can be more significantly suppressed.

(F) Examples of commercially available products include DISPERBYK-140, 142, 145, 2001, 2025, 9076 (all manufactured by Big Chemie Japan, “DISPERBYK” registered by the company), etc. Among the above commercially available products, DISPERBYK-140, 142, and 9076 are preferable, and DISPERBYK-140 and 9076 are more preferable.

(F) The compounding quantity of the dispersant is preferably 0.01% by mass or more and 0.5% by mass or less with respect to the total mass of the photosensitive resin composition containing the solvent.

The ratio (mF/mE) of the total mass (mF) of the component (F) to the total mass (mE) of the component (E) is preferably 0.02 or more and 0.6 or less, and more preferably 0.03 or more and 0.4 or less. If the ratio of the total mass (mF) of the (F) component to the total mass (mE) of the (E) component is within the above range, the reflectance on the glass substrate side and the film surface side is reduced while the dispersibility of the silica particles is improved, It is possible to suppress the generation of aggregated foreign substances derived from silica particles.

7. (G) Ingredients

(G) Component is a solvent. In the present embodiment, the photosensitive resin composition contains, as component (G), a first solvent that is propylene glycol monomethyl ether, and a second solvent (represented by the following general formula (1)) having a vapor pressure at 20°C of less than 250 Pa. The solvent includes at least (excluded from the second solvent).

RO-(CH ₂ CH ₂ O)nR···(1)

In General Formula (1), R independently represents an alkyl group or an aryl group which may have a substituent, and n is an integer of 2 to 5.

The second solvent, which has a low vapor pressure at 20°C and is difficult to evaporate, slows the drying rate of the coating film formed by applying the photosensitive resin composition to a substrate or the like when drying the coating film before prebaking. According to the present inventor's new knowledge, during this drying, as the amount of solvent in the coating film decreases from the surface side of the coating film, component (E) moves to the bottom side (substrate side) of the coating film where a large amount of solvent remains. Therefore, the amount of component (E) on the film surface side of the cured film formed by subsequent curing tends to decrease. In contrast, by using a second solvent that is difficult to evaporate, the solvent is likely to remain on the surface side of the coating film for a long time during drying, thereby suppressing the movement of component (E) to the bottom side (substrate side) of the coating film, and further reducing the solvent As evaporation occurs, component (E) can be moved to the membrane surface side, so that component (E) can be localized on the membrane surface side. As a result, the cured film formed by subsequent curing is believed to have a sufficient amount of component (E) also on the film surface side, so that the refractive index on the film surface side is adjusted and the reflectance on the film surface side also decreases. From the above viewpoint, the second solvent more preferably has a vapor pressure at 20°C of more than 1 Pa and less than 100 Pa, and even more preferably more than 10 Pa and less than 50 Pa.

In addition, in the present embodiment, since the above-mentioned dispersant that is unlikely to cause agglomeration of silica is used as the (F) component in an appropriate amount, movement restrictions due to agglomeration of the (E) component are unlikely to occur, and a sufficient amount of the (E) component is formed into the film. Since it can be localized on the surface side, it is thought that the reflectance on the film surface side can be reduced more sufficiently.

However, according to the present inventor's additional knowledge, this effect cannot be confirmed with the solvent represented by general formula (1), and therefore the solvent represented by general formula (1) is not included in the second solvent. However, there is no particular problem even if the solvent represented by General Formula (1) is used as a third solvent or other solvent.

Examples of the second solvent include methoxybutyl acetate, 3-ethoxyethyl propionate, 3-methoxy-3-methyl-1-butyl acetate, dipropylene glycol monomethyl ether, and 3-methoxy-3-methyl-1. -Butanol, propylene glycol diacetate, ethylene glycol, propylene glycol, methyl carbitol, ethyl carbitol, butyl carbitol, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol mono. Ethyl ether acetate, etc. are included. Among these, 3-methoxy-3-methyl-1-butylacetate, 3-methoxy-3-methyl-1-butanol, and propylene glycol diacetate are preferred.

Moreover, it is preferable that component (G) contains a third solvent whose relative dielectric constant at 23°C is 10.0 or more and 30.0 or less. The third solvent can stabilize the silanol groups on the surface of the silica particles by solvation, thereby suppressing aggregation of component (E) in the photosensitive resin composition. From the above viewpoint, the relative dielectric constant at 23°C of the third solvent is preferably 13.0 or more and 20.0 or less, and more preferably 13.0 or more and 18.0 or less. The photosensitive resin composition may, unlike the second solvent, contain a 3-1 solvent whose relative dielectric constant is in the above range, or the second solvent may include a 3-2 solvent that satisfies the above requirements for relative dielectric constant. Alternatively, the 3-1 solvent and the 3-2 solvent may be included together. In addition, the 3-2 solvent is a solvent included in both the second solvent and the third solvent.

(G) From the viewpoint of appropriately adjusting the dielectric constant of the entire component and increasing the agglomeration-inhibiting effect of the component (E), the component (G) contains the 3-1 solvent, or the second solvent contains the solvent at 23°C. It is preferable to include a solvent having a relative dielectric constant of less than 10.0 and a 3-2 solvent having a relative dielectric constant of 10.0 or more and 30.0 or less at 23°C. Among these, the vacuum drying time can be adjusted to an appropriate range, and from the viewpoint of preventing film formation defects caused by solvent remaining due to insufficient vacuum drying, component (G) contains the 3-1 solvent. It is more desirable to do so.

The third solvent is preferably saturated ketones having a linear, branched or cyclic structure having 3 to 12 carbon atoms, or unsaturated alcohols having a linear, branched or cyclic structure having 3 to 12 carbon atoms.

Examples of the saturated ketones as the third solvent include acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. Examples of the saturated alcohol as the third solvent include ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 1-methoxy-2-propanol, ethyl lactate, and 3-methoxy-3-methyl-1-butanol. etc. are included. Examples of other third solvents include glycol ethers such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol mono. These include methyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether. Among these, cyclohexanone, ethyl lactate, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, and propylene glycol monoethyl ether are preferred, and cyclohexanone, ethyl lactate, and 3-methoxy-3-methyl-1-butanol is more preferred.

The compounding amount of the first solvent is preferably 10% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and 30% by mass or more and 70% by mass or less, based on the total mass of component (G). More preferably, it is most preferable that it is 45 mass% or more and 70 mass% or less. By increasing the compounding amount of the first solvent, the solubility of component (A) and (B) and the dispersibility of component (D) can be further improved.

The amount of the second solvent mixed is preferably 10% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and 10% by mass or more and 40% by mass or less, based on the total mass of component (G). More preferably, it is most preferable that it is 10 mass% or more and 35 mass% or less. By increasing the amount of the second solvent, more component (E) can be present on the film surface side of the cured film, and the reflectance on the film surface side of the cured film can be sufficiently reduced. By appropriately suppressing the amount of the second solvent, the vacuum drying time can be adjusted to an appropriate range. In addition, film formation defects caused by solvent remaining due to insufficient vacuum drying may be less likely to occur. In addition, the compounding amount of the second solvent was calculated including the content of the 3-2 solvent.

The compounding amount of the third solvent is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 50% by mass or less, and 15% by mass or more and 40% by mass or less, based on the total mass of component (G). More preferably, it is most preferable that it is 15 mass% or more and 25 mass% or less. By increasing the amount of the third solvent, aggregation of component (E) can be suppressed and the reflectance can be reduced more efficiently. By appropriately suppressing the amount of the third solvent, the applicability of the photosensitive resin composition can be further improved. In addition, the compounding amount of the third solvent was the total amount of the content of the 3-1 solvent and the content of the 3-2 solvent.

When the component (G) contains the 3-1 solvent as the third solvent, the compounding amount of the 3-1 solvent is preferably 10% by mass or more and 50% by mass or less with respect to the total mass of the component (G), and is preferably 15% by mass. It is more preferable that it is 15 mass% or more and 50 mass % or less, more preferably 15 mass % or more and 40 mass % or less, and most preferably 15 mass % or more and 25 mass % or less. By increasing the amount of the 3-1 solvent, agglomeration of component (E) is suppressed and the reflectance is reduced more efficiently, and the vacuum drying time can be adjusted to an appropriate range, so that the solvent remains due to insufficient vacuum drying. This can make it difficult for film formation defects to occur. By appropriately suppressing the amount of the 3-1 solvent, the applicability of the photosensitive resin composition can be further improved.

The amount of component (G) mixed is preferably 40% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 90% by mass or less, and even more preferably 80% by mass or more and 90% by mass or less, based on the total mass of the photosensitive resin composition. desirable.

8. Other ingredients

The photosensitive resin composition may optionally contain resins other than component (A) such as epoxy resin, curing agent, curing accelerator, thermal polymerization inhibitor and antioxidant, plasticizer, filler other than silica, leveling agent, anti-foaming agent, surfactant, coupling agent, etc. Additives can be mixed.

Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include glass fiber, mica, alumina, etc. Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc. This is included.

9. Preparation of photosensitive resin composition

The photosensitive resin composition can be prepared by mixing and dispersing the components (A) to (G) and optionally other components. For example, a light-shielding component dispersion containing component (A), (B) component, (C) component, and (D) component, and a silica particle dispersion containing component (E) and (F) component. A photosensitive resin composition can be obtained by mixing.

By containing the (F) dispersant in the (E) silica particle dispersion in advance, it becomes possible to improve the dispersion stability of the silica dispersion and prevent the generation of aggregated foreign substances when mixed with other resin components.

10. Sunshade

The photosensitive resin composition can be used to produce a light-shielding film by applying it to a substrate or the like, drying the solvent, and curing it by irradiating light (including ultraviolet rays, radiation, etc.). At this time, a light-shielding film having a desired pattern shape can be obtained by forming a portion that is exposed to light and a portion that is not exposed to light using a photomask, hardening only the portion that is exposed to light, and dissolving the other portions in an alkaline solution.

Specifically, application of the photosensitive resin composition to a substrate can be performed by a known solution dipping method, a spray method, a roller coater, a land coater, a slit coater, or a spinner method. By these methods, a coating film is formed by applying to a desired thickness, drying, and then further removing the solvent (prebaking).

Drying may be performed by a method such as vacuum drying under conditions such that the ultimate pressure is 10 to 1000 Pa in 10 to 180 seconds. Additionally, the pressure may be degassed all at once until the target pressure is reached, or the pressure may be reduced step by step to prevent defects in the film such as dolby.

Prebaking is performed by heating using an oven, hot plate, etc., vacuum drying, or a combination of these. The heating temperature and heating time in prebaking can be appropriately selected depending on the solvent used, but is preferably carried out at, for example, 80 to 120°C for 1 to 10 minutes.

As radiation used for exposure, for example, visible light, ultraviolet ray, deep ultraviolet ray, electron beam, X-ray, etc. can be used, but the wavelength of the radiation is preferably in the range of 250 to 450 nm. In addition, as a developer suitable for this alkaline development, for example, aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. These developers can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant as needed. The developing temperature is preferably 20 to 35°C, and fine images can be formed precisely using a commercially available developing device or ultrasonic cleaner. Additionally, after alkali development, it is usually washed with water. As a development method, shower development method, spray development method, dip (immersion) development method, puddle (liquid mounting) development method, etc. can be applied.

After development in this way, heat treatment (post-baking) may be performed at 70 to 250°C for 20 to 100 minutes to increase the adhesion between the light shielding film and the substrate. Post-baking, like pre-baking, can be performed by heating in an oven, hot plate, etc.

The light-shielding film obtained in this way can be used as a black resist in a display device. For example, the light shielding film can be used as a color filter, a black matrix of a touch panel, a black column spacer, a frame, etc.

For example, in the color filter having the light-shielding film as a black matrix, a light-shielding film having a film thickness of 1.0 to 2.0 μm is formed on a transparent substrate, and each pixel of red, blue and green is formed by photolithography after forming the light-shielding film, or Alternatively, it is produced by adding red, blue, and green ink into a light-shielding film using an inkjet process.

Additionally, when using the light-shielding film as a black column spacer, a single black resist may be used to produce multiple parts with different film thicknesses, one of which may function as a spacer, and the other may function as a black matrix.

In addition, the method of producing a light-shielding film having a pattern shape is not limited to the photolithographic method of performing exposure and alkali development, and the pattern may be formed by screen printing or the like.

The light-shielding film is a film obtained by applying a photosensitive resin composition on a glass substrate, prebaking it at 90°C for 1 minute on a hot plate, and irradiating ultraviolet rays of 50 mJ/cm2 with an ultra-high pressure mercury lamp with an i-ray illuminance of 30 mW/cm2. The reflectance of the light-shielding film with a thickness of 1.2 μm is preferably 6% or less on the glass surface side, and more preferably 5% or less. Moreover, on the film side, it is preferable that it is 6.5% or less, and it is more preferable that it is 5.5% or less.

The photosensitive resin composition can be suitably used for each of the above-mentioned purposes and also as various other coating materials. In particular, ink for color filters used in liquid crystal display devices or imaging devices, and light-shielding films formed therefrom are useful as color filters, black matrices for liquid crystal projection, etc. In addition, the photosensitive resin composition is used for color fractionation in various multicolor displays such as organic electroluminescent devices represented by organic EL elements, color liquid crystal displays, color facsimiles, and image sensors, in addition to color filter inks for color liquid crystal displays. Alternatively, it can also be used as a light-shielding ink material.

In particular, the light shielding film can lower the reflectance on the film side, so when it is used for applications where the film surface is disposed inside a display device such as a liquid crystal display, loss due to reflection inside the device of light from an internal light source can be suppressed. You can. In addition, when a film surface such as an organic LED (OLED) is used for placement on the outside of a display device, bright spot contrast is improved by reducing reflection of external light, and light extraction efficiency from the light emitting side is improved. This can improve luminous efficiency.

Example

Hereinafter, embodiments of the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited to these. Additionally, in the present invention, when the first decimal place is 0 for the content of each component, the notation below the decimal point may be omitted.

First, the synthesis examples of the alkali-soluble resin containing an unsaturated group, which is component (A), will be described. However, evaluation of the resins in these synthesis examples was performed as follows, unless otherwise specified.

[Solids concentration]

1 g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)], and the weight [W ₂ (g)] after heating at 160°C for 2 hours was obtained as follows. Obtained from Eq.

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

[Sanga]

The resin solution was dissolved in dioxane, and titrated with a 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sankyo Co., Ltd.) to determine the result.

[Molecular Weight]

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

[Average particle diameter]

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

The symbols used in synthesis examples are as follows.

BPFE: Bisphenol fluorene type epoxy compound (reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane. In the compound of formula (2), Diyl group, a compound where R ₁ to R ₄ are hydrogen.)

AA: Acrylic acid

BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride

THPA: tetrahydrophthalic anhydride

TEAB: tetraethylammonium bromide

PGMEA: propylene glycol monomethyl ether acetate

[Synthesis example]

BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were injected into a 500 ml four-necked flask equipped with a reflux condenser, and stirred at 100-105°C for 20 hours to react. I ordered it. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were injected into the flask and stirred at 120 to 125°C for 6 hours to obtain an alkali-soluble resin (A) containing an unsaturated group. The solid content concentration of the obtained resin solution was 56.0% by mass, the acid value (converted to solid content) was 103 mgKOH/g, and the Mw according to GPC analysis was 3600.

The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 12 were prepared in the mixing amounts (unit: parts by mass) shown in Tables 1 to 4. The mixing ingredients used in Tables 1 to 4 are as follows.

(Alkali-soluble resin containing unsaturated groups)

(A): Alkali-soluble resin solution containing an unsaturated group obtained in the above synthesis example (solid content concentration 56.0% by mass)

(Photopolymerizable compound)

(B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Toa Kosei Co., Ltd., “Aronix” is a registered trademark of the company)

(Photopolymerization initiator)

(C)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (Irgacure OXE-02, Made by BASF Japan, “Irgacure” is the company’s registered trademark)

(C)-2: Adeka Ackles NCI-831, manufactured by ADEKA Corporation, “Adeka Ackles” is the company’s registered trademark)

(carbon black dispersion)

(D): Carbon black concentration of 25.0% by mass, polymer dispersant concentration of 2.0% by mass, PGMEA dispersion of dispersion resin (alkali-soluble resin (A) of the synthesis example (solid content 8.0% by mass))

(Solid content 35.0% by mass)

(E): PGMEA dispersion of silica particles “YA050C” (manufactured by Admatex Co., Ltd., solid content concentration 30% by mass, average particle diameter 50nm)

(Dispersant)

(F)-1: DISPERBYK-140 (propylene glycol monomethyl ether acetate dispersion with solid content concentration of 52 mass%, acid value 73 mgKOH/g, amine value 76 mgKOH/g)

(F)-2: DISPERBYK-142 (propylene glycol monomethyl ether acetate dispersion with solid content concentration of 60% by mass, acid value of 46mgKOH/g, amine value of 43mgKOH/g)

(F)-3: DISPERBYK-9076 (solid concentration 100 mass%, acid value 38 mgKOH/g, amine value 44 mgKOH/g)

Additionally, (F)-1 to (F)-3 are all manufactured by Big Chemie Japan, and “DISPERBYK” is the company’s registered trademark.

In addition, (F)-1 is a dispersant having an alkylammonium salt structure of an acidic polymer, (F)-2 is a phosphoric acid ester salt type dispersant of a polymer copolymer, and (F)-3 is an alkylammonium salt of a polymer copolymer having an acid group. It is a dispersant with a structure.

(solvent)

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

(G)-2: Ethyl lactate (EL)

(G)-3: Methoxybutylacetate (MBA)

(G)-4: 3-Ethoxypropionate (EEP)

(G)-5: 3-methoxy-3-methyl-1-butanol (MMB)

(G)-6: 3-methoxy-3-methyl-1-butylacetate (MMBA)

(G)-7: Propylene glycol diacetate (PDGA)

(G)-8: 1-methoxy-2-propanol (MMPG)

(G)-9: 3-Methoxypropionate (MMP)

(G)-10: Cyclohexanone (ANON)

(G)-11: Diethylene glycol dimethyl ether (MDM)

(G)-12: Diethylene glycol diethyl ether (EDE)

(G)-13: Diethylene glycol ethyl methyl ether (EDM)

(G)-14: Diethylene glycol dibutyl ether (BDB)

In addition, in Tables 1 to 4, the vapor pressure at 20°C and relative dielectric constant at 23°C of each solvent are shown in parentheses.

[evaluation]

A light-shielding film formed by curing the photosensitive resin composition for black resist to be used for evaluation was produced as follows.

(Production of a light shield for evaluation)

The photosensitive resin composition shown in Table 1 was previously irradiated with ultraviolet rays with a wavelength of 254 nm and an illuminance of 1000 mJ/cm2 using a low-pressure mercury lamp, and the surface was cleaned. A 125 mm × 125 mm glass substrate “#1737” (manufactured by Corning Corporation) (hereinafter “glass substrate”) ) was applied using a spin coater so that the film thickness after heat curing was 1.2㎛, the solvent was evaporated by reducing the pressure to 50Pa in 45 seconds using a vacuum dryer at 23°C, and then the solvent was evaporated using a hot plate. A light shield was produced by prebaking at 90°C for 1 minute. Next, the exposure gap was adjusted to 100㎛, a negative photomask with line/space = 10㎛/50㎛ was placed on the dry light shielding film, and ultraviolet rays of 50mJ/cm2 were irradiated with an ultra-high pressure mercury lamp with an i-line illuminance of 30mW/cm2. Then, a photocuring reaction of the photosensitive portion was performed.

Next, the exposed light-shielding film was developed at 25°C with a 0.04% potassium hydroxide solution at a shower pressure of 1 kgf/cm2 for +10 seconds and +20 seconds from the development time (break time = BT) at which the pattern begins to appear. Afterwards, spray water washing at 5kgf/cm2 was performed, the unexposed portion of the light-shielding film was removed, a light-shielding film pattern was formed on a glass substrate, and main curing (post-baking) was carried out at 230°C for 30 minutes using a hot air dryer. Light-shielding films for evaluation according to Examples 1 to 10 and Comparative Examples 1 to 7 were obtained.

The produced light-shielding film for evaluation was evaluated for the following items.

[Reflectance evaluation (substrate side, film side)]

(Assessment Methods)

For a substrate with a light-shielding film manufactured in the same manner as the above-mentioned light-shielding film for evaluation, the substrate (glass substrate) side and the film side were measured at an incident angle of 2° using an ultraviolet-visible-near-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.). The reflectance was measured. In addition, △ and above were considered passing.

(Evaluation criteria (board side))

○: Reflectance is 5% or less

△: Reflectance is greater than 5% and less than 6%

×: Reflectance is 6% or more

(Evaluation criteria (membrane side))

○: Reflectance is 5.5% or less.

△: Reflectance is greater than 5.5% and less than 6.5%

×: Reflectance is greater than 6.5%

[Optical density evaluation]

(Assessment Methods)

The optical density (OD) of the produced light-shielding film for evaluation was determined using a Macbeth transmission densitometer. Additionally, the film thickness of the light-shielding film formed on the substrate was measured, and the value obtained by dividing the optical density (OD) by the film thickness was taken as OD/μm.

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

Optical density (OD)=-log ₁₀ T (1)

(T represents transmittance)

[Evaluation of aggregated foreign matter]

(Assessment Methods)

The light-shielding film for evaluation after main curing (post-baking) was observed using an optical microscope to confirm the presence or absence of aggregated foreign matter. In addition, △ and above were considered passing.

(Evaluation standard)

○: No aggregated foreign matter is confirmed on the light shielding film.

△: Agglomerated foreign matter is confirmed in a part of the light shielding film.

×: Agglomerated foreign matter is confirmed on the entire surface of the light shielding film.

The evaluation results are shown in Tables 5 to 7.

As shown in Tables 5 to 7, a dispersant having both an acid value and an amine value of 10 mgKOH/g to 80 mgKOH/g is used, the first solvent is propylene glycol monomethyl ether acetate as the solvent, and the vapor pressure at 20°C is By using a second solvent (excluding the solvent represented by General Formula (1)) of less than 250 Pa, the reflectance not only on the glass substrate side but also on the film surface side could be lowered.

According to the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition for a black matrix that achieves both high light-shielding properties and low reflectance, and a light-shielding film, color filter, and touch panel using the same. Additionally, according to this color filter and touch panel, various display devices with excellent visibility can be provided.

Claims (16)

(A) a photosensitive resin containing an unsaturated group,
(B) a photopolymerizable compound having at least two or more unsaturated bonds,
(C) a photopolymerization initiator,
(D) at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments, and light-shielding materials,
(E) silica particles,
(F) a dispersant,
(G) contains a solvent;
The (F) dispersant has an acid value and an amine value, and both the acid value and the amine value are 10 mgKOH/g or more and 80 mgKOH/g or less,
The ratio (mF/mE) of the total mass (mF) of the (F) dispersant to the total mass (mE) of the (E) silica particles is 0.02 or more and 0.60 or less,
The solvent (G) is a first solvent that is propylene glycol monomethyl ether acetate, and a second solvent that has a vapor pressure of less than 250 Pa at 20°C (the solvent represented by the following general formula (1) is excluded from the second solvent). A photosensitive resin composition for a black resist, comprising:
RO-(CH ₂ CH ₂ O)nR···(1)
(In General Formula (1), R independently represents an alkyl group or aryl group that may have a substituent, and n is an integer of 2 to 5.) According to claim 1,
The (A) unsaturated group-containing photosensitive resin is a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (2) and (meth)acrylic acid, and a polybasic carboxylic acid or a polybasic carboxylic acid thereof. A photosensitive resin composition for black resist, which is a photosensitive resin containing an unsaturated group obtained by further reacting with an anhydride.

(In General Formula (2), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ₂ -, - C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9- represented by general formula (3) D is a diary group or a single bond, and l is an integer between 0 and 10.)
According to claim 1,
The photosensitive resin composition for black resist, wherein the (F) dispersant is a polymer compound having an alkylammonium salt structure. According to claim 1,
The solvent (G) includes the 3-1 solvent whose relative dielectric constant at 23°C is 10.0 or more and 30.0 or less (however, excluding the second solvent), or
The photosensitive resin composition for black resists in which the second solvent contains a solvent having a relative dielectric constant at 23°C of less than 10.0, and a 3-2 solvent having a relative dielectric constant at 23°C of 10.0 or more and 30.0 or less. According to claim 4,
The photosensitive resin composition for black resist, wherein the solvent (G) includes the 3-1 solvent. According to claim 1,
The photosensitive resin composition for black resist, wherein the (E) silica particles have an average particle diameter of 1 nm or more and 100 nm or less. According to claim 1,
The photosensitive resin composition for black resist, wherein the ratio (mE/mD) of the total mass (mE) of the (E) silica particles to the total mass (mD) of the (D) light-shielding component is 0.01 or more and 0.20 or less. According to claim 1,
The photosensitive resin composition for black resists, wherein the second solvent is a solvent whose vapor pressure at 20°C is less than 100 Pa. According to claim 1,
The second solvent includes at least one solvent selected from the group consisting of 3-methoxy-3-methyl-1-butylacetate, 3-methoxy-3-methyl-1-butanol, and propylene glycol diacetate. A photosensitive resin composition for black resist. According to claim 1,
A photosensitive resin composition for black resists, wherein a light-shielding film having a reflectance of 6.5% or less on the film surface side can be obtained by curing the photosensitive resin composition for black resists. According to claim 1,
A photosensitive resin composition for black resists, wherein a light-shielding film having a reflectance of 5.5% or less on the film surface side can be obtained by curing the photosensitive resin composition for black resists. A light-shielding film formed by curing the photosensitive resin composition for black resists according to any one of claims 1 to 11. A color filter comprising the light-shielding film according to claim 12 as a black matrix. A touch panel comprising the light-shielding film according to claim 12. A display device having the color filter according to claim 13. A display device comprising the touch panel according to claim 14.