JP2022173086A - Photosensitive resin composition for black resist, cured film, method for producing cured film, and color filter and partition having cured film - Google Patents

Abstract

To provide a photosensitive resin composition for black resist that can reduce reflectance on the formed film surface, allows fine pattern formation, and allows for forming a light blocking film having high adhesion to a glass substrate even after PCT.SOLUTION: A photosensitive resin composition for black resist contains (a) an alkali-soluble resin having an ethylenically unsaturated bond, (b) a photopolymerizable compound, (c) an oxime ester-based photopolymerization initiator, (d) a light blocker, (e) a coupling agent, (f) a surfactant having a fluorine atom and an ethylenically unsaturated bond in each molecule, and (g) a solvent. The component (a) is a resin having a specific structure. The solid content, excluding the solvent, includes the component (e) of 0.01-10 mass% and the component (f) of 0.01-10 mass%.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition for black resist, a cured film using the composition, a method for producing the cured film, and a light-shielding film such as a color filter to which the cured film is applied. It also relates to barrier ribs applied as a pixel definition layer (PDL) of organic EL, a light conversion layer, and the like.

In various display devices, it is necessary to add a phase difference function to prevent reflection on the surface and correct the viewing angle. For example, organic EL display devices often use a circular polarizer, which has a sufficient anti-reflection effect on the surface, but on the other hand, it also has the effect of absorbing part of the light emitted by the organic EL. , lowers the luminous efficiency of the organic EL, resulting in increased power consumption in mobile devices. For this reason, as a member to replace the circularly polarizing plate, a method of combining a color filter and an antireflection film has been studied. In order to reduce the reflection, it is also required to reduce the reflection of the black matrix of the color filter.

In a display device, depending on the configuration of the device, the black matrix may be viewed through a transparent substrate such as glass, or it may be viewed from the side of the light shielding film called the black matrix. Low reflectivity and the like have been studied by lowering the refractive index of .

WO2016/129324

However, according to the findings of the present inventors, the light-shielding resin composition described in Patent Document 1 can satisfy the condition that a high-definition black matrix of 10 μm or less can be formed with high light-shielding at a film thickness of 1 to 2 μm. However, there are still problems with the flexible resin composition. In addition, when forming a partition wall for forming an organic EL light emitting layer or a light conversion layer for color gamut adjustment with a film thickness of 2 to 10 μm by an inkjet method or the like, a pattern formed with a photosensitive resin composition There are still problems with the technology that can satisfy the required characteristics at the same time, such as making the cross-sectional shape of the mirror appropriate and providing a low-reflection function.

The present inventors have devised a formulation design of a photosensitive resin composition for black resist containing an unsaturated group-containing alkali-soluble resin having a specific structure to form a high-definition black matrix for color filters and various partition walls. The present invention has been completed by finding that it is suitable for

(1) The photosensitive resin composition of the present invention is
(a) an alkali-soluble resin having an ethylenically unsaturated bond;
(b) a photopolymerizable compound having at least two ethylenically unsaturated bonds;
(c) an oxime ester photopolymerization initiator;
(d) a light blocking agent;
(e) a coupling agent having at least a functional group reactive with a carboxy group;
(f) a surfactant having a fluorine atom and an ethylenically unsaturated bond in the molecule;
(g) a solvent;
A photosensitive resin composition for black resist, comprising
The (a) component is a resin represented by the following general formula (1), and the (e) component is 0.01 to 10% by mass and the (f) component is 0.01 to 10% by mass in the solid content excluding the solvent. % by mass of a photosensitive resin composition for a black resist.

(In formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and part of the bonded hydrogen atoms are alkyl groups having 1 to 10 carbon atoms, substituted with a substituent selected from the group consisting of 10 aryl or arylalkyl groups, cycloalkyl or cycloalkylalkyl groups having 3 to 10 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen groups; Each R ₁ is independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number of 0 to 3, each G is independently a (meth)acryloyl group, A substituent represented by the following general formula (2) or a substituent represented by the following general formula (3), Y is a tetravalent carboxylic acid residue, Z is independently a hydrogen atom or a substituent represented by the following general formula (4), one or more of which is a substituent represented by the following general formula (4). n is a number with an average value of 1 to 20.)

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a 20 divalent saturated or unsaturated hydrocarbon groups, and p is a number from 0 to 10.)

（式（４）中、Ｗは２価または３価のカルボン酸残基であり、ｍは１または２の数である。）

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a number of 1 or 2.)

(2) The present invention is also characterized in that, in the photosensitive resin composition of (1), the component (d) is carbon black, and the solid content excluding the component (g) is 30 to 60% by mass. It is a photosensitive resin composition for a black resist.

(3) The present invention is also a cured film obtained by curing the photosensitive resin composition of (1) or (2). This cured film can be used as a light-shielding film as a black matrix of a color filter or as various partition walls.

(4) The present invention also provides a coating film forming step of applying the photosensitive resin composition of (1) or (2) onto a substrate and drying to form a coating film of the photosensitive resin composition. ,
An exposure step of irradiating a part of the coating film with radiation through a photomask;
a developing step of developing the coating film irradiated with radiation and removing an unexposed portion;
A heat-curing step of heat-curing the developed coating film;
A method for producing a cured film, comprising:

According to the present invention, it is possible to form a high-definition black matrix of 10 μm or less with high light-shielding at a film thickness of 1 to 2 μm, and even on a highly light-shielding cured film surface of OD 3 / μm, the reflectance is at a low level of 5% or less. I have found that it can be suppressed. In addition, it was found that when the barrier ribs were formed with a film thickness of 2 μm or more, it was possible to provide the pattern cross-sectional shape and the surface ink repellency required for the barrier ribs.

Hereinafter, the photosensitive resin composition for black resist of the present invention will be described in detail. The photosensitive resin composition for a black resist of the present invention comprises (a) an alkali-soluble resin having an ethylenically unsaturated bond and (b) a photopolymerizable compound having at least two ethylenically unsaturated bonds. , (c) an oxime ester-based photopolymerization initiator, (d) a light-shielding agent, (e) a coupling agent having at least a functional group reactive with a carboxy group, and (f) a fluorine atom and ethylenically unsaturated A surfactant having an intramolecular bond, and (g) a solvent.

1. Photosensitive resin composition [(a) component]
Component (a) is an alkali-soluble resin having an ethylenically unsaturated bond. By containing the component (a), the photosensitive resin composition can be provided with photocurability in combination with the photopolymerizable monomer and solubility in alkali development.

The alkali-soluble resin as component (a) is represented by the following formula (1).

(In formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and part of the bonded hydrogen atoms are alkyl groups having 1 to 10 carbon atoms, substituted with a substituent selected from the group consisting of 10 aryl or arylalkyl groups, cycloalkyl or cycloalkylalkyl groups having 3 to 10 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen groups; Each R ₁ is independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number of 0 to 3, each G is independently a (meth)acryloyl group, A substituent represented by the following general formula (2) or a substituent represented by the following general formula (3), Y is a tetravalent carboxylic acid residue, Z is independently a hydrogen atom or a substituent represented by the following general formula (4), one or more of which is a substituent represented by the following general formula (4). n is a number with an average value of 1 to 20.)
In addition, "(meth)acryloyl group" is a generic term for acryloyl group and methacryloyl group, and means one or both of them. Similarly, "(meth)acrylic acid", "(meth)acrylate", etc., which will be described later, also refer to generic terms.

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a 20 divalent saturated or unsaturated hydrocarbon groups, and p is a number from 0 to 10.)

（式（４）中、Ｗは２価または３価のカルボン酸残基であり、ｍは１または２の数である。）

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a number of 1 or 2.)

Next, a method for producing (a) an ethylenically unsaturated bond-containing alkali-soluble resin represented by the general formula (1) will be described in detail.

First, an epoxy compound (a-1) having a bisarylfluorene skeleton, which may have several oxyalkylene groups in one molecule, represented by the following general formula (5) (hereinafter simply referred to as "epoxy compound (a-1)”) is (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (6), or a (meth)acrylic acid derivative represented by the following general formula (7) Any one or two or more of the acrylic acid derivatives are reacted to obtain a diol compound which is an epoxy (meth)acrylate. The bisarylfluorene skeleton is preferably a bisphenolfluorene skeleton.

(In formula (5), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and part of the bonded hydrogen atoms are alkyl groups having 1 to 10 carbon atoms, 1 to 10 aryl or arylalkyl groups, 3 to 10 carbon cycloalkyl or cycloalkylalkyl groups, 1 to 5 carbon alkoxy groups, and halogen groups. Each R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number of 0 to 3.)

(In formulas (6) and (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a 20 divalent saturated or unsaturated hydrocarbon groups, and p is a number from 0 to 10.)

A known method can be used for the reaction of the epoxy compound (a-1) with the (meth)acrylic acid and/or (meth)acrylic acid derivative. For example, Japanese Patent Laid-Open No. 4-355450 discloses a diol compound containing a polymerizable unsaturated group by using about 2 mol of (meth)acrylic acid per 1 mol of an epoxy compound having two epoxy groups. is obtained. In the present invention, the compound obtained by the above reaction is a diol (h) containing a polymerizable unsaturated group represented by formula (8) (hereinafter simply referred to as "diol (h) represented by general formula (8) ”).

(In formula (8), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and part of the bonded hydrogen atoms are an alkyl group having 1 to 10 carbon atoms, 1 to 10 aryl or arylalkyl groups, 3 to 10 carbon cycloalkyl or cycloalkylalkyl groups, 1 to 5 carbon alkoxy groups, and halogen groups. Each G is independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or a substituent represented by the following general formula (3), and R ₁ is Each independently represents an alkylene group having 2 to 4 carbon atoms, and each 1 independently represents a number of 0 to 3.)

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a 20 divalent saturated or unsaturated hydrocarbon groups, and p is a number from 0 to 10.)

Synthesis of diol (h) represented by general formula (8), followed by reaction with polyvalent carboxylic acid or its anhydride, ethylenically unsaturated group-containing alkali-soluble represented by general formula (1) In the production of resins, the reaction is usually carried out in a solvent using a catalyst if necessary.

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; Ketone solvents such as diisobutyl ketone and the like are included. Although there are no particular restrictions on the reaction conditions such as the solvent and catalyst used, it is preferable to use, as the reaction solvent, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature.

In addition, it is preferable to use a catalyst in the reaction between an epoxy group and a carboxyl group or a hydroxyl group. Phosphines such as tris(2,6-dimethoxyphenyl)phosphine are described.

Next, the diol (h) represented by the general formula (8) obtained by reacting the epoxy compound (a-1) with the (meth)acrylic acid and/or (meth)acrylic acid derivative, and a dicarboxylic acid Alternatively, a tricarboxylic acid or its acid anhydride (i) is reacted with a tetracarboxylic acid or its acid dianhydride (j) to form a carboxy group and a polymerizable compound in one molecule represented by the following general formula (1) An alkali-soluble resin having unsaturated groups can be obtained.

(In formula (1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and part of the bonded hydrogen atoms are an alkyl group having 1 to 10 carbon atoms, 1 to 10 aryl or arylalkyl groups, 3 to 10 carbon cycloalkyl or cycloalkylalkyl groups, 1 to 5 carbon alkoxy groups, and halogen groups. Each R ₁ is independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number of 0 to 3, and each G is independently a (meta ) an acryloyl group, a substituent represented by the following general formula (2) or a substituent represented by the following general formula (3), Y is a tetravalent carboxylic acid residue, Z is independently is a hydrogen atom or a substituent represented by the following general formula (4), and at least one is a substituent represented by the following general formula (4), n is a number with an average value of 1 to 20 be.)

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a 20 divalent saturated or unsaturated hydrocarbon groups, and p is a number from 0 to 10.)

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

The acid component used for synthesizing the unsaturated group-containing alkali-soluble resin represented by the general formula (1) is a polyvalent compound capable of reacting with the hydroxyl group in the diol (h) molecule represented by the general formula (8). It is necessary to use a dicarboxylic acid or tricarboxylic acid or their monoanhydride (i) and a tetracarboxylic acid or their dianhydride (j) in combination. The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may contain a bond containing a heteroatom such as —O—, —S—, or a carbonyl group.

Examples of the above dicarboxylic acids or tricarboxylic acids or their monoanhydrides (i) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, Acids, their monoanhydrides, and the like are included.

Examples of monoanhydrides of the above chain hydrocarbon dicarboxylic 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, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like, and dicarboxylic or tricarboxylic acid monoanhydrides introduced with optional substituents.

Further, examples of acid unianhydrides of the above alicyclic dicarboxylic acids or tricarboxylic acids include acid unianhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid, and Acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which arbitrary substituents have been introduced are included.

In addition, examples of the above aromatic dicarboxylic acid or tricarboxylic acid monoanhydrides include acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid. and monoanhydrides of dicarboxylic or tricarboxylic acids into which optional substituents have been introduced.

Among the unianhydrides of dicarboxylic acids or tricarboxylic acids, preferred are succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid.

Moreover, it is preferable to use those acid monoanhydrides in dicarboxylic acid or tricarboxylic acid. The acid 1 anhydrides of dicarboxylic acids or tricarboxylic acids described above may be used alone or in combination of two or more thereof.

Examples of the tetracarboxylic acid or its acid dianhydride (j) include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, or acid dianhydrides thereof. Anhydrides and the like are included.

Examples of the chain hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chains introduced with substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups. Formula hydrocarbon tetracarboxylic acids and the like are included.

Examples of the alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, chain hydrocarbon groups, Alicyclic tetracarboxylic acids into which substituents such as saturated hydrocarbon groups have been introduced are included.

Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and naphthalene-1,4,5,8-tetracarboxylic acid. , naphthalene-2,3,6,7-tetracarboxylic acid and the like.

Also, bis-trimellitic anhydride aryl esters can be used. The bis-trimellitic anhydride aryl esters are, for example, a group of compounds produced by the method described in International Publication No. 2010/074065, and are structurally aromatic diols (naphthalene diol, biphenol, terphenyl diol etc.) and the carboxyl groups of two molecules of trimellitic anhydride are reacted to form an ester bond. These compounds are hereinafter referred to as bis-trimellitic anhydride esters of aromatic diols.

Among the above tetracarboxylic acids or acid dianhydrides thereof, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferred. Moreover, it is preferable to use the tetracarboxylic acid or its acid dianhydride in the said tetracarboxylic acid or its acid dianhydride. The tetracarboxylic acid or its acid dianhydride and the bis-trimellitic anhydride ester of the aromatic diol may be used singly or in combination of two or more thereof.

The reaction between the diol (h) represented by formula (8) and the acid components (i) and (j) is not particularly limited, and known methods can be employed. For example, JP-A-9-325494 describes a method of reacting epoxy (meth)acrylate and tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

Here, epoxy (meth)acrylate (h), dicarboxylic acid or tricarboxylic acid or their acid unihydride (i), tetracarboxylic dianhydride (j) so that the terminal of the compound is a carboxy group It is preferable to carry out the reaction so that the molar ratio (h):(i):(j)=1.0:0.01-1.0:0.2-1.0.

For example, when using acid dianhydride (i) or acid dianhydride (j), the amount of acid component relative to diol (h) containing a polymerizable unsaturated group [(i)/2+(j)] It is preferable to carry out the reaction so that the molar ratio of [[(i)/2+(j)]/(h)] is 0.5 to 1.0. Here, when the molar ratio is 0.5 or more, the content of the diol containing an unreacted polymerizable unsaturated group is not increased, so that the aging stability of the alkali-soluble resin composition is improved. can be done. On the other hand, when the molar ratio is 1.0 or less, the end of the alkali-soluble resin represented by the formula (2) does not become an acid anhydride, so that the content of unreacted acid dianhydride does not increase. Since it can be suppressed, the stability over time of the alkali-soluble resin composition can be improved. In addition, for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (1), the molar ratio of each component (h), (i) and (j) is arbitrarily within the above range. can be changed.

At this time, the molar ratio (i)/(j) of (i) dicarboxylic acid or tricarboxylic acid or its monoanhydride and (j) tetracarboxylic acid or its acid dianhydride is 0.01 or more and 10.0. The following are preferable, and 0.02 or more and less than 3.0 are more preferable. When the molar ratio (i)/(j) is within the above range, it is possible to obtain an optimum molecular weight for obtaining a photosensitive resin composition having good photopatternability. The smaller the molar ratio (i)/(j), the larger the molecular weight and the lower the alkali solubility.

Further, the ethylenically unsaturated bond-containing alkali-soluble resin synthesized by the above reaction preferably has a weight average molecular weight (Mw) of 1000 or more and 20000 or less, and 2000 or more and 10000 or less, from the viewpoint of adjusting the dissolution rate. More preferably, the acid value is 30 mgKOH/g or more and 200 mgKOH/g or less. The weight average molecular weight of the alkali-soluble resin can be determined, for example, by gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation). Also, the acid value can be determined using, for example, a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The ethylenically unsaturated group-containing alkali-soluble resin, which is the component (a), may be used alone or in combination of two or more.

[(b) component]
Component (b) is a photopolymerizable compound having at least two ethylenically unsaturated bonds. By including the component (b), the exposure sensitivity and developability can be improved.

Component (b) The photopolymerizable compound having at least two ethylenically unsaturated bonds preferably has two or more (meth)acryloyl groups, and has three to ten (meth)acryloyl groups. is more preferable. When the photopolymerizable compound has two or more (meth)acryloyl groups, high sensitivity of the photopolymerizable compound to radiation (for example, ultraviolet rays) can be obtained.

Examples of the (b) photopolymerizable compound 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, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) ) acrylates, or (meth)acrylic acid esters such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate , dendrimer-type polyfunctional acrylates, and dendritic polymers having (meth)acrylic groups as compounds having ethylenic double bonds. These photopolymerizable compounds may be used alone or in combination of two or more.

Examples of the above dendritic polymers include dendritic polymers obtained by adding a polyvalent mercapto compound to part of the carbon-carbon double bonds in the (meth)acryloyl groups of polyfunctional (meth)acrylates. . Specifically, it is obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by general formula (9) with a thiol group of a polyvalent mercapto compound represented by general formula (10). Included are dendritic polymers.

(In the formula (9), R ₆ is a hydrogen atom or a methyl group, and R ₇ is the residue of s hydroxyl groups among the k hydroxyl groups of R ₅ (OH) _k donated to the ester bond in the formula. Preferable R ₅ (OH) _k is a polyhydric alcohol based on a straight or branched non-aromatic hydrocarbon skeleton having 2 to 8 carbon atoms, or a plurality of such polyhydric alcohols Molecules are polyhydric alcohol ethers formed by dehydration condensation of alcohols linked through ether bonds, or esters of these polyhydric alcohols or polyhydric alcohol ethers with hydroxy acids, k and s independently It is an integer from 2 to 20, and k≧s.)

(In formula (10), R ₈ is a single bond or a divalent to hexavalent C1 to C6 hydrocarbon group, q is 2 when R ₈ is a single bond, and R ₈ is divalent to hexavalent When it is a group, it is an integer of 2 to 6.)

Examples of polyfunctional (meth)acrylates represented by general formula (9) 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, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolethane 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 Acid di(meth)acrylate, hydroxypivalic acid 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) Acrylates, trimethylolpropane benzoate (meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, alkoxy-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri( (Meth)acrylic acid esters such as meth)acrylates and ditrimethylolpropane tetra(meth)acrylates are included. These compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of polyvalent mercapto compounds represented by general formula (10) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, and trimethylol. Propanetri (mercaptoacetate), Trimethylolpropanetri (mercaptopropionate), Pentaerythritol tetra (mercaptoacetate), Pentaerythritol tri (mercaptoacetate), Pentaerythritol tetra (mercaptopropionate), Dipentaerythritol hexa(mercapto) acetate), dipentaerythritol hexa(mercaptopropionate), and the like. These compounds may be used individually by 1 type, and may use 2 or more types together.

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

The weight ratio (a)/(b) of component (a) and component (b) is preferably 50/50 or more and 90/10 or less, more preferably 60/40 or more and 80/20 or less. When the blending ratio of the component (a) is 50/50 or more, the hardness of the cured film after photocuring is sufficient, and the acid value of the coating film is sufficiently high in the unexposed area, so that the alkali developability is improved. Good, straight and sharp patterns can be formed. Further, when the blending ratio of the component (a) is 90/10 or less, the ratio of the photoreactive functional groups in the resin is sufficient, so that a desired crosslinked structure can be formed. In addition, since the acid value of the resin component is appropriate and the solubility in the alkaline developer in the exposed area is not excessively high, it is possible to suppress the formed pattern from becoming thinner than the target line width and the lack of the pattern. be able to.

[(c) component]
Component (c) is an oxime ester photopolymerization initiator containing a ketoxime. By including the component (c), even in a photosensitive resin composition for a black resist that contains a light shielding agent at a certain level or more and has a large light shielding degree, the reaction in the portion irradiated with radiation (for example, ultraviolet rays) proceeds sufficiently, and development A desired pattern can be formed by reducing the solubility of the hardened portion.

Examples of oxime ester photoinitiators include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane- 1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9 -ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane -1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-acetate, 1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]-ethan-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- ethane-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione 2-o-benzoyloxime, 1-[9-ethyl-6-(2- methylbenzoyl)carbazol-3-yl]ethanone-o-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, Ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyloxime), Ethanone, 1-(-9,9-dibutyl- 7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanediene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 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)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl- 9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime and the like are included.

Furthermore, O-acyloxime-based photopolymerization initiators represented by general formula (11) or general formula (12) are included as a group of compounds with higher sensitivity. Among these compounds, when forming a light-shielding film pattern using a light-shielding agent at a high pigment concentration, an O-acyloxime-based photopolymerization initiator having a molar absorption coefficient at 365 nm of 10000 L/mol·cm or more is used. It is preferable to use

In formula (11), R ₉ and R ₁₀ are each independently a C1-C15 alkyl group, a C6-C18 aryl group, a C7-C20 arylalkyl group or a C4-C12 heterocyclic group; ₁₁ is a C1-C15 alkyl group, a C6-C18 aryl group or a C7-C20 arylalkyl group. Here, the alkyl group and the aryl group may be substituted with a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkanoyl group, or halogen, and the alkylene portion may be an unsaturated bond, an ether bond, It may contain a thioether bond and an ester bond. Also, the alkyl group may be a linear, branched or cyclic alkyl group.

In formula (12), R ₁₂ and R ₁₃ are each independently 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 It is an alkylcycloalkyl group or a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms. R ₁₄ is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the —CH ₂ — groups in the alkyl or alkenyl group are substituted with —O— groups may have been Furthermore, some of the hydrogen atoms in these R ₁₂ to R ₁₄ groups may be substituted with halogen atoms.

The oxime ester photopolymerization initiators exemplified above may be used alone or in combination of two or more.

Examples of photopolymerization initiators that can be used in combination with oxime ester photopolymerization initiators include acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and the like. In addition, the photoinitiator as used in the field of this invention is used in the meaning containing a sensitizer.

A compound that does not act as a photopolymerization initiator or sensitizer by itself, but can be used in combination with the above-mentioned compounds to increase the ability of the photopolymerization initiator or sensitizer can be added. good. Examples of such compounds include amine-based compounds that are effective when used in combination with benzophenone.

The content of component (c) is preferably 3 parts by mass or more and 30 parts by mass or less, and 4 parts by mass or more and 10 parts by mass or less with respect to a total of 100 parts by mass of components (a) and (b). is more preferable. When the content of the component (c) is 3 parts by mass or more, a suitable photopolymerization rate is obtained, and sufficient sensitivity can be ensured. Further, when the content of the component (c) is 30 parts by mass or less, it is possible to reproduce a line width faithful to the mask and to sharpen the pattern edge.

[(d) component]
Component (d) is a light-shielding agent, and examples thereof include black pigments and mixed-color organic pigments.

Examples of black pigments include perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, chromium oxide, iron oxide, and the like.

Examples of mixed color organic pigments include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketo Pseudo-blackening by mixing at least two colors selected from organic pigments such as pyrrolopyrrole pigments and thioindigo pigments is included.

The component (d) may be used alone or in combination of two or more depending on the desired function of the photosensitive resin composition.

Examples of organic pigments that can be used when a mixed-color organic pigment is used as the component (d) include, but are not limited to, those with the following color index names.

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.

Among the above light-shielding agents, carbon black, which is a black pigment, is preferable in terms of light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins.

The blending ratio of component (d) can be arbitrarily determined depending on the desired degree of light blocking, but is preferably 30% by mass or more and 60% by mass or less, and 40% by mass or more, based on the solid content in the photosensitive resin composition. 60% by mass or less is more preferable, and 45% by mass or more and 60% by mass or less is even more preferable. When the amount of the light-shielding agent is 30% by mass or more relative to the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. When the light shielding agent is 60% by mass or less, it contains a sufficient amount of photosensitive resin, so that desired developing properties and film-forming ability can be obtained.

The above component (d) is usually mixed with other ingredients as a light-shielding agent dispersion dispersed in a dispersion medium, and a dispersant can be added at that time. As the dispersant, known compounds used for dispersing pigments (light-shielding components) (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. .

Examples of dispersion media include propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and the like.

Examples of dispersants include cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative dispersants (dispersing aids). In particular, the dispersant has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the light-shielding agent, and has an amine value of 1 mgKOH/g. A cationic polymeric dispersant having a number average molecular weight (Mn) of 1,000 to 100,000 is preferable. The content of the dispersant is preferably 1% by mass or more and 35% by mass or less, more preferably 2% by mass or more and 25% by mass or less, relative to the light shielding agent. High-viscosity substances such as resins generally have the effect of stabilizing dispersion, but those that do not have dispersion-promoting properties are not treated as dispersants. However, it does not limit its use for the purpose of stabilizing the dispersion.

[(e) component]
(e) Component is a coupling agent. The photosensitive resin composition for black resist according to the present invention contains a silane coupling agent and a titanium coupling agent from the viewpoint of improving the adhesion due to chemical bonding between the surface of an inorganic material such as glass and the cured film. .

As the coupling agent, those having a reactive group that has a certain level or more of reactivity with the carboxy group contained in the component (a), etc., which contributes to development with an alkaline developer, can be preferably used. Examples of groups include an amino group, an isocyanate group, a ureido group, an epoxy group, and a mercapto group. Specific examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3 - Ureidopropyltriethoxysilane and the like. When storage stability is emphasized, it is preferable to select a ureido group or a group having the same level of reactivity with the carboxy group, since those with relatively low reactivity with the carboxy group are advantageous. .

The content of the coupling agent is 0.01% by mass or more and 10% by mass or less with respect to the solid content of the photosensitive resin composition. 0.01 mass % or more and 5 mass % or less are preferable. When the content of the coupling agent is 0.01% by mass or more, sufficient adhesion can be obtained between the glass substrate and the cured film. When the content of the coupling agent is 10% by mass or less, generation of agglomerated foreign matter can be suppressed.

[(f) component]
Component (f) is a surfactant having a fluorine atom and an ethylenically unsaturated bond in its molecule. By containing such a component (f), the refractive index of the resin composition excluding the light-shielding agent in the solid content can be induced in a smaller direction, and the surfactant present near the film surface during film formation is eluted during alkali development, and the ink repellent effect of the formed film can be suppressed from being reduced after alkali development. can be kept to a low level. Further, when the partition walls are formed with a film thickness of 2 μm or more, it is possible to impart the pattern cross-sectional shape and the surface ink repellency required for the partition walls. In particular, by having an ethylenically unsaturated bond, it is possible to bond with the above components (a) and (b), so it is presumed that the above effects can be effectively exhibited. .

Examples of the component (f) are polymers having a side chain having an ethylenically unsaturated group and a side chain having a perfluoroalkyl group or a perfluoroether group, such as JP-A-2010-164965 and JP-A-2010-250256. can be used without particular limitation. Specific surfactants include Megafac RS-56, RS-72-A, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 (manufactured by DIC Corporation) and the like can be exemplified. The content of component (f) is 0.01% by mass or more and 10% by mass or less relative to the solid content of the photosensitive resin composition. A preferable lower limit is 0.05% by mass or more, and a more preferable lower limit is 0.1% by mass or more. On the other hand, a preferable upper limit is 5.0% by mass or less, a more preferable upper limit is 3.0% by mass or less, and a further preferable upper limit is 2.5% by mass or less. If the amount is less than 0.01% by mass, the expected effects may not be imparted to the cured film. It is because there exists a possibility that uniform film production may become impossible when it is set to.

[(g) component]
Component (g) is a solvent. By including the component (g), it is possible to obtain a liquid photosensitive resin composition containing the above-described components (a) to (f).

Examples of component (g) include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl- Ketones such as 2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ribs Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like are included. The component (g) may be used alone or in combination of two or more.

Although the content of component (g) varies depending on the target viscosity, it is preferably 60% by mass or more and 90% by mass or less with respect to the total mass of the photosensitive resin composition. When the content of the component (g) is 60% by mass or more, the viscosity can be made easy to apply the photosensitive resin composition on the substrate, and when it is 90% by mass or less, the photosensitive resin The time required for drying after application of the composition can be shortened.

[Other ingredients]
The photosensitive resin composition for a black resist according to the present invention may optionally contain other resin components other than the component (a), a curing agent, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, Additives such as fillers, leveling agents, antifoaming agents, and surfactants other than component (f) may be added.

Examples of resin components other than component (a) include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, melamine resins, epoxy resins, and the like.

Examples of epoxy resins include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol fluorene-type epoxy compounds, bisnaphtholfluorene-type epoxy compounds, diphenylfluorene-type epoxy compounds, phenol novolac-type epoxy compounds, cresol novolak-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.), biphenyl-type epoxy compounds (e.g., JER YX4000: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl-type epoxy compounds , trisphenolmethane-type epoxy compound (eg, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenolethane-type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, methacrylic acid and glycidyl methacrylate A copolymer of a monomer having a (meth)acryloyl group containing glycidyl (meth)acrylate as a unit, typified by a copolymer of hydrogenated bisphenol A diglycidyl ether (for example, Ricaresin HBE-100: Shin Nippon Rika Co., Ltd. company), 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro (3,4 -epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175: manufactured by Huntsman), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical), 3',4' -epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g. Celoxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g. Epolead GT401: Co., Ltd.) Daicel), an epoxy compound having an epoxycyclohexyl group (eg, HiREM-1: manufactured by Shikoku Kasei Co., Ltd.), a polyfunctional epoxy compound having a dicyclopentadiene skeleton (eg, HP7200 series: manufactured by DIC Corporation), 2, 1,2-epoxy-4-(2-oxiranyl)cyclo of 2-bis(hydroxymethyl)-1-butanol Alicyclic epoxy compounds such as rohexane adducts (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd.), epoxy compounds having a silicone skeleton, and the like. included.

Examples of curing agents include amine-based compounds, polycarboxylic acid-based compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, and the like, which contribute to curing of epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to accelerating the curing of epoxy resins. be

Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds and the like. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include glass fibers, silica, mica, alumina, and the like. Examples of leveling agents and antifoaming agents include silicone-based, fluorine-based, and acrylic-based compounds.

Examples of surfactants other than component (f) include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate, and cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride. Amphoteric surfactants such as lauryldimethylamine oxide, 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, non-surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate Examples include ionic surfactants, silicone-based surfactants having polydimethylsiloxane as a main skeleton, and fluorine-based surfactants.

The photosensitive resin composition for black resist of the present invention can be obtained by mixing the above components (a) to (g). In addition, the solid content excluding the solvent (the solid content includes monomers that become solid content after curing) preferably contains 80% by mass or more of the above components (a) to (f) in total, and 90% by mass. It is desirable to include the above.

2. Method for Manufacturing Light-Shielding Film and Partition The method for manufacturing a light-shielding film such as a color filter and a partition is substantially the same in terms of steps, and will be described below.

The method for producing a light-shielding film according to the present invention includes: (1) applying the above-described photosensitive resin composition for black resist onto a substrate and drying to form a coating film of the above-described photosensitive resin composition for black resist; (2) an exposure step of irradiating a portion of the coating film with radiation through a photomask; and (3) developing the coating film irradiated with radiation to remove the unexposed portion. and (4) a heat-curing step of heat-curing the developed coating film. Each step will be described below.

[Coating film forming process]
The coating film forming step is a step of applying the above-described photosensitive resin composition for black resist onto a substrate and drying to form a coating film.

A well-known thing can be used for the said base material. Examples of substrates include glass substrates, silicon wafers, and plastic substrates (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, etc.). Also included are those in which a transparent electrode is vapor-deposited or patterned. It also includes a base material after forming a display function such as a light-emitting layer such as an organic EL on the base material.

A known coating method can be used as a method for coating the photosensitive resin composition. Examples of the coating method include a method using a known solution dipping method, spray method, roller coater, land coater, slit coater or spinner. By these methods, the photosensitive resin composition can be applied to a desired thickness.

A known drying method can be used for drying the photosensitive resin composition applied by the above-described method. The drying method can be carried out by heating with an oven, a hot air blower, a hot plate, an infrared heater, etc., vacuum drying, or a combination thereof. The heating temperature and heating time can be appropriately selected according to the solvent used, and in consideration of the heat resistance temperature of the substrate to be used, for example, it is preferably performed at 60 to 110° C. for 1 to 5 minutes.

[Exposure process]
The exposure step is a step of irradiating a part of the coating film layer with radiation through a photomask and photocuring the part corresponding to the pattern of the coating film (photosensitive resin composition).

A known photomask can be used as the photomask. Examples of photomasks include multi-tone masks such as halftone masks and graytone masks. A gray-tone mask has a light-shielding portion and a diffraction grating formed on a light-transmitting substrate. In the diffraction grating, the intervals between light transmission regions such as slits, dots, and meshes are intervals equal to or less than the resolution limit of light used for exposure, and this configuration controls the transmittance of light. A halftone mask has a light-shielding portion and a semi-transmissive portion formed on a light-transmitting substrate. Transmittance of light used for exposure is controlled by the semi-transmissive portion.

The exposure device and its exposure irradiation conditions in the exposure step can be selected as appropriate. Examples of irradiated radiation include visible light, ultraviolet light, deep ultraviolet light, electron beams, X-rays, and the like. Among the above radiations, ultraviolet rays are preferred. Moreover, a known exposure device (ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, far ultraviolet lamp, etc.) can be used as a device for irradiating radiation. Moreover, the wavelength of the radiation to be irradiated is preferably 250 nm or more and 400 nm or less. The exposure dose of radiation is preferably 25 mJ/cm ² or more and 3000 mJ/cm ² or less.

[Development process]
The development step is a step of alkali-developing the coating film irradiated with radiation to remove the coating film in the unexposed areas.

Examples of coating film development methods include shower development, spray development, dip development, and puddle development. The above developing method can be carried out using a commercially available developing machine, an ultrasonic cleaning machine, or the like.

Examples of developer suitable for development include an aqueous solution of carbonate of alkali metal or alkaline earth metal, an aqueous solution of hydroxide of alkali metal, and the like. Among these, it is preferable to use a weakly alkaline aqueous solution containing 0.05 to 3% by mass of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate at a temperature of 23 to 28°C. In addition, in the development process, a commercially available developing machine, an ultrasonic washing machine, or the like can be used.

[Heat curing step]
The heat-curing step is a step of heat-treating the exposed portion (coating film) after development to perform final curing (post-baking).

The exposed portion (coating film) after development can be heated by a known method (heating with an oven, hot air blower, hot plate, infrared heater, etc., vacuum drying, or a combination thereof). The heating temperature is the temperature at which the coating film is fully cured (post-baking), and is not particularly limited as long as it is a temperature in consideration of the heat resistance of the base material. The heating temperature is preferably 80 to 250° C. for 20 to 120 minutes.

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

First, synthesis examples of the alkali-soluble resin, which is the component (a) of the present invention, will be described. Unless otherwise specified, the resins in the synthesis examples were evaluated as follows.

Note that when the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second position. Further, in the examples, all the glass substrates used for the production of the cured film-attached substrates for measurement were subjected to the same treatment. Moreover, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[Solid content concentration]
The solid content concentration is the weight [W ₁ (g)] obtained by impregnating a glass filter [weight: W ₀ (g)] with 1 g of the resin solution obtained in Synthesis Example, and after heating at 160 ° C. for 2 hours. It was obtained from the following equation using the weight [W ₂ (g)] of .
Solid content concentration (% by weight) = 100 × (W ₂ - W ₀ )/(W ₁ - W ₀ )

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

[Molecular weight]
The molecular weight is determined by gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 ( 1 piece) + TSKgelSuper H-5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) conversion A weight average molecular weight (Mw) was obtained as a value.

Abbreviations used in Synthesis Examples are as follows.
BPFE: bisphenol fluorene type epoxy resin (Ar in the compound of general formula (5) is a phenylene group, l is 0, and the epoxy equivalent is 250 g/eq)
AA: acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride TEAB: tetraethylammonium bromide PGMEA: propylene glycol monomethyl ether Acetate MAA: methacrylic acid MMA: methyl methacrylate CHMA: cyclohexyl methacrylate GMA: glycidyl methacrylate AIBN: azobisisobutyronitrile TPP: triphenylphosphine PTMA: pentaerythritol tetra(mercaptoacetate)
DPHA: mixture of dipentaerythritol pentaacrylate and hexaacrylate HQ: hydroquinone BzDMA: benzyldimethylamine

[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 placed in a 500 mL four-neck flask equipped with a reflux condenser. The mixture was charged and reacted with stirring at 100 to 105° C. for 20 hours. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask and stirred at 120 to 125° C. for 6 hours to prepare an alkali-soluble A resin solution (a)-1 was obtained. The solid content concentration of the resin solution was 56.5% by mass, the acid value (in terms of solid content) was 103 mgKOH/g, and the Mw by GPC analysis was 3600.

[Synthesis Example 2]
MAA (61.98 g, 0.72 mol), MMA (43.25 g, 0.43 mol), and CHMA (48.45 g, 0.43 mol) were placed in a 1000 ml four-necked flask with nitrogen inlet and reflux condenser. 29 mol), AIBN (7.09 g), and diethylene glycol dimethyl ether (432 g) were charged and polymerized by stirring at 80 to 85° C. for 8 hours under a nitrogen stream. Furthermore, GMA (73.69 g, 0.52 mol), TPP (1.76 g), 2,6-di-tert-butyl-p-cresol (0.10 g), and was charged and stirred at 80 to 85 ° C. for 16 hours, acrylate resin solution (a)-2 (solid content concentration: 35.5% by mass, weight average molecular weight (Mw): 21500, acid value (in terms of solid content): 50 mg KOH /g) was obtained.

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

Black resist photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared in the amounts shown in Tables 1 and 2 (unit: % by mass). The ingredients used in Tables 1 and 2 are as follows, but the mass figures of the components (a) to (f) listed in Tables 1 and 2 are the masses of the solid content only, and the solvent content. The mass was added to the (g) component.

(alkali-soluble resin)
(a)-1: Resin obtained in Synthesis Example 1 above (a)-2: Resin obtained in Synthesis Example 2 above

(Photopolymerizable compound)
(b)-1: Dipentaerythritol penta/hexaacrylate mixture (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., "KAYARAD" is a registered trademark of the company)
(b)-2: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Aronix M-450, manufactured by Toagosei Co., Ltd., "Aronix" is a registered trademark of the company)
(b)-3: Dendritic polymer of Synthesis Example 3

(Photoinitiator)
(c): Adeka Arkles NCI-831 (manufactured by ADEKA Co., Ltd., "Adeka Arkles" is a registered trademark of the company)

(Light shielding agent)
The component (d) was mixed as a pigment dispersion liquid (solid content: 25%) of a PGMEA solvent with a carbon black concentration of 20% by mass and a polymer dispersant concentration of 5% by mass. In Tables 1 and 2, the amount of component (d) and dispersant as solid content.

(coupling agent)
(e)-1: 3-(glycidyloxy)propyltrimethoxysilane (e)-2: vinyltriethoxysilane

(Surfactant)
(f) UV-reactive surface modifier Megafac RS-72-A (manufactured by DIC, "Megafac" is a registered trademark of the same company)
(h) Fluorine-containing group/lipophilic group-containing oligomer Megafac F-560 (manufactured by DIC, "Megafac" is a registered trademark of the same company)
(solvent)
(g): propylene glycol monomethyl ether acetate

[evaluation]
(Preparation of cured film for optical density and reflectance evaluation and contact angle evaluation)
The photosensitive resin compositions shown in Tables 1 and 2 were applied onto a glass substrate using a spin coater so that the film thickness after heat curing treatment was 1.5 μm, and then heated at 90° C. using a hot plate. A cured film was produced by pre-baking for 1 minute. Next, without passing through a negative type photomask for pattern formation, a high-pressure mercury lamp with an i-line illuminance of 30 mW/cm ² was used to irradiate ultraviolet light with a wavelength of 365 nm for exposure.

After the exposed cured film was developed using a 0.15% sodium carbonate aqueous solution at 23° C., it was subjected to main curing (post-baking) at 230° C. for 30 minutes using a hot air dryer. A cured film for reflectance evaluation was obtained.

[Optical Density Evaluation]
(Evaluation method)
The film thickness after main curing (post-baking) was measured using a profilometer "Tencor P-17", and the optical density (OD) was measured using a Macbeth transmission densitometer "X-rite 361T (V)". . The optical density (OD) per 1 μm of film thickness was calculated from the measured film thickness and optical density (OD).

[Reflectance evaluation]
(Evaluation method)
For the substrate with a cured film for reflectance evaluation, an ultraviolet-visible near-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) was used at an incident angle of 2 ° on the cured film side (opposite side to the glass substrate) ) was measured.

[Contact angle evaluation]
(Evaluation method)
The contact angle of PGMEA was measured at 25° C. using a contact angle meter “PCA-11” (manufactured by Kyowa Interface Science Co., Ltd.) on the substrate with the cured film for contact angle evaluation.
○: contact angle is 20 ° or more ×: contact angle is less than 20 °

(Preparation of substrate with cured film (coating film) for pattern developability evaluation)
The photosensitive resin compositions for black resist shown in Tables 1 and 2 were coated on a glass substrate of 125 mm × 125 mm using a spin coater so that the film thickness after heat curing treatment was 1.2 μm. °C for 1 minute. After that, the exposure gap was adjusted to 100 μm, the dried coating film was covered with a negative photomask having openings of 5, 7, and 10 μm, and an ultra-high pressure mercury lamp (wavelength 365 nm, i-line illuminance 30 mW/cm ² ) was applied at 80 mJ/cm. A photocuring reaction (exposure) of the photosensitive portion was performed by irradiating ultraviolet rays of cm ² .

Next, the exposed cured film (coating film) was developed in a 0.05% potassium hydroxide aqueous solution at 25° C. under a shower pressure of 1 kgf/cm ² for +10 seconds from the development time when the pattern started to appear. After that, it was washed with water spray of 5 kgf/cm ² to remove the unexposed portion of the coating film, and it was confirmed whether a pixel pattern was formed on the glass substrate.

[Pattern developability evaluation]
(Evaluation method)
○: A pattern formed by a mask with openings of 5, 7, and 10 μm is formed on the substrate. △: A pattern formed by a mask with an opening of 7 and 10 μm is formed on the substrate. ×: An opening of 10 μm. Only the pattern formed by the mask is formed on the substrate

(Preparation of cured film for evaluation of adhesion to glass substrate (PCT adhesion))
Each of the photosensitive resin compositions shown in Tables 1 and 2 was applied onto a glass substrate using a spin coater so that the film thickness after heat curing treatment was 1.0 μm, and heated at 90° C. using a hot plate. A cured film was produced by pre-baking for 1 minute. After that, using a hot air dryer, it was subjected to main curing (post-baking) at 230° C. for 30 minutes. This cured film-coated substrate was exposed to pressure cooker test (PCT) conditions of 121° C., 2 atm, and 100% humidity for 5 hours to obtain a cured film for evaluation of PCT adhesion.

[PCT adhesion evaluation]
(Evaluation method)
The cured film for evaluation is cut so that 100 squares of 1 mm × 1 mm are formed using the product name "Super Cutter Guide" manufactured by Taiyu Kizai Co., Ltd. Cellophane tape (Nichiban A tape peeling test was carried out by sticking and then peeling off the tape (manufactured by the manufacturer), and evaluation was made according to the following criteria.
○: The cured product in the grid is not peeled at all ×: Some peeling is seen in the cured product in the grid

The above evaluation results are shown in Tables 3 and 4.

The coating films obtained from the photosensitive resin compositions of Examples 1 to 10 were obtained by using a surfactant having a fluorine atom and an ethylenically unsaturated bond in the molecule, so that the surfactant was not blended. Compared to Example 1 and Comparative Example 5 using a surfactant (h) having a fluorine-containing group in the molecule but not having an ethylenically unsaturated bond, the reflectance on the coating surface side is reduced. I understand. Moreover, it turns out that there exists a difference also in contact angle evaluation. A contact angle of 20° or more is suitable for applications that require ink repellency, such as barrier ribs for OLEDs. Further, by comparing Examples 1 to 10 and Comparative Example 2, it was found that when the resin of general formula (1) was used as the component (a), the reflectance was reduced, and at a film thickness of 1.2 μm, It can be seen that a fine pattern such as 5 μm can be formed. Furthermore, by comparing Examples 1 to 10 and Comparative Examples 3 to 4, by using a reactive group that can interact with a carboxyl group as a coupling agent and has a certain reactivity, high temperature It was found that sufficient adhesion to the glass substrate on which the film was formed after exposure to high humidity conditions could be ensured.

The photosensitive resin composition for black resist of the present invention can reduce the reflectance on the formed film surface side, can form a fine pattern, and has high adhesion to the glass substrate even after PCT. In particular, various display devices such as organic EL and various It is useful as a light-shielding film for color filters of sensors. It can also be used as a partition wall for partitioning pixels in various display devices including μLEDs.

Claims (6)

(a) an alkali-soluble resin having an ethylenically unsaturated bond;
(b) a photopolymerizable compound having at least two ethylenically unsaturated bonds;
(c) an oxime ester photopolymerization initiator;
(d) a light blocking agent;
(e) a coupling agent having at least a functional group reactive with a carboxy group;
(f) a surfactant having a fluorine atom and an ethylenically unsaturated bond in the molecule;
(g) a solvent;
A photosensitive resin composition for black resist, comprising
The (a) component is a resin represented by the following general formula (1), and the (e) component is 0.01 to 10% by mass and the (f) component is 0.01 to 10% by mass in the solid content excluding the solvent. % by mass of a photosensitive resin composition for a black resist.

(In formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and part of the bonded hydrogen atoms are alkyl groups having 1 to 10 carbon atoms, substituted with a substituent selected from the group consisting of 10 aryl or arylalkyl groups, cycloalkyl or cycloalkylalkyl groups having 3 to 10 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen groups; Each R ₁ is independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number of 0 to 3, each G is independently a (meth)acryloyl group, A substituent represented by the following general formula (2) or a substituent represented by the following general formula (3), Y is a tetravalent carboxylic acid residue, Z is independently a hydrogen atom or a substituent represented by the following general formula (4), one or more of which is a substituent represented by the following general formula (4). n is a number with an average value of 1 to 20.)

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a 20 divalent saturated or unsaturated hydrocarbon groups, and p is a number from 0 to 10.)

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a number of 1 or 2.) 2. The photosensitive resin composition for a black resist according to claim 1, wherein the component (d) is carbon black and is contained in the solid content excluding the component (g) in an amount of 30 to 60% by mass. A cured film obtained by curing the photosensitive resin composition for a black resist according to claim 1 or 2. A coating film forming step of applying the photosensitive resin composition for black resist according to claim 1 or 2 onto a substrate and drying to form a coating film of the photosensitive resin composition for black resist;
An exposure step of irradiating a part of the coating film with radiation through a photomask;
a developing step of developing the coating film irradiated with radiation and removing an unexposed portion;
A heat-curing step of heat-curing the developed coating film;
A method for producing a cured film, comprising: A color filter comprising the cured film according to claim 3 as a light shielding film. A partition made of the cured film according to claim 3.