KR20230170903A - Photosensitive resin composition, and organic EL device partition - Google Patents

Abstract

Provision of a highly sensitive photosensitive resin composition containing a black colorant that allows development and pattern formation even at low exposure doses. (A) a binder resin, (B1) a first quinonediazide adduct that is a quinonediazide adduct to a first phenol compound, and (B2) a second quinonediazide adduct that is a quinonediazide adduct to a second phenol compound. A photosensitive resin composition containing a sieve and (C) a black colorant, wherein the difference between the molecular weight of the first phenol compound and the molecular weight of the second phenol compound is 40 to 500, and the molecular weight of the first phenol compound is the molecular weight of the second phenol compound. Smaller photosensitive resin composition.

Description

Photosensitive resin composition, and organic EL device partition

The present invention relates to a photosensitive resin composition, and an organic EL device barrier rib, an organic EL device insulating film, and an organic EL device using the same. More specifically, the present invention relates to a photosensitive resin composition containing a black colorant, and an organic EL device barrier rib, an organic EL device insulating film, and an organic EL device using the same.

In display devices such as organic EL displays (OLED), partition materials are used in gaps between colored patterns within the display area or edges around the display area to improve display characteristics. In the manufacture of an organic EL display device, partition walls are first formed to prevent organic material pixels from contacting each other, and then organic material pixels are formed between the partition walls. This partition is generally formed by photolithography using a photosensitive resin composition and has insulating properties. In detail, the photosensitive resin composition is applied onto the substrate using a coating device, the volatile components are removed by means such as heating, and then exposed through a mask, and then, in the case of negative type, the unexposed portion is exposed to the positive type. In this case, the exposed portion is developed by removing it with a developing solution such as an aqueous alkaline solution, and the obtained pattern is heat treated to form a partition (insulating film). Next, an organic material that emits three colors of red, green, and blue light is deposited between the partition walls using an inkjet method or the like to form pixels of an organic EL display device.

In the above field, in recent years, with the miniaturization of display devices and the diversification of displayed content, there has been a demand for higher performance and higher resolution of pixels. In order to increase the contrast in a display device and improve visibility, attempts are being made to give partition materials light-shielding properties using colorants. However, when the partition material is provided with light-shielding properties, the photosensitive resin composition tends to have reduced sensitivity, and as a result, the exposure time becomes long and there is a risk that productivity may decrease. Therefore, the photosensitive resin composition used to form the partition material containing the colorant is required to have higher sensitivity.

Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-281440) is a radiation-sensitive resin composition that exhibits high light-shielding properties by heat treatment after exposure, and is a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound. A composition containing titanium black is described.

Patent Document 2 (Japanese Patent Application Laid-Open No. 2002-116536) discloses a radiation-sensitive resin composition containing [A] alkali-soluble resin, [B] 1,2-quinonediazide compound, and [C] colorant, wherein carbon A method of blackening a partition material using black is described.

Patent Document 3 (Japanese Patent Application Laid-Open No. 2010-237310) is a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure, and describes a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound. A composition containing a heat-sensitive dye is described.

Patent Document 4 (International Publication No. 2017/069172) discloses at least one type of black dye selected from (A) a binder resin, (B) a quinonediazide compound, and (C) a solvent black dye defined by a color index of 27 to 47. A positive type photosensitive resin composition containing black dye is described.

Japanese Patent Publication No. 2001-281440 Japanese Patent Publication No. 2002-116536 Japanese Patent Publication No. 2010-237310 International Publication No. 2017/069172

In the photosensitive resin composition used to form a colored partition material, it is necessary to use a significant amount of a colorant in order to sufficiently increase the light-shielding properties of the cured film. When such a large amount of colorant is used, the radiation irradiated to the film of the photosensitive resin composition is absorbed by the colorant, so the effective intensity of the radiation in the film decreases, and the photosensitive resin composition is not sufficiently exposed, resulting in pattern formation. Sexuality decreases.

In forming a barrier rib in an organic EL device, it is important that the material forming the barrier rib be highly sensitive from the viewpoint of productivity and the like. However, when using a black photosensitive resin composition containing a colorant, exposure defects occur under the exposure conditions normally used, so, for example, it is necessary to lengthen the exposure time, which has become a factor in reducing productivity. Therefore, there is a strong desire to reduce the exposure amount of the photosensitive resin composition, reduce energy costs, and increase throughput.

The purpose of the present invention is to provide a highly sensitive photosensitive resin composition containing a black colorant that allows development and pattern formation even at low exposure doses.

The present inventor has described a photosensitive resin composition containing a binder resin, a quinonediazide adduct of a phenol compound, and a black colorant, comprising a plurality of quinonediazide adducts having different molecular weights of the phenolic compounds constituting the quinonediazide adduct. It was found that by using the system, development and pattern formation became possible even at a low exposure amount, despite containing a black colorant.

That is, the present invention includes the following forms.

[One]

(A) binder resin,

(B1) a first quinonediazide adduct that is a quinonediazide adduct to a first phenol compound,

(B2) a second quinonediazide adduct, which is a quinonediazide adduct to a second phenol compound,

(C) Black colorant

A photosensitive resin composition comprising a photosensitive resin, wherein the difference between the molecular weight of the first phenol compound and the molecular weight of the second phenol compound is 40 to 500, and the molecular weight of the first phenol compound is smaller than the molecular weight of the second phenol compound. Composition.

[2]

The photosensitive resin composition according to [1], wherein the first phenol compound and the second phenol compound each have 3 or more phenolic hydroxyl groups.

[3]

The photosensitive resin composition according to [1] or [2], wherein the phenolic hydroxyl equivalent weight of the first quinonediazide adduct is 100 to 1500, and the phenolic hydroxyl equivalent weight of the second quinonediazide adduct is 180 to 800.

[4]

The average number of phenolic hydroxyl groups of the first quinonediazide adduct is 0.1 to 3.0 per molecule, and the average number of phenolic hydroxyl groups of the second quinonediazide adduct is 0.5 to 5.0 per molecule. 3] The photosensitive resin composition according to any one of the above.

[5]

[1] to [4, wherein the first quinonediazide adduct is a 1,2-naphthoquinonediazide-4-sulfonic acid ester or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of the first phenol compound. ] The photosensitive resin composition according to any one of the above.

[6]

[1] to [5, wherein the second quinonediazide adduct is 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of the second phenol compound. ] The photosensitive resin composition according to any one of the above.

[7]

The photosensitive resin composition according to any one of [1] to [6], wherein the first phenol compound has a molecular weight of 230 or more and less than 300, and the second phenol compound has a molecular weight of 300 or more and 600 or less.

[8]

Based on 100 parts by mass of the binder resin, [1] comprising 5 to 70 parts by mass of the first quinonediazide adduct and 5 to 70 parts by mass of the second quinonediazide adduct. The photosensitive resin composition according to any one of to [7].

[9]

[ The photosensitive resin composition according to any one of 1] to [8].

[10]

The binder resin includes a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, and the copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is represented by formula (1)

(In formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.)

The photosensitive resin composition according to any one of [1] to [9], which has a structural unit represented by .

[11]

The binder resin includes a resin having an epoxy group and a phenolic hydroxyl group, and the resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and the formula (7)

(In formula (7), b is an integer of 1 to 5, and * represents the bonding portion of a compound having at least two epoxy groups in one molecule with a residue excluding the epoxy group involved in the reaction.)

The photosensitive resin composition according to any one of [1] to [10], which is a compound having the structure.

[12]

The photosensitive resin composition according to [11], wherein the compound having at least two epoxy groups in one molecule is a novolak-type epoxy resin.

[13]

The binder resin is expressed in equation (4)

(In formula (4), R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁰ is an acid decomposable group, r is an integer of 0 to 5, s is an integer of 0 to 5, However, r+s is an integer from 1 to 5.)

The photosensitive resin composition according to any one of [1] to [12], which contains a resin having a structural unit represented by at least one structural unit represented by formula (4) where s is an integer of 1 or more.

[14]

The photosensitive resin composition according to any one of [1] to [13], wherein the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm of film thickness.

[15]

The photosensitive resin composition according to any one of [1] to [14], wherein the black colorant is a dye defined by a color index (C.I.) of solvent black 27 to 47.

[16]

The photosensitive resin composition according to any one of [1] to [15], comprising 10 to 150 parts by mass of the black colorant based on 100 parts by mass of the binder resin.

[17]

An organic EL device partition comprising a cured product of the photosensitive resin composition according to any one of [1] to [16].

[18]

An organic EL device insulating film comprising a cured product of the photosensitive resin composition according to any one of [1] to [16].

[19]

An organic EL device comprising a cured product of the photosensitive resin composition according to any one of [1] to [16].

According to the present invention, a highly sensitive photosensitive resin composition containing a black colorant capable of development and pattern formation even at a low exposure amount can be provided.

The present invention will be described in detail below.

In the present disclosure, “alkali solubility” and “alkali aqueous solution solubility” mean that the photosensitive resin composition or its components, or the film or cured film of the photosensitive resin composition is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. “Alkali-soluble functional group” means a group that imparts such alkali solubility to the photosensitive resin composition or its components, or to the coating or cured coating of the photosensitive resin composition. Examples of alkali-soluble functional groups include phenolic hydroxyl group, carboxyl group, sulfo group, phosphoric acid group, acid anhydride group, and mercapto group.

In the present disclosure, “acid-decomposable group” means a group that decomposes (deprotects) and generates an alkali-soluble functional group by heating as necessary in the presence of an acid.

In the present disclosure, “radical polymerizable functional group” means an ethylenically unsaturated group, and “radically polymerizable compound” means a compound having one or more ethylenically unsaturated groups.

In the present disclosure, “structural unit” means an atomic group constituting a part of the basic structure of a polymer, and this atomic group may have a pendant atom or a pendant atomic group. For example, in the case of a radical (co)polymer, it means a unit derived from a radically polymerizable compound used as a monomer, and in the case of a phenol novolak resin, it means one molecule of phenol (C ₆ H ₅ OH) and one molecule of form. It refers to the following units formed from the condensation reaction of aldehyde (HCHO). With respect to a structural unit having a pendant group (side group), a structural unit having a pendant group or a group derived therefrom used in the formation of a cross-linking site and a structural unit having a free pendant group not involved in the formation of the cross-linking site are mutually exclusive. considered different. For a polymer having a branched molecular chain (branched chain), the structural unit (branched unit) containing the branch point and the structural unit included in the linear molecular chain are considered to be different from each other.

In the present disclosure, “(meth)acrylic” means acrylic or methacryl, “(meth)acrylate” means acrylate or methacrylate, and “(meth)acryloyl” means acryloyl or It means methacryloyl.

In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin, polymer or copolymer are measured at 40° C. by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase. It refers to the standard polystyrene conversion value being measured.

In the present disclosure, “solid content” refers to (A) binder resin, (B1) first quinonediazide adduct, (B2) second quinonediazide adduct, (C) black colorant, and optional dissolution accelerator (D) ), and the total mass of components including the optional component (E) and excluding the solvent (F).

[Photosensitive resin composition]

The photosensitive resin composition of one embodiment includes (A) a binder resin, (B1) a first quinonediazide adduct that is a quinonediazide adduct to a first phenol compound, and (B2) a second phenol different from the first phenol compound. It contains a second quinonediazide adduct, which is a quinonediazide adduct to the compound, and (C) a black colorant.

<Binder Resin (A)>

The binder resin (A) is not particularly limited, but it preferably has an alkali-soluble functional group and is alkali-soluble. The alkali-soluble functional group is not particularly limited, and examples include a carboxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, and a mercapto group. You may use a binder resin having two or more types of alkali-soluble functional groups.

Examples of the binder resin (A) include homopolymers or copolymers of polymerizable monomers having an alkali-soluble functional group, and resins having an epoxy group and a phenolic hydroxyl group. Other binder resins (A) include, for example, acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamic acid resin, polybenzoxazole resin, polybenzoxazole resin precursor, and silicone resin. , cyclic olefin polymers, cardo resins, derivatives of these resins, and those in which an alkali-soluble functional group is bonded to these resins. For example, as a derivative of a phenol resin, a polyalkenylphenol resin in which an alkenyl group is bonded to a benzene ring, and as a derivative of a polystyrene resin, a hydroxypolystyrene resin derivative in which a phenolic hydroxyl group, a hydroxyalkyl group, or an alkoxy group is bonded to a benzene ring. You can. These resins can be used individually or in combination of two or more types.

The binder resin (A) may have a radically polymerizable functional group. In one embodiment, the binder resin (A) has a (meth)acryloyloxy group, allyl group, or methallyl group as a radically polymerizable functional group.

Some or all of the alkali-soluble functional groups of the binder resin (A), such as phenolic hydroxyl groups, may be protected by acid-decomposable groups. The alkali solubility of the binder resin (A) protected with an acid-decomposable group before exposure is suppressed. The quinonediazide adducts (B1) and (B2) described later generate alkali-soluble carboxylic acid compounds when irradiated with radiation such as visible light, ultraviolet light, γ-ray, or electron beam. The produced carboxylic acid compound promotes decomposition of the acid-decomposable group of the binder resin (A) and regenerates the alkali-soluble functional group, thereby increasing the alkali solubility of the binder resin (A). As a result, the change in alkali solubility before and after exposure of the binder resin (A) (before and after decomposition of the acid-decomposable group) increases, and the resolution of the pattern can be further improved.

(Copolymer (a1) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers)

In one embodiment, the binder resin (A) is a copolymer (a1) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer (in the present disclosure, it is also simply referred to as “alkali aqueous solution-soluble copolymer (a1)”). Includes. Examples of the alkali-soluble functional group include a carboxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, and a mercapto group. Polymerizable functional groups possessed by the polymerizable monomer include radically polymerizable functional groups, for example, CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CHCO-, CH ₂ =C(CH ₃ ) CO-, -OC-CH=CH-CO-, etc. can be mentioned.

The aqueous alkali solution-soluble copolymer (a1) can be produced, for example, by radically polymerizing a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers. After synthesizing a copolymer by radical polymerization, a derivative obtained by adding an alkali-soluble functional group to the copolymer may be used. Examples of polymerizable monomers having an alkali-soluble functional group include (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chlor(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid. Acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimide propionic acid, 4-maleic acid. Polymerizable monomers having a carboxyl group such as midbutyric acid and 6-maleimide hexanoic acid; Phenolics such as 4-hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenylacrylamide, and 4-hydroxyphenyl maleimide Polymerizable monomer having a hydroxyl group; Polymerizable monomers having a sulfo group such as (meth)allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, and styrenesulfonic acid; Polymerizable monomers having a phosphoric acid group such as mono(2-(meth)acryloyloxyethyl) phosphate; and polymerizable monomers having an acid anhydride group such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Other polymerizable monomers include, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; Ether compounds of vinyl alcohol such as vinyl-n-butyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec- Butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate Rate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2,2 (meth)acrylic acid esters such as 2-trifluoroethyl (meth)acrylate and 2,2,3,3-tetrafluoropropyl (meth)acrylate; N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide can be mentioned. From the viewpoint of heat resistance and the like, the alkali aqueous solution-soluble copolymer (a1) preferably has one or more types of cyclic structures such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure.

The polymerizable monomer having an alkali-soluble functional group preferably has one or more types of cyclic structures. The polymerizable monomer having an alkali-soluble functional group preferably has a phenolic hydroxyl group. The polymerizable monomer having an alkali-soluble functional group is a radically polymerizable functional group, such as a (meth)acrylic compound having CH ₂ =CHCO- or CH ₂ =C(CH ₃ )CO-, and -OC-CH=CH-CO- It is preferable that it is at least one type selected from the group consisting of maleimide compounds having. A polymerizable monomer having an alkali-soluble functional group, which after polymerization has formula (1)

It is more preferable to form a structural unit represented by . In formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. R ¹ is preferably a hydrogen atom or a methyl group. It is preferable that a is an integer of 1 to 3, and it is more preferable that it is 1. As a polymerizable monomer having such an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is particularly preferred.

As other polymerizable monomers, after polymerization, formula (2)

Polymerizable monomers that form structural units represented by are preferred. In formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom, R ⁴ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. It is a phenyl group substituted with at least one type selected from the group. R ² and R ³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. R ⁴ is a phenyl group substituted with at least one member selected from the group consisting of a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. It is preferable, and it is more preferable that it is a cyclic alkyl group with 3 to 12 carbon atoms, or a phenyl group. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

Alkaline aqueous solution soluble copolymer (a1) is expressed by formula (1)

(In formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.)

It is preferable to have a structural unit represented by .

Alkaline aqueous solution-soluble copolymer (a1) is expressed by formula (2)

(In formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom. , R ⁴ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. It is a phenyl group substituted with at least one member selected from the group consisting of:

It is preferable to have a structural unit represented by .

It is particularly preferable to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having an alkali-soluble functional group, and to use phenylmaleimide or N-cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radically polymerizing these polymerizable monomers, shape retention and developability can be improved, and outgassing can also be reduced.

The polymerization initiator when producing the alkali aqueous solution-soluble copolymer (a1) by radical polymerization is not limited to the following, but includes 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbuty) Ronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethyl) azo polymerization initiators such as valeronitrile (AVN); Dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl Peroxide polymerization initiators with a 10-hour half-life temperature of 100 to 170°C, such as hydroperoxide and cumene hydroperoxide; Alternatively, peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, and tert-butylperoxypivalate can be used. It is preferable that the amount of the polymerization initiator used is generally 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less. .

A RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with a polymerization initiator. The RAFT agent is not limited to the following, but thiocarbonylthio compounds such as dithioester, dithiocarbamate, trithiocarbonate, and xanthate can be used. The RAFT agent can be used in the range of 0.005 to 20 parts by mass, and is preferably used in the range of 0.01 to 10 parts by mass, based on a total of 100 parts by mass of the polymerizable monomer.

The weight average molecular weight (Mw) of the aqueous alkali solution-soluble copolymer (a1) can be 3,000 to 80,000, preferably 4,000 to 70,000, and more preferably 5,000 to 60,000. The number average molecular weight (Mn) can be 1,000 to 30,000, preferably 1,500 to 25,000, and more preferably 2,000 to 20,000. Polydispersity (Mw/Mn) can be set to 1.0 to 3.5, preferably 1.1 to 3.0, and more preferably 1.2 to 2.8. By setting the weight average molecular weight, number average molecular weight, and polydispersity within the above ranges, a photosensitive resin composition excellent in alkali solubility and developability can be obtained.

In one embodiment, the photosensitive resin composition contains 1 mass% to 50 mass% of the alkali aqueous solution-soluble copolymer (a1), preferably 2 mass% to 40 mass%, more preferably, based on 100 mass% of the solid content. It contains 5% by mass to 30% by mass. If the content of the alkali aqueous solution-soluble copolymer (a1) is 1% by mass or more based on 100% by mass of solid content, dissolution of the exposed area can be promoted, high sensitivity can be achieved, and stability and durability of the film after heat curing can be secured. there is. If the content of the alkali aqueous solution-soluble copolymer (a1) is 50% by mass or less based on 100% by mass of solid content, the solubility of the unexposed area can be suppressed low and the residual film rate can be maintained high.

(Protection Resin (a2))

The binder resin (A) may contain the above-described alkali aqueous solution-soluble copolymer (a1) as a base resin, and may contain a protective resin (a2) in which at least a part of the alkali-soluble functional group is protected by an acid-decomposable group. The protective resin (a2) has a large change in alkali solubility before and after exposure (before and after decomposition of the acid-decomposable group), and as a result, the resolution of the pattern can be further increased. The acid generated during exposure catalytically promotes the decomposition (deprotection) of the acid-decomposable group and the phenolic hydroxyl group is regenerated. After exposure, post exposure bake (PEB) may be performed as needed. This promotes alkali dissolution of the protective resin (a2) in the exposed area during development. Protective resin (a2) can be used individually or in combination of two or more types. For example, the protective resin (a2) may be a combination of two or more types of resins that differ in the protection rate of polymer structural units, acid-decomposable groups, and alkali-soluble functional groups, or a combination thereof.

The alkali-soluble functional group in the protective resin (a2) is preferably a phenolic hydroxyl group. Because part of the phenolic hydroxyl group is protected by an acid-decomposable group, the alkali solubility of the protective resin (a2) before exposure to light is suppressed. The base resin of the protective resin (a2) preferably has a phenolic hydroxyl group on the benzene ring pendant to the polymer main chain. In the base resin of the protective resin (a2) having this structure, a benzene ring having a phenolic hydroxyl group constitutes the polymer main chain, and compared to a novolak resin having an equivalent hydroxyl value, an alkaline compound in a developer solution easily approaches the phenolic hydroxyl group. High alkali solubility.

(Protection of phenolic hydroxyl group by acid-decomposable group)

In an embodiment in which the alkali-soluble functional group of the protective resin (a2) is a phenolic hydroxyl group, the protective resin (a2) uses the above-mentioned alkali aqueous solution-soluble copolymer (a1) having a phenolic hydroxyl group as a base resin, and the alkali-soluble functional group of the protective resin (a2) is a phenolic hydroxyl group. It can be obtained by protecting a part of it with an acid-decomposable group. The protective resin (a2) having a phenolic hydroxyl group protected by an acid-decomposable group has a partial structure of Ar-OR ⁵ , where Ar represents an aromatic ring derived from phenol and R ⁵ represents an acid-decomposable group.

An acid-decomposable group is a group that decomposes (deprotects) and generates an alkali-soluble functional group by heating as necessary in the presence of an acid. Specifically, for example, tert-butyl group, 1,1-dimethyl-propyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1 -Groups having tertiary alkyl groups such as methyl adamantyl group, 1-ethyl adamantyl group, tert-butoxycarbonyl group, and 1,1-dimethyl-propoxycarbonyl group; Silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group, and t-butyldiphenylsilyl group; and equation (3)

-CR ⁶ R ⁷ -OR ⁸ (3)

(In formula (3), R ⁶ and R ⁷ are each independently a hydrogen atom, a straight-chain alkyl group with 1 to 4 carbon atoms, or a branched alkyl group with 3 to 4 carbon atoms, and R ⁸ is an alkyl group with 1 to 4 carbon atoms. It is a straight chain alkyl group of 12 carbon atoms, a branched alkyl group of 3 to 12 carbon atoms, a cyclic alkyl group of 3 to 12 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms, and R ⁶ Alternatively, one side of R ⁷ and R ⁸ may be combined to form a ring structure with a reduced number of 3 to 10, and R ⁶ , R ⁷ and R ⁸ may be substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine. .) can be mentioned. The group represented by formula (3) forms an acetal structure or a ketal structure together with the oxygen atom derived from the phenolic hydroxyl group. These acid-decomposable groups can be used individually or in combination of two or more types.

Since a highly sensitive photosensitive resin composition can be obtained even at a low exposure dose, the acid-decomposable group is preferably a group represented by formula (3). R ⁶ and R ⁷ are each independently a hydrogen atom, a straight-chain alkyl group with 1 to 4 carbon atoms, or a branched alkyl group with 3 to 4 carbon atoms, and R ⁸ is selected from the group consisting of fluorine, chlorine, bromine and iodine. More preferably, it is a straight-chain alkyl group with 1 to 12 carbon atoms that may be substituted with a halogen atom, a branched alkyl group with 3 to 12 carbon atoms, or a cyclic alkyl group with 3 to 12 carbon atoms. Examples of such acid-decomposable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-( Examples include 2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group, and 1-ethoxyethyl group and 1-n-propoxyethyl group is preferred. As the acid-decomposable group, a group represented by formula (3) in which one of R ⁶ or R ⁷ and R ⁸ are combined to form a ring structure with a reduction number of 3 to 10 can also be preferably used. At this time, R ⁶ or R ⁷ that is not involved in the formation of the ring structure is preferably a hydrogen atom. Examples of such acid-decomposable groups include 2-tetrahydrofuranyl group and 2-tetrahydropyranyl group, with 2-tetrahydrofuranyl group being preferred.

The protection reaction of the phenolic hydroxyl group can be carried out under known conditions using a general protecting agent. For example, the protective resin (a2) can be obtained by reacting the base resin and the protective agent in the presence of an acid or base at a reaction temperature of -20 to 50°C without a solvent or in a solvent such as toluene or hexane.

As a protective agent, a known protective agent capable of protecting phenolic hydroxyl groups can be used. As a protective agent, for example, isobutene can be used when the acid-decomposable group is a tert-butyl group, and di-tert-butyl bicarbonate can be used when the acid-decomposable group is a tert-butoxycarbonyl group. If the acid-decomposable group is a silyl group such as trimethylsilyl group or triethylsilyl group, use silicon-containing chloride such as trimethylsilyl chloride or triethylsilyl chloride, or silicon-containing triflate compound such as trimethylsilyl triflate or triethylsilyl triflate. You can use it. If the acid-decomposable group is a methoxymethyl group, it is chloromethyl methyl ether, if it is a 1-ethoxyethyl group, it is ethyl vinyl ether, if it is a 1-n-propoxyethyl group, it is n-propyl vinyl ether, and if it is a 2-tetrahydrofuranyl group. 2,3-dihydrofuran, and in the case of a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran, etc. can be used.

Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid. Salts of organic acids, such as the pyridinium salt of p-toluenesulfonic acid, can also be used as an acid source. Examples of bases include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate and cesium carbonate, metal hydrides such as sodium hydride, and pyridine, N,N-dimethyl-4. -Amine compounds such as aminopyridine, imidazole, triethylamine, and diisopropylethylamine can be mentioned.

In another embodiment, the phenolic hydroxyl group of the polymerizable monomer having a phenolic hydroxyl group is protected by an acid-decomposable group, and then the polymerizable monomer having a phenolic hydroxyl group protected by an acid-decomposable group and, if necessary, other polymerizable monomers are polymerized or copolymerized. By doing so, protective resin (a2) can also be obtained. Protection of the phenolic hydroxyl group of the polymerizable monomer having a phenolic hydroxyl group can be performed in the same manner as protection of the phenolic hydroxyl group of the base resin.

The protective resin (a2) is expressed in equation (4)

(In formula (4), R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁰ is an acid decomposable group, r is an integer from 0 to 5, s is an integer from 0 to 5, However, it is preferable to have at least one structural unit represented by formula (4) where r+s is an integer of 1 to 5) and where s is an integer of 1 or more. The acid-decomposable group for R ¹⁰ is preferably a group represented by the above formula (3).

The protective resin (a2) is expressed in equation (2)

(In formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom. , R ⁴ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. It is a phenyl group substituted with at least one type selected from the group consisting of). It is preferable to have a structural unit represented by. R ² and R ³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. R ⁴ is a phenyl group substituted with at least one member selected from the group consisting of a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. It is preferable, and it is more preferable that it is a cyclic alkyl group with 3 to 12 carbon atoms, or a phenyl group.

In one embodiment, the number of structural units represented by formula (4) where s is an integer of 1 or more, that is, structural units represented by formula (4) where at least one phenolic hydroxyl group is protected by an acid-decomposable group, is the protective resin ( It is 5% to 95%, preferably 15% to 70%, and more preferably 25% to 60% of the total number of structural units of a2). By setting the ratio of the above structural units to 5% or more, a chemical amplification function can be imparted to the photosensitive resin composition, making it possible to realize high sensitivity. By setting the ratio of the structural units to 95% or less, the remaining amount of unreacted acid-decomposable groups can be reduced, solubility in the exposed area can be increased, and high sensitivity can be realized.

In one embodiment, the photosensitive resin composition contains 5% by mass to 50% by mass of the protective resin (a2), preferably 10% by mass to 40% by mass, more preferably 15% by mass to 15% by mass, based on 100% by mass of solid content. Contains 30% by mass. If the content of the protective resin (a2) is 5% by mass or more based on 100% by mass of solid content, dissolution of the exposed area can be promoted and a difference can be provided in the solubility of the unexposed area and the exposed area, so that high sensitivity can be achieved. The stability and durability of the film after heat curing can be secured. If the content of the protective resin (a2) is 50% by mass or less based on 100% by mass of solid content, the solubility of the unexposed area can be suppressed low and the residual film rate can be maintained high.

(Resin (a3) having an epoxy group and a phenolic hydroxyl group)

The binder resin (A) may contain a resin (a3) having an epoxy group and a phenolic hydroxyl group. Resin (a3) having an epoxy group and a phenolic hydroxyl group is an aqueous alkaline solution-soluble resin. Resin (a3) having an epoxy group and a phenolic hydroxyl group may have an alkali-soluble functional group other than the phenolic hydroxyl group. The phenolic hydroxyl group and other alkali-soluble functional groups may be protected by an acid-decomposable group. Resin (a3) having an epoxy group and a phenolic hydroxyl group is, for example, a portion of the epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as “epoxy compound”) and hydroxybenzoic acid. It can be obtained by reacting the carboxyl group of the compound. The epoxy group of the resin (a3) having an epoxy group and a phenolic hydroxyl group forms a crosslink by reaction with the phenolic hydroxyl group during heat treatment (post-baking) after development, thereby improving the chemical resistance, heat resistance, etc. of the film. there is. Since the phenolic hydroxyl group contributes to the solubility in the aqueous alkaline solution during development, the resin (a3) having an epoxy group and a phenolic hydroxyl group is a binder resin (A3) in which the acid-decomposable group is not sufficiently decomposed (deprotected) when exposed to low exposure dose. ) also functions as a dissolution accelerator, thereby making it possible to make the photosensitive resin composition highly sensitive.

An example of a reaction in which one epoxy group of an epoxy compound reacts with a carboxyl group of a hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group is shown in Scheme 1 below.

Compounds having at least two epoxy groups in one molecule include, for example, novolak-type epoxy resins such as phenol novolak-type epoxy resins and cresol novolak-type epoxy resins, bisphenol-type epoxy resins, biphenol-type epoxy resins, and naphthalene skeleton-containing compounds. Examples include epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds just need to have two or more epoxy groups in one molecule and can be used individually or in combination of two or more types. Since these compounds are thermosetting types, their structures cannot be described in the same manner due to differences in the presence or absence of an epoxy group, type of functional group, degree of polymerization, etc., according to the common sense of those skilled in the art. An example of the structure of a novolak-type epoxy resin is shown in equation (6). In formula (6), for example, R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group or hydroxyl group having 1 to 2 carbon atoms, and m is an integer of 1 to 50.

Examples of the phenol novolak-type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC Chemical Industries, Ltd.), and jER (registered trademark) -152 (manufactured by Mitsubishi Chemical Corporation). Examples of the cresol novolak-type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Chemical Industry Co., Ltd.), and EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Chemical Co., Ltd.). Examples of bisphenol-type epoxy resins include bisphenol such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Chemical Co., Ltd.), and YD-128 (brand name, manufactured by Nittetsu Chemical & Materials Co., Ltd.) A-type epoxy resin, and bisphenol F-type epoxy resins such as jER (registered trademark) 806 (manufactured by Mitsubishi Chemical & Chemical Co., Ltd.) and YDF-170 (brand name, manufactured by Nittetsu Chemical & Materials Co., Ltd.). Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000, and jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation). Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Chemical Co., Ltd.) and EXA-4750 (trade name, manufactured by DIC Chemical Industry Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE (registered trademark)-3150 (manufactured by Daicel Chemical Industry Co., Ltd.). Examples of heterocyclic epoxy resins include TEPIC (registered trademark), TEPIC-L, TEPIC-H, and TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.).

The compound having at least two epoxy groups in one molecule is preferably a novolak-type epoxy resin, and more preferably is at least one type selected from the group consisting of phenol novolak-type epoxy resin and cresol novolak-type epoxy resin. The photosensitive resin composition containing resin (a3) having an epoxy group and a phenolic hydroxyl group derived from a novolak-type epoxy resin has excellent pattern formation properties, easy control of alkali solubility, and low outgassing.

Hydroxybenzoic acid compounds are compounds in which at least one position from 2 to 6 of benzoic acid is substituted with a hydroxyl group, for example, salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxy Benzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3- Examples include hydroxy-4-nitrobenzoic acid and 4-hydroxy-3-nitrobenzoic acid, and dihydroxybenzoic acid compounds are preferred from the viewpoint of improving alkali developability. Hydroxybenzoic acid compounds can be used individually or in combination of two or more types.

In one embodiment, the resin (a3) having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and has the formula (7)

It has a structure of In formula (7), b is an integer of 1 to 5, and * represents a bonding portion of a compound having at least two epoxy groups in one molecule with a residue other than the epoxy group involved in the reaction.

In the method of obtaining resin (a3) having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound can be used relative to 1 equivalent of the epoxy group of the epoxy compound, preferably Use 0.3 to 0.9 equivalents, more preferably 0.4 to 0.8 equivalents. If the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if the hydroxybenzoic acid compound is 0.95 equivalent or less, an increase in molecular weight due to side reactions can be suppressed.

A catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of catalyst used can be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture consisting of an epoxy compound and a hydroxybenzoic acid compound. The reaction temperature can be 60 to 150°C and the reaction time can be 3 to 30 hours. Catalysts used in this reaction include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate. You can.

The number average molecular weight (Mn) of the resin (a3) having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and still more preferably 1000 to 5000. If the number average molecular weight is 500 or more, it is good as a resin for photosensitive materials because alkali solubility is appropriate, and if it is 8000 or less, coatability and developability are good.

In one embodiment, the epoxy equivalent weight of resin (a3) having an epoxy group and a phenolic hydroxyl group is 300 to 7,000, preferably 400 to 6,000, and more preferably 500 to 5,000. If the epoxy equivalent of the resin (a3) having an epoxy group and a phenolic hydroxyl group is 300 or more, sufficient alkali solubility can be provided to the resin (a3) having an epoxy group and a phenolic hydroxyl group. If the epoxy equivalent of the resin (a3) having an epoxy group and a phenolic hydroxyl group is 7000 or less, the strength of the film after curing can be increased. Epoxy equivalent weight is determined by JIS K 7236:2009.

In one embodiment, the hydroxyl equivalent weight of resin (a3) having an epoxy group and a phenolic hydroxyl group is 160 to 500, preferably 170 to 400, and more preferably 180 to 300. If the hydroxyl group equivalent of the resin (a3) having an epoxy group and a phenolic hydroxyl group is 160 or more, the strength of the film after curing can be increased. If the hydroxyl equivalent of the resin (a3) having an epoxy group and a phenolic hydroxyl group is 500 or less, sufficient alkali solubility can be provided to the resin (a3) having an epoxy group and a phenolic hydroxyl group. Hydroxyl equivalent weight is determined by JIS K 0070:1992.

In one embodiment, the photosensitive resin composition contains 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, and more preferably 10% by mass to 40% by mass of the resin (a3) having an epoxy group and a phenolic hydroxyl group, based on 100% by mass of solid content. It contains 15% by mass to 30% by mass. If the content of resin (a3) having an epoxy group and a phenolic hydroxyl group is 5% by mass or more based on 100% by mass of solid content, dissolution of the exposed area can be promoted, high sensitivity can be achieved, and stability and durability of the film after heat curing are ensured. can do. If the content of resin (a3) having an epoxy group and a phenolic hydroxyl group is 50% by mass or less based on 100% by mass of solid content, the solubility of the unexposed area can be suppressed low and the residual film rate can be maintained high.

<First quinonediazide adduct (B1) and second quinonediazide adduct (B2)>

The photosensitive resin composition is a radiation-sensitive compound, and is a quinonediazide adduct of at least two types of phenol compounds, namely, a first quinonediazide adduct (B1), which is a quinonediazide adduct to a first phenol compound, and a first quinonediazide adduct. Other than the azide adduct (B1), it includes a second quinonediazide adduct (B2), which is a quinonediazide adduct to a second phenol compound. In the present disclosure, the first quinonediazide adduct (B1) and the second quinonediazide adduct (B2) are also collectively referred to as quinonediazide adduct (B). Likewise, in the present disclosure, the first phenol compound and the second phenol compound are collectively referred to as phenol compounds. For example, the quinonediazide adduct (B) is a quinonediazide adduct (B) whose skeleton is a trivalent phenol compound represented by formula (8),

It refers to the following compounds in which at least one of the three phenolic hydroxyl groups of the phenol compound is substituted with a group having a quinonediazide structure, for example, a naphthoquinonediazide sulfonate group shown below. Substitution with a naphthoquinone diazide sulfonate group can be performed by esterifying (sulfonating) the phenolic hydroxyl group of the phenolic compound with a quinone diazide sulfonate halide.

In the above structural formula, R is each independently a hydrogen atom,

or

represents.

When the quinonediazide adduct (B) is irradiated with ultraviolet light, etc., it generates a carboxyl group through the reaction shown in Scheme 2 below. By generating a carboxyl group, the exposed portion (film) becomes soluble in an aqueous alkaline solution, and alkali developability occurs in that portion.

The present inventor has disclosed a first quinonediazide adduct (B1), which is a quinonediazide adduct to a first phenol compound, and a second quinonediazide adduct (B2), which is a quinonediazide adduct to a second phenol compound, as a radiation-sensitive compound. By using and setting the difference in molecular weight between the first phenol compound and the second phenol compound to 40 to 500, preferably 42 to 400, and more preferably 45 to 350, the sensitivity of the photosensitive resin composition is maintained while maintaining pattern formation. We found out that we can increase . Here, the molecular weight of the first phenol compound constituting the first quinonediazide adduct (B1) is smaller than the molecular weight of the second phenol compound constituting the second quinonediazide adduct (B2). Without being bound by any theory, the quinonediazide adduct to the lower molecular weight first phenolic compound (the first quinonediazide adduct (B1)) is the quinonediazide adduct to the higher molecular weight second phenolic compound. Compared to the second quinonediazide adduct (B2), the solubility in the exposed area is improved. The second quinonediazide adduct (B2) suppresses excessive dissolution of the unexposed area during development, and generates and dissolves a carboxylic acid compound in the exposed area like the first quinonediazide adduct (B1). Therefore, by using the first quinonediazide adduct (B1) and the second quinonediazide adduct (B2) together, pattern formation can be maintained while increasing the sensitivity of the photosensitive resin composition. The present invention suggests that, as a means of adjusting the sensitivity of the photosensitive resin composition, not only the type and composition of the binder resin and additives such as a dissolution accelerator, but also the quinonediazide adduct (B), which is a radiation-sensitive compound, can be used. It has the technical significance of increasing the degree of freedom in designing the photosensitive resin composition.

Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, and BisP-IPZ. , BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML- PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML -HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, brand name, manufactured by Honshu Chemical Industry Co., Ltd.), 2,6-bis(methoxymethyl)- 4-tert-butylphenol, 2,6-bis(methoxymethyl)-p-cresol, 2,6-bis(acetoxymethyl)-p-cresol, naphthol, trihydroxybenzophenone, tetrahydroxybenzophenone , bisphenol A, bisphenol E, methylenebisphenol, and BisP-AP (brand name, manufactured by Honshu Chemical Industry Co., Ltd.), but are not limited to these. The first phenol compound and the second phenol compound can be selected in combination so as to have a predetermined molecular weight difference.

It is preferable that the first phenol compound and the second phenol compound each have three or more phenolic hydroxyl groups. The first quinonediazide adduct (B1) and the second quinonediazide adduct (B2) obtained from a phenol compound having three or more phenolic hydroxyl groups have a high balance of photosensitivity and solubility, and therefore are photosensitive. The sensitivity of the resin composition can be improved.

The molecular weight of the first phenol compound is preferably 230 or more and less than 300, more preferably 230 or more and 280 or less, and even more preferably 230 or more and 260 or less. When the molecular weight of the first phenol compound is 230 or more, excessive dissolution of the unexposed area can be suppressed and a difference can be provided in the solubility of the unexposed area and the exposed area. When the molecular weight of the first phenol compound is less than 300, the solubility of the exposed area can be maximized.

The molecular weight of the second phenol compound is preferably 300 or more and 600 or less, more preferably 300 or more and 590 or less, and even more preferably 300 or more and 580 or less. When the molecular weight of the second phenol compound is 300 or more, excessive dissolution of the unexposed area can be suppressed and a difference can be provided in the solubility of the unexposed area and the exposed area. When the molecular weight of the second phenol compound is 600 or less, residues in the exposed area can be suppressed and good pattern formation properties can be obtained.

Preferred phenol compounds include those having the following structural formula.

The quinonediazide adduct (B) can be obtained, for example, by carrying out an esterification reaction between the phenolic hydroxyl group of a phenol compound and the compound represented by formula (9) or formula (10).

In formulas (9) and (10), R ^a to R ^d each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and X is a halogen atom or It represents OH.

R ^a to R ^d are each independently preferably a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or an alkoxy group with 1 to 3 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a methoxy group, More preferably, it is a hydrogen atom. X is preferably a chlorine atom. Examples of compounds represented by formula (9) and formula (10) include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

In one embodiment, in the quinonediazide adduct (B), the phenolic hydroxyl group of the phenol compound is substituted with a group having a quinonediazide structure represented by formula (11) or formula (12).

In formulas (11) and (12), R ^a to R ^d each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and * represents the phenol compound. It represents the bonding portion of the phenolic hydroxyl group with the oxygen atom. R ^a to R ^d are each independently preferably a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or an alkoxy group with 1 to 3 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a methoxy group, More preferably, it is a hydrogen atom.

The first quinonediazide adduct (B1) and the second quinonediazide adduct (B2) are each independently 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphtho of a phenol compound. It is preferable that it contains quinonediazide-5-sulfonic acid ester, and more preferably it is 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of a phenolic compound. desirable. The first quinonediazide adduct (B1) and the second quinonediazide adduct (B2) each independently contain a 1,2-naphthoquinonediazide-4-sulfonic acid ester bond and a 1,2-naph in one molecule. It may have both toquinonediazide-5-sulfonic acid ester bonds. In one embodiment, the quinonediazide adduct (B) is 1,2-naphthoquinonediazide-4-sulfonic acid ester. In another embodiment, the quinonediazide adduct (B) is 1,2-naphthoquinonediazide-5-sulfonic acid ester.

The degree of substitution in the quinonediazide adduct (B) (the ratio in which the phenolic hydroxyl group of the phenolic compound is substituted with a group having a quinonediazide structure, based on the entire molecule of the quinonediazide adduct (B)) is Preferably it is 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more. By setting the degree of substitution to 20 mol% or more, the difference in solubility between the unexposed portion and the exposed portion can be increased. The degree of substitution may be 100 mol% or less, 95 mol% or less, or 93 mol% or less.

Degree of substitution in the first quinonediazide adduct (B1) (based on the entire molecule of the quinonediazide adduct (B1), the phenolic hydroxyl group of the first phenolic compound is substituted with a group having a quinonediazide structure The proportion) is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more. By setting the degree of substitution to 20 mol% or more, the difference in solubility between the unexposed portion and the exposed portion can be increased. The degree of substitution may be 100 mol% or less, 95 mol% or less, or 93 mol% or less.

The degree of substitution in the second quinonediazide adduct (B2) (based on the entire molecule of the quinonediazide adduct (B2), the phenolic hydroxyl group of the second phenolic compound is substituted with a group having a quinonediazide structure. The proportion) is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more. By setting the degree of substitution to 20 mol% or more, the difference in solubility between the unexposed portion and the exposed portion can be increased. The degree of substitution may be 100 mol% or less, 95 mol% or less, or 93 mol% or less.

The degree of substitution in the first quinonediazide adduct (B1) is preferably greater than or equal to the degree of substitution in the second quinonediazide adduct (B2).

The phenolic hydroxyl equivalent weight of the first quinonediazide adduct (B1) is preferably 100 to 1,500, more preferably 130 to 1,400, and even more preferably 140 to 1,300. By setting the phenolic hydroxyl group equivalent of the first quinonediazide adduct (B1) to 100 or more, dissolution of the unexposed portion can be suppressed. By setting the phenolic hydroxyl group equivalent of the first quinonediazide adduct (B1) to 1500 or less, sufficient solubility can be provided to the exposed area after photosensitization.

The phenolic hydroxyl group equivalent of the second quinonediazide adduct (B2) is preferably 180 to 800, more preferably 180 to 700, and still more preferably 180 to 600. By setting the phenolic hydroxyl group equivalent of the second quinonediazide adduct (B2) to 180 or more, dissolution of the unexposed portion can be suppressed. By setting the phenolic hydroxyl group equivalent of the second quinonediazide adduct (B2) to 800 or less, sufficient solubility can be provided to the exposed area after photosensitization.

The average number of phenolic hydroxyl groups in the first quinonediazide adduct (B1) is preferably 0.1 to 3.0, more preferably 0.2 to 2.5, and still more preferably 0.2 to 2.0 per molecule. By setting the average number of phenolic hydroxyl groups in the first quinonediazide adduct (B1) to 0.1 or more, sufficient solubility can be provided to the exposed area after photosensitization. By setting the average number of phenolic hydroxyl groups in the first quinonediazide adduct (B1) to 3.0 or less, dissolution of the unexposed portion can be suppressed.

The average number of phenolic hydroxyl groups in the second quinonediazide adduct (B2) is preferably 0.5 to 5.0, more preferably 1.0 to 4.5, and still more preferably 1.0 to 4.0 per molecule. By setting the average number of phenolic hydroxyl groups in the second quinonediazide adduct (B2) to 0.5 or more, sufficient solubility can be provided to the exposed area after photosensitization. By setting the average number of phenolic hydroxyl groups in the second quinonediazide adduct (B2) to 5.0 or less, dissolution of the unexposed portion can be suppressed.

The photosensitive resin composition preferably contains 5 to 70 parts by mass, more preferably 8 to 60 parts by mass, of the first quinonediazide adduct (B1), based on 100 parts by mass of the binder resin (A). More preferably, it contains 10 to 50 parts by mass. If the content of the first quinonediazide adduct (B1) is 5 parts by mass or more based on 100 parts by mass of the binder resin (A), high sensitivity can be achieved. If the content of the first quinonediazide adduct (B1) is 70 parts by mass or less based on 100 parts by mass of the binder resin (A), alkali developability is good.

The photosensitive resin composition preferably contains 5 to 70 parts by mass, more preferably 8 to 60 parts by mass, of the second quinonediazide adduct (B2), based on 100 parts by mass of the binder resin (A). More preferably, it contains 10 to 50 parts by mass. If the content of the second quinonediazide adduct (B2) is 5 parts by mass or more based on 100 parts by mass of the binder resin (A), high sensitivity can be achieved. If the content of the second quinonediazide adduct (B2) is 70 parts by mass or less based on 100 parts by mass of the binder resin (A), alkali developability is good.

The mass ratio of the first quinonediazide adduct (B1) and the second quinonediazide adduct (B2) (mass of the first quinonediazide adduct:mass of the second quinonediazide adduct) is preferably 1: 13 to 13:1, more preferably 1:10 to 10:1, even more preferably 1:8 to 8:1. By setting the mass ratio to 1:13 to 13:1, the sensitivity of the photosensitive resin composition can be improved.

Without being bound by any theory, in the embodiment in which the binder resin (A) includes the protective resin (a2), the carboxylic acid compound produced from the quinonediazide adduct causes decomposition of the acid-decomposable group of the protective resin (a2). This promotes regeneration of alkali-soluble functional groups, such as phenolic hydroxyl groups, to increase the alkali solubility of the protective resin (a2). The quinonediazide adduct interacts with the alkali-soluble functional group of the binder resin (for example, forms a hydrogen bond) before photosensitization, thereby making the binder resin insoluble in an aqueous alkaline solution. On the other hand, the presence of an alkali-soluble carboxylic acid compound in the irradiated area makes it easy for the resin in that area to dissolve in an aqueous alkaline solution together with the carboxylic acid compound. In addition, carboxylic acid compounds have a relatively larger molecular structure than acids generated from photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and are difficult to diffuse in the film. As a result of these acting synergistically, it is believed that the difference in alkali solubility between the unexposed area and the exposed area can be increased, thereby forming a high-resolution pattern with high sensitivity even at a low exposure amount.

In the embodiment in which the binder resin (A) contains the protective resin (a2), a high-resolution pattern can be formed without performing the post-exposure heat treatment (PEB) required for general chemically amplified resist. The quinonediazide adduct has a relatively high quantum yield, and carboxylic acid compounds are efficiently generated in the exposed area. If an acid-decomposable group that can be decomposed into a carboxylic acid compound exists in the surrounding area, the acid-decomposable group is decomposed even at room temperature by the produced carboxylic acid compound, and alkali-soluble functional groups, such as phenolic hydroxyl groups, are regenerated, resulting in The difference in alkali solubility between the unexposed area and the exposed area can be increased. By omitting PEB, it is possible to suppress the decline in pattern formability caused by excessive diffusion of the acid generated from the photoacid generator into the unexposed area under the high temperature environment during PEB. In addition, when the binder resin (A) contains a resin (a3) having an epoxy group and a phenolic hydroxyl group, if PEB is omitted, ring-opening polymerization of the epoxy group of the resin (a3) having an epoxy group and a phenolic hydroxyl group does not proceed, During development, the alkali solubility of the resin (a3) having an epoxy group and a phenolic hydroxyl group can be maintained.

<Black colorant (C)>

As the black colorant (C), at least one type selected from the group consisting of black dye and black pigment can be used. Black dye and black pigment may be used together. For example, by forming a black partition in an organic EL element using a photosensitive resin composition containing a black colorant (C), the visibility of a display device such as an organic EL display can be improved.

In one embodiment, the black colorant (C) comprises a black dye. As a black dye, a dye specified by a color index (C.I.) of solvent black 27 to 47 can be used. The black dye is preferably one specified as Solvent Black with a C.I. of 27, 29 or 34. When at least one type of dye specified by C.I. of Solvent Black 27 to 47 is used as a black dye, the light-shielding property of the film of the photosensitive resin composition after curing can be maintained. Compared to the photosensitive resin composition containing a black pigment, the photosensitive resin composition containing a black dye leaves less residue of the black colorant (C) during development and can form a high-definition pattern on the film.

A black pigment may be used as the black colorant (C). Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene-based pigments, and lactam-based pigments. These black pigments that have been subjected to surface treatment can also be used. Examples of commercially available perylene-based pigments include K0084, K0086, and Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF. An example of a commercially available lactam pigment includes Irgaphor (registered trademark) Black S0100CF manufactured by BASF. Since it has high light-shielding properties, the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactam-based pigments.

In one embodiment, the photosensitive resin composition contains 10 to 150 parts by mass of the black colorant (C), preferably 30 to 100 parts by mass, more preferably 40 to 40 parts by mass, based on 100 parts by mass of the binder resin. Contains 70 parts by mass. If the content of the black colorant (C) is 10 parts by mass or more based on the total of 100 parts by mass, the light-shielding property of the film after curing can be maintained. If the content of the black colorant (C) is 150 parts by mass or less based on the total of 100 parts by mass, the film can be colored without impairing alkali developability.

<Dissolution accelerator (D)>

The photosensitive resin composition may further contain a dissolution accelerator (D) for improving the solubility of the alkali-soluble portion in the developing solution during development. As the dissolution accelerator (D), a low molecular weight organic compound selected from the group consisting of compounds having a carboxyl group and compounds having a phenolic hydroxyl group can be mentioned. The dissolution accelerator (D) can be used individually or in combination of two or more types.

In the present disclosure, “low molecular weight compound” refers to a compound with a molecular weight of 1000 or less. The low molecular weight organic compound has a carboxyl group and/or a phenolic hydroxyl group and is alkali soluble. The low molecular weight organic compound may have only a carboxyl group, may have only a phenolic hydroxyl group, or may have both a carboxyl group and a phenolic hydroxyl group. It is preferable that the total number of carboxyl groups and phenolic hydroxyl groups contained in one molecule of the low molecular weight organic compound is 2 or more.

Examples of such organic low-molecular-weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbalylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemimellitic acid, and mesitylenic acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, and pyromellitic acid; Aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; Other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbelic acid, etc. ; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

The content of the dissolution accelerator (D) in the photosensitive resin composition can be 0.1 parts by mass to 50 parts by mass, preferably 1 part by mass to 35 parts by mass, more preferably 2 parts by mass, based on 100 parts by mass of the binder resin. It is ~20 parts by mass. If the content of the dissolution accelerator (D) is 0.1 parts by mass or more based on the above total of 100 parts by mass, dissolution of the resin component can be effectively promoted, and if it is 50 parts by mass or less, excessive dissolution of the resin component is suppressed, thereby forming a pattern of the film. Formability, surface quality, etc. can be improved.

<Random component (E)>

The photosensitive resin composition may contain a thermosetting agent, a surfactant, a colorant other than the black colorant (C), etc. as an optional component (E). In the present disclosure, optional component (E) is defined as not corresponding to any of (A) to (D).

As a thermal curing agent, a thermal radical generator can be used. Preferred thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, and di-tert. -Organic peroxides with a 10-hour half-life temperature of 100 to 170°C, such as butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, and cumene hydroperoxide.

The content of the thermosetting agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the thermosetting agent.

The photosensitive resin composition may contain a surfactant, for example, to improve coatability, improve the smoothness of the film, or improve the developability of the film. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylenenonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaulate and polyoxyethylene distearate; Megapark (registered trademark) F-251, F-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559 (above, brand name, manufactured by DIC Kabushiki Kaisha), Suplon (registered trademark) S-242, S-243, S-386, S-420, S-611 (above, brand name, AGC Semi Chemical Kabu) fluorine-based surfactants such as those manufactured by Shikigai Co., Ltd.; and organosiloxane polymers KP323, KP326, and KP341 (above, brand name, manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants can be used individually or in combination of two or more types.

The content of the surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 parts by mass or less, based on 100 parts by mass of the total solid content excluding the surfactant.

The photosensitive resin composition may contain a second colorant other than the black colorant (C). Examples of the second colorant include dyes, organic pigments, and inorganic pigments. The second colorant can be used according to the purpose. The second colorant can be used in an amount that does not impair the effect of the disclosure of the present invention.

Examples of dyes include azo-based dyes, benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, cyanine-based dyes, squaryllium-based dyes, croconium-based dyes, melocyanine-based dyes, stilbene-based dyes, and Examples include phenylmethane-based dyes, triphenylmethane-based dyes, fluorane-based dyes, spiropyran-based dyes, phthalocyanine-based dyes, indigo-based dyes, fulgid-based dyes, nickel complex-based dyes, and azulene-based dyes. Among dyes, red dye is preferable. As red dye, for example, VALIFAST (registered trademark) RED 3312 (red dye specified in C.I. of Solvent Red 122, manufactured by Orient Kagaku Kogyo Kabushiki Kaisha), and VALIFAST (registered trademark) RED 3311 (C.I. of Solvent Red 8) Red dye specified as C.I., manufactured by Orient Kagaku Kogyo Kabushiki Kaisha Co., Ltd.) can be mentioned.

Pigments include, for example, C.I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. Pigment Green 7, and C.I. Pigment browns 23, 25, and 26 may be mentioned.

[Coating composition]

<Solvent (F)>

The photosensitive resin composition can be dissolved in a solvent (F) and used as a coating composition in a solution state (however, when it contains a black pigment, the pigment is in a dispersed state). For example, the first quinonediazide adduct (B1), the second quinonediazide adduct (B2), and a black colorant (C) are added to the solution obtained by dissolving the binder resin (A) in the solvent (F). and, if necessary, optional components (E) such as a dissolution accelerator (D), a heat curing agent, and a surfactant at a predetermined ratio, thereby preparing a coating composition containing the photosensitive resin composition. The coating composition can be adjusted to a viscosity suitable for the application method used by changing the amount of solvent (F).

Examples of the solvent (F) include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycol compounds such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; Propylene glycol monoalkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and cyclohexanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate , esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used individually or in combination of two or more types.

The solid content concentration of the coating composition can be appropriately determined depending on the purpose of use. For example, the solid content concentration of the coating composition may be 1 to 60 mass%, 3 to 50 mass%, or 5 to 40 mass%.

Known methods can be used for dispersion and mixing methods when using pigments. For example, ball types such as ball mills, sand mills, bead mills, paint shakers, and rocking mills, blade types such as kneaders, paddle mixers, planetary mixers, and Henschel mixers, roll types such as three roll mixers, and other brain types. You can use a gauge, colloid mill, ultrasonic wave, homogenizer, rotation/revolution mixer, etc. It is preferable to use a bead mill from the viewpoint of dispersion efficiency and microdispersion.

The prepared coating composition is usually filtered prior to use. As a means of filtration, for example, a Millipore filter with a pore diameter of 0.05 to 1.0 μm may be used.

The coating composition prepared in this way also has excellent long-term storage stability.

[Method of using photosensitive resin composition]

When using the photosensitive resin composition in radiation lithography, first, the photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition can be applied to the surface of the substrate, the solvent can be removed by means such as heating, and a film can be formed. The method of applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, roll coating method, slit method, or spin coating method can be used.

After the coating composition is applied to the surface of the substrate, the solvent is usually removed by heating to form a film (prebake). Heating conditions vary depending on the type and mixing ratio of each component, but a film can be obtained by generally heating at 70 to 130°C, for example, for 30 seconds to 20 minutes on a hot plate or 1 to 60 minutes in an oven. .

Next, the prebaked film is irradiated with radiation (for example, visible rays, ultraviolet rays, deep ultraviolet rays, X-rays, electron rays, gamma rays, or synchrotron radiation) through a photomask with a predetermined pattern (exposure process). Preferred radiation is ultraviolet to visible light with a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-ray. In another embodiment, the radiation is ghi radiation.

When the binder resin (A) contains the protective resin (a2), heat treatment (PEB) to promote decomposition of acid-decomposable groups may be performed after the exposure process. PEB can further increase the alkali solubility of the protective resin (a2) in the exposed area. Heating conditions vary depending on the type and mixing ratio of each component, but PEB can usually be performed by heating at 70 to 140°C, for example, for 30 seconds to 20 minutes on a hot plate, or for 1 to 60 minutes in an oven. . In one embodiment, PEB after the exposure process can be omitted.

After the exposure process or PEB process, the film is developed by contacting it with a developer, and unnecessary parts are removed to form a pattern on the film (development process). Examples of developing solutions include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; Primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; Aqueous solutions of alkaline compounds such as cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant to an aqueous alkaline solution can also be used as a developing solution. Development time is usually 30 to 180 seconds. The development method may be any of a liquid mounting method, a shower method, or a dipping method. After development, a pattern can be formed on the film by washing under running water for 30 to 90 seconds to remove unnecessary parts and air-drying with compressed air or compressed nitrogen.

Afterwards, a cured film can be obtained by heat-treating the patterned film using a heating device such as a hot plate or oven at, for example, 100 to 350°C for 20 to 200 minutes (post-bake, heat treatment process). . In the heat treatment, the temperature may be kept constant, the temperature may be raised continuously, or the temperature may be raised in steps. Heat treatment is preferably performed in a nitrogen atmosphere.

The optical density (OD value) of the cured film of the photosensitive resin composition is preferably 0.5 or more, more preferably 0.7 or more, and still more preferably 1.0 or more per 1 μm of film thickness. If the OD value of the cured film is 0.5 or more per 1 μm of film thickness, sufficient light-shielding properties can be obtained.

A method of manufacturing an organic EL device barrier rib or an organic EL device insulating film according to an embodiment includes dissolving or dispersing a photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a film, and including the coating composition. Drying the film by removing the solvent, exposing the dried film by irradiating radiation through a photo mask, developing the film after exposure by contacting it with a developer to form a pattern on the film, and forming a pattern on the film. It includes heat treatment at a temperature of 100°C to 350°C to form an organic EL device barrier rib or insulating film. The above PEB may be performed after exposure or before development.

One embodiment is an organic EL device partition containing a cured product of a photosensitive resin composition.

One embodiment is an organic EL device insulating film containing a cured product of a photosensitive resin composition.

One embodiment is an organic EL device containing a cured product of a photosensitive resin composition.

Example

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

(1) Raw materials

The raw materials used in Examples and Comparative Examples were manufactured or obtained as follows.

The weight average molecular weight and number average molecular weight of each resin contained in the binder resin (A) were calculated using a calibration curve prepared using a polystyrene standard material under the following measurement conditions.

Device name: Shodex (registered trademark) GPC-101

Column: Shodex (registered trademark) LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: Shodex (registered trademark) RI-71

Temperature: 40℃

[Preparation Example 1] Preparation of copolymer (a1) (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and other polymerizable monomers

29.0 g of 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) and 5.12 g of N-cyclohexylmaleimide (produced by Nippon Shokubai Co., Ltd.) were mixed with 1-methoxy- as a solvent. To 96.5 g of 2-propyl acetate (manufactured by Daicel, Kabushiki Kaisha), 3.41 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added to 1-methoxy-2-propyl acetate (manufactured by Daicel, Kabushiki Kaisha). Cell product) were each completely dissolved in 13.7 g. The two obtained solutions were simultaneously added dropwise to 40.0 g of 1-methoxy-2-propyl acetate (manufactured by Daicel, Inc.) heated to 85°C in a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. Then, it was reacted at 85°C for 3 hours. The reaction solution cooled to room temperature was added dropwise into 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, dried under vacuum at 90°C for 4 hours, and 32.4 g of white powder was recovered. The number average molecular weight of the obtained PCX-02e was 3100 and the weight average molecular weight was 6600.

[Preparation Example 2] Preparation of protective resin (a2) (PCX-02e-THF55) in which the phenolic hydroxyl group is protected by a 2-tetrahydrofuranyl group

In a 100 mL three-necked flask, 10.0 g of copolymer (a1) (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and other polymerizable monomers, and pyridinium salt of p-toluenesulfonic acid as an acid catalyst (Tokyo Kasei Kogyo) 0.60 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 50.0 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). After that, it was ice-cooled in a nitrogen gas atmosphere, and 6.69 g of 2,3-dihydrofuran (manufactured by Tokyo Kasei Kogyo Kabushiki Kaisha Co., Ltd.) was added dropwise over 1 hour. Afterwards, it was stirred at room temperature for 16 hours. After neutralizing the acid catalyst with a saturated aqueous sodium bicarbonate solution, the aqueous layer was removed. Additionally, the organic layer was washed twice with water. After that, tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of toluene to precipitate the product. The precipitate was recovered by filtration, dried under vacuum at 80°C for 4 hours, and 11.0 g of white powder was recovered. The obtained powder was dissolved in propylene glycol monomethyl ether acetate to obtain a 20 mass% solid content solution of protective resin (a2) (PCX-02e-THF55) in which the phenolic hydroxyl group was protected by a 2-tetrahydrofuranyl group. The number average molecular weight of the obtained PCX-02e-THF55 is 3716, the weight average molecular weight is 6806, the proportion of phenolic hydroxyl groups protected by acid-decomposable groups is 55 mol%, and at least one phenolic hydroxyl group is protected by acid-decomposable groups ( The number of structural units represented by 4) was 55% of the total number of structural units of PCX-02e-THF55. The proportion of phenolic hydroxyl groups protected by acid-decomposable groups was determined at room temperature under the conditions of a temperature increase rate of 10°C/min in a nitrogen gas stream using a thermogravimetric differential thermal analysis device (TG/DTA6200, manufactured by Hitachi High-Tech Science, Ltd.). It was calculated from the weight loss rate (%) of PCX-02e-THF55 at 260°C when the temperature was raised to 250°C, held for 10 minutes, and further raised to 400°C at a temperature increase rate of 10°C/min. .

[Preparation Example 3] Preparation of resin (a3) (N695OH70) having an epoxy group and a phenolic hydroxyl group

In a 300 mL three-necked flask, 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent, and EPICLON (registered trademark) N-695 (cresol manufactured by DIC Chemical Co., Ltd.) as a compound having at least two epoxy groups in one molecule. 42.8 g of novolak-type epoxy resin (epoxy equivalent weight 214) was added and dissolved at 60°C in a nitrogen gas atmosphere. In addition, 20.1 g (0.65 equivalents per 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (Fuji Film Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound, and triphenylphosphine (Tokyo Kasei Kogyo) as a reaction catalyst. 0.166 g (0.633 mmol) (manufactured by Kabuki Kaisha) was added and reacted at 110°C for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain 304.2 g of a solution of resin (a3) (N695OH70) having an epoxy group and a phenolic hydroxyl group. The number average molecular weight of the obtained reactant was 3000, the weight average molecular weight was 7500, and the epoxy equivalent was 2200.

<Binder Resin (A)>

As the binder resin (A), PCX-02e, PCX-02e-THF55, and N695OH70 were used.

<Quinonediazide adduct (B)>

As the quinonediazide adduct (B), the compounds shown in Table 1 were used.

[Table 1]

The structural formula of the quinonediazide adduct (B) is shown in Table 2. In the structural formula, R is a hydrogen atom or

represents.

[Table 2-1]

[Table 2-2]

<Black colorant (C)>

As a black colorant (C), a black dye, VALIFAST (registered trademark) BLACK 3820 (a black dye defined by C.I. of Solvent Black 27, manufactured by Orient Chemical Co., Ltd.) was used.

<Dissolution accelerator (D)>

As a dissolution promoter (D), phloroglucinol was used.

<Solvent (F)>

As the solvent (F), a mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA=40:60 (mass ratio)) was used.

(2) Evaluation method

The evaluation methods used in the examples and comparative examples are as follows.

[Sensitivity]

The photosensitive resin composition was bar coated on a glass substrate (size 100 mm x 100 mm x 1 mm) to a dry film thickness of 1.5 μm, and prebaked by heating on a hot plate at 100°C for 1 minute. The film was exposed through a quartz photomask (having an aperture pattern of ?10 μm) using an exposure apparatus equipped with an ultra-high pressure mercury lamp (trade name: Multilight ML-251A/B, manufactured by Ushio Denki Kabushiki Kaisha). The exposure amount was measured using an ultraviolet integrated photometer (product name: UIT-150 light receiving unit UVD-S365, manufactured by Ushio Denki Chemical Co., Ltd.). After exposure, alkaline development was performed for 60 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution using a spin developing device (AD-1200, manufactured by Takizawa Sankyo Chemical Co., Ltd.). The above procedure was repeated while changing the exposure amount, and the minimum irradiation amount (mJ/cm ² ) that can form a pattern with a hole diameter of 10 μm after development was set as the sensitivity.

[OD value of hardened film]

The photosensitive resin composition was spin coated on a glass substrate (size 100 mm After that, the film was obtained by curing at 250°C for 60 minutes in a nitrogen gas atmosphere. The OD value of the cured film was measured with a transmission densitometer (BMT-1, Sakata Inks Engineering Co., Ltd.), corrected to the OD value of glass alone, and converted to an OD value per 1 μm of film thickness. The thickness of the film was measured using an optical film thickness measuring device (F20-NIR, manufactured by Peel Matrix Chemical Industry Co., Ltd.).

(3) Preparation and evaluation of photosensitive resin composition

[Examples 1 to 12, and Comparative Examples 1 to 3]

The binder resin (A) was mixed and dissolved in the composition shown in Table 3, and the resulting solution was mixed with the quinonediazide adduct (B), black colorant (C), dissolution accelerator (D), and GBL/PGMEA shown in Table 3. Solvent (F) was added and further mixed. After visually confirming that the components were dissolved, it was filtered through a Millipore filter with a pore diameter of 0.22 μm to prepare a photosensitive resin composition with a solid content concentration of 12% by mass. The mass portion of the composition in Table 3 is the solid content conversion value. The evaluation results of the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 are shown in Table 3.

[Table 3-1]

[Table 3-2]

When comparing Examples 1 to 11 and Comparative Examples 1 and 3 in which the binder resin (A) contains PCX-02e-THF55 as the protective resin (a2), Examples 1 to 11 had higher sensitivity (less exposure amount). Additionally, when Comparative Example 2 is compared with Example 12 in which the binder resin (A) does not contain PCX-02e-THF55 as the protective resin (a2), Example 12 similarly had higher sensitivity (lower exposure amount).

The photosensitive resin composition according to the present disclosure can be suitably used in radiation lithography to form a partition or insulating film of an organic EL device. An organic EL element provided with a partition or an insulating film formed from the photosensitive resin composition according to the present disclosure is preferably used as an electronic component of a display device showing good contrast.

Claims (19)

(A) binder resin,
(B1) a first quinonediazide adduct that is a quinonediazide adduct to a first phenol compound,
(B2) a second quinonediazide adduct, which is a quinonediazide adduct to a second phenol compound,
(C) A photosensitive resin composition containing a black colorant, wherein the difference between the molecular weight of the first phenol compound and the molecular weight of the second phenol compound is 40 to 500, and the molecular weight of the first phenol compound is that of the second phenol compound. A photosensitive resin composition with a molecular weight smaller than that of the photosensitive resin composition. According to claim 1,
A photosensitive resin composition in which the first phenol compound and the second phenol compound each have three or more phenolic hydroxyl groups. The method of claim 1 or 2,
A photosensitive resin composition wherein the first quinonediazide adduct has a phenolic hydroxyl equivalent weight of 100 to 1500, and the second quinonediazide adduct has a phenolic hydroxyl equivalent weight of 180 to 800. The method according to any one of claims 1 to 3,
A photosensitive resin composition wherein the average number of phenolic hydroxyl groups of the first quinonediazide adduct is 0.1 to 3.0 per molecule, and the average number of phenolic hydroxyl groups of the second quinonediazide adduct is 0.5 to 5.0 per molecule. The method according to any one of claims 1 to 4,
A photosensitive resin composition wherein the first quinonediazide adduct is 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of the first phenol compound. The method according to any one of claims 1 to 5,
A photosensitive resin composition wherein the second quinonediazide adduct is 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of the second phenol compound. The method according to any one of claims 1 to 6,
A photosensitive resin composition in which the molecular weight of the first phenol compound is 230 to 300, and the molecular weight of the second phenol compound is 300 to 600. The method according to any one of claims 1 to 7,
A photosensitive resin composition comprising 5 to 70 parts by mass of the first quinonediazide adduct and 5 to 70 parts by mass of the second quinonediazide adduct, based on 100 parts by mass of the binder resin. . The method according to any one of claims 1 to 8,
Photosensitive where the mass ratio of the first quinonediazide adduct and the second quinonediazide adduct (mass of the first quinonediazide adduct: mass of the second quinonediazide adduct) is 1:13 to 13:1. Resin composition. The method according to any one of claims 1 to 9,
The binder resin includes a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, and the copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is expressed in formula (1). A photosensitive resin composition having the structural units shown.

(In formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.) The method according to any one of claims 1 to 10,
The binder resin includes a resin having an epoxy group and a phenolic hydroxyl group, and the resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and the formula (7) A photosensitive resin composition that is a compound having a structure.

(In formula (7), b is an integer of 1 to 5, and * represents the bonding portion of a compound having at least two epoxy groups in one molecule with a residue excluding the epoxy group involved in the reaction.) According to claim 11,
A photosensitive resin composition wherein the compound having at least two epoxy groups in one molecule is a novolak-type epoxy resin. The method according to any one of claims 1 to 12,
A photosensitive resin composition including a resin in which the binder resin has a structural unit represented by Formula (4) and at least one structural unit represented by Formula (4) where s is an integer of 1 or more.

(In formula (4), R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁰ is an acid decomposable group, r is an integer from 0 to 5, and s is an integer from 0 to 5, provided that r+s is an integer from 1 to 5.) The method according to any one of claims 1 to 13,
A photosensitive resin composition wherein the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm of film thickness. The method according to any one of claims 1 to 14,
A photosensitive resin composition wherein the black colorant is a dye defined by a color index (CI) of solvent black 27 to 47. The method according to any one of claims 1 to 15,
A photosensitive resin composition comprising 10 to 150 parts by mass of the black colorant based on 100 parts by mass of the binder resin. An organic EL device partition comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 16. An organic EL device insulating film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 16. An organic EL device comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 16.